CN1643669A - Organic compositions for low dielectric constant material - Google Patents

Abstract

The present invention provides a composition comprising: a dielectric material and b porogen comprising at least two fused aromatic rings wherein each of the fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of the alkyl substituents on adjacent aromatic rings. Preferably, the dielectric material is a composition comprising a thermosetting component comprising 1 optionally monomer of Formula I as set forth below and 2 at least one oligomer or polymer of Formula II as set forth below where Q, G, h, I, I, and w are as set forth below and b porogen. Preferably, the porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthylene copolymer, polynorbornene, polycaprolactone, poly 2-vinyl naphthalene, vinyl anthracene, 1s polystyrene, polystyrene derivatives, polysiloxane, polyester, polyether, polyacrylate, aliphatic polycarbonate, polysulfone, polylactide, and blends thereof. The present compositions are particularly useful as dielectric substrate material in microchips, multichip modules, laminated circuit boards, and printed wiring boards.

Description

Organic composition for low dielectric constant material

Benefits of Pending Applications

This application is a Continuation-in-Part of pending 10/158513, filed May 30, 2002, which claims the benefit of the following pending commonly assigned provisional patent application: 60/376219, filed April 29, 2002 and 60/378424, filed May 7, 2002. The contents of these applications are hereby incorporated by reference in their entirety.

field of invention

The present invention relates to a semiconductor device, and in particular, the present invention relates to a semiconductor device having an organic material with a low dielectric constant and a manufacturing method thereof.

Background of the invention

In an effort to increase the performance and speed of semiconductor devices, semiconductor device manufacturers have been seeking to reduce the line width and spacing of interconnects while minimizing transmission losses and reducing capacitive coupling of the interconnects. One way to reduce power dissipation and capacitance is by lowering the dielectric constant (also known as "k") of the insulating material or dielectric that separates the interconnects. Insulating materials with low dielectric constants are particularly desirable because they generally enable faster signal propagation, lower capacitance and crosstalk between wires, and lower voltages required for integrated circuits to operate.

Since the dielectric constant of air is 1.0, the main goal is to reduce the dielectric constant of insulating materials to the theoretical limit of 1.0. There are several methods in the prior art to reduce the dielectric constant of insulating materials. These techniques include adding elements such as fluorine to the composition to lower the dielectric constant of the bulk material. Other methods of lowering k include the use of alternative dielectric material substrates. Another approach is to introduce pores in the matrix.

Therefore, as the interconnect line width decreases, the dielectric constant of the insulating material is required to decrease at the same time to obtain the improved performance and speed demanded by future semiconductor devices. For example, devices with interconnect line widths of 0.13 or 0.10 microns and below require insulating materials with a dielectric constant (k)<3.

Silicon dioxide (SiO ₂ ) and modified silicon dioxide such as fluorosilica or fluorosilica glass (hereinafter FSG) are currently used. These oxides, which have a dielectric constant in the range of about 3.5-4.0, are commonly used as dielectrics in semiconductor devices. While _SiO2 and FSG have the mechanical and thermal stability necessary for thermal cycling and processing steps in semiconductor device production, materials with low dielectric constants are highly desired by the semiconductor industry.

Methods for depositing dielectric materials can be classified into two categories: spin-on deposition (hereinafter referred to as SOD) and chemical vapor deposition (hereinafter referred to as CVD). Some approaches to develop low dielectric constant materials include changing the chemical composition (organic, inorganic, organic/inorganic blends) or changing the dielectric matrix (porous, non-porous). Table 1 summarizes the research status of several materials with a dielectric constant ranging from 2.0 to 3.5 (PE=enhanced plasma; HDP=high density plasma). However, the dielectric materials and substrates published in Table 1 fail to exhibit many comprehensive physical and chemical properties that are expected and even necessary for effective dielectric materials, such as high mechanical stability, high thermal stability, high glass transition temperature, high modulus or hardness while still being able to form solvates, spin-deposited or deposited on substrates, wafers or other surfaces. Therefore, it would be beneficial to study other compounds and materials that can be used as insulating materials and insulating layers, even if these compounds or materials cannot be considered as dielectric materials in their current state.

Table 1 Material deposition method Dielectric constant (k) references Fluorinated silicon oxide (SiOF) PE-CVD; HDP-CVD 3.3-3.5 US Patent 6,278,174 Silsesquihydrosiloxane (HSQ) SOD 2.0-2.5 U.S. Patents 4,756,977; 5,370,903 and 5,486,564; International Patent Publication WO 00/40637; E, S. Moyer et al. "Ultra Low k Silsesquioxane Based Resins", Concepts and Needs for Low Dielectric Constant<0.15μm Funded by the American Chemical Society, pp. 128-146 (November 14-17, 1999) Sesquimethylsiloxane (MSQ) SOD 2.4-2.7 US Patent 6,143,855 polysilicone SOD 2.5-2.6 US Patent 6,225,238 Fluorine Amorphous Carbon (aC:F) HDP-CVD 2.3 US Patent 5,900,290 Benzocyclobutene (BCB) SOD 2.4-2.7 US Patent 5,225,586 Polyarylene Ether (PAE) SOD 2.4 US Patents 5,986,045; 5,874,516; and 5,658,994 Parylene (N and F) CVD 2.4 US Patent 5,268,202 Polyphenylene SOD 2.6 US Patents 5,965,679 and 6,288,188 B1; and Waeterloos et al., "Integration Feasibility of PorousSiL K Semiconductor Dielectric",

Proceedings of the 2001 International Conference on Interconnection Technology, pp. 253-254 (2001) Thermosetting benzocyclobutene, polyarylene, thermosetting perfluoroethylene monomer SOD 2.3 International Patent Publication WO 00/31183 Poly(phenylquinoxaline), organopolysiloxane SOD 2.3-3.0 US Patents 5,776,990; 5,895,263; 6,107,357 and 6,342,454 and US Patent Publication 2001/0040294 organopolysiloxane SOD No report US Patent 6,271,273 organic and inorganic materials SOD 2.0-2.5 US Patent 6,156,812 organic and inorganic materials SOD 2.0-2.3 US Patent 6,171,687 organic material SOD No report US Patent 6,172,128 organic matter SOD 2.12 US Patent 6,214,746 organosilsesquioxane CVD, SOD ＜3.9 WO 01/29052 Fluorosilsesquioxane CVD, SOD ＜3.9 WO 01/29141

Unfortunately, many organic SOD systems under development with a dielectric constant in the range of 2.0-3.5 have some deficiencies in mechanical and thermal properties as described above, so the semiconductor industry needs to develop Improved process and performance of dielectric films. In addition, there is a need in the industry for materials with low dielectric constant scalability, ie, materials that can be lowered to lower dielectric constants (eg, 2.7-2.5 to 2.2-2.0 and below).

Reichert and Mathias describe compounds and monomers comprising adamantane (hereinafter abbreviated as C ₁₀ adamantane) molecules, a class of cage-like molecules that can be used as diamond substitutes. (Polym, Prepr. (Am.Chem.Soc., Div.Polym.Chem.), 1993, Vol. 34(1), pp. 495-6; Polym, Prepr. (Am.Chem.Soc., Div.Polym .Chem.), 1992, Vol. 33(2), pp. 144-5; Chem.Mater., 1993, Vol. 5(1), pp. 4-5;

Macromolecules, 1994, Volume 27(24), Pages 7030-7034; Macromolecules, 1994, Volume 27(24), Pages 7015-7023; Polym, Prepr. (Am.Chem.Soc., Div.Polym.Chem. ), 1995, Vol. 36(1), pp. 741-742; ^205th ACS National Meeting, Conference Program, 1993, pp. 312; Macromolecules, 1994, Vol. 27(24), pp. 7024-9; Macromolecules, 1992 , Vol. 25(9), pp. 2294-306; Macromolecules, 1991, Vol. 24(18), pp. 5232-3; Veronica R. Reichert, PhD Dissertation, 1994, Vol. 55-06B; ACS Symp. Ser.: Step-Growth Polymers for High-Performance Materials, 1996, volume 624, pages 197-207; Macromolecules, 2000, volume 33(10), pages 3855-3859; Polym, Prepr. (Am.Chem.Soc., Div. Polym.Chem.), 1999, Vol. 40(2), pp. 620-621; Polym, Prepr. (Am.Chem.Soc., Div.Polym.Chem.), 1999, Vol. 40(2), 577 -78 pages; Macromolecules, 1997, volume 30(19), pages 5970-5975; J.Polym.Sci, PartA: Polymer Chemistry, 1997, volume 35(9), pages 1743-1751; Polym, Prepr.( Am.Chem.Soc., Div.Polym.Chem.), 1996, Vol. 37(2), pp. 243-244; Polym, Prepr. (Am.Chem.Soc., Div.Polym.Chem.), 1996 Year, Volume 37(1), Pages 551-552; J.Polym.Sci., Part A: Polymer Chemistry, 1996, Volume 34(3), Pages 397-402; Polym, Prepr.(Am.Chem.Soc ., Div.Polym.Chem.), 1995, Vol. 36(2), pp. 140-141; Polym, Prepr. (Am.Chem.Soc., Div.Polym.Chem.), 1992, 33(2 ), pp. 146-147; J.Appl.Polym.Sci., 1998, vol. 68(3), pp. 475-482). The _C10 adamantane compounds and monomers described by Reichert and Mathias are preferably used to form polymers in which the _C10 adamantane molecule serves as the thermosetting core. However, the compounds disclosed by Reichert and Mathias include only one isomer of the _C10 adamantyl compound selected by design. Structure A shows the symmetrical para-isomer-1,3,5,7-tetrakis[4'-(phenylethynyl)phenyl] _C10 adamantane:

Structure A

In other words, Reichert and Mathias, in their respective and joint work, refer to a useful polymer comprising only one isomeric form of the targeted _C10 adamantyl monomer. However, when 1,3,5,7 _- tetrakis[4′-(phenylethynyl)phenyl]C ₁₀ adamantane (symmetrical “all-para” isomers) to form polymers and process them, there is a serious problem. According to Reichert's paper (supra) and Macromolecules volume 27, pages 7015-7034 (supra), the symmetrical all-para isomer 1,3,5,7-tetra[4'-(phenylethynyl ) phenyl]C ₁₀ adamantane "is sufficiently soluble in chloroform that ^{a 1} H NMR spectrum can be obtained. However, a solution ¹³ CNMR spectrum cannot be obtained from the acquisition time". This indicates that all para isomers are less soluble. Thus, Reichert's symmetrical all-para isomer 1,3,5,7-tetrakis[4'-(phenylethynyl)phenyl] _C10 adamantane is insoluble in standard organic solvents and, therefore, will not For use in any solvent-based or solvent-based processing application such as flow coating, spin coating, dip coating.

In our commonly assigned pending patent application PCT/US01/22204, filed October 17, 2001 (claiming interest in our commonly assigned pending patent application: filed April 7, 2000 U.S. Patent Serial No. 09/545058, filed July 19, 2000, U.S. Patent Serial No. 09/618945, filed July 5, 2001, U.S. Patent Serial No. 09/897936, filed July 10, 2001 09/902924; and the benefit of International Publication WO 01/78110, published October 18, 2001), we discovered a composition comprising a mixture of isomeric thermosetting monomers or dimers, Wherein said mixture comprises at least one monomer or dimer having the following corresponding structures,

Wherein Z is selected from a clathrate compound and a silicon atom; R' ₁ , R' ₂ , R' ₃ , R' ₄ , R' ₅ and R' ₆ are independently selected from aryl, branched aryl and arylene ether; At least one of the aryl group, branched aryl group and arylene ether has an ethynyl group; _R'7 is an aryl group or a substituted aryl group. We also disclose methods of making these thermosetting mixtures. This new isomeric thermosetting monomer or dimer mixture is useful as a dielectric material in the field of microelectronics and is soluble in many solvents such as cyclohexanone. These desirable properties make the isomeric thermosetting monomer or dimer mixture highly desirable for forming films having a thickness of about 0.1 micron to 1.0 micron.

A mixture of the aforementioned isomers in porous form is claimed in our patent application 60/384304 filed concurrently with the present application.

In the Background Art section of our International Patent Publication WO 01/78110 published on October 18, 2001, we mentioned a method for introducing nano-sized cavities, which includes physical blending or chemical grafting of thermally stable or intolerant hot part. The disclosed invention points out that a cage structure (such as C ₁₀ adamantane or C ₁₄ adamantane) can be used to introduce nano-holes into dielectric materials to obtain low-k materials and define the dielectric properties of low-k materials. The electrical constant is lower than 3.0. However, this publication does not report the dielectric constant of any of its examples.

International Patent Publication WO 00/31183 states in its background section that although known porous thermoplastic materials have acceptable dielectric constants, the pores tend to collapse during subsequent high temperature processing. Therefore, the patent teaches not to add porosity to a cage structure into which nanocavities have been introduced (International Patent Publication WO 01/78110 published on October 18, 2001). Additionally, U.S. Patents 5,776,990, 5,895,263, 6,107,357, and 6,342,454, and U.S. Patent Publication 2001/0040294 indicate that while dielectric constants of 2.3-2.4 are achievable to porosity levels below about 20%, they do not include small domain sizes and/or In the case of non-interconnected pore structures, the pore content cannot be further increased. Likewise, U.S. Patents 6,271,273, 6,156,812, 6,171,687, and 6,172,128 teach limiting the amount of thermolabile monomer units to less than about 30% by volume, because when more than about 30% by volume of thermolabile monomer is used, the resulting The dielectric material will have columnar or layered regions rather than hole or cavity structures. Thus, upon removal, ie, thermally degraded, heat-labile monomer units, interconnected or collapsed structures will form.

Although there are various methods for reducing the dielectric constant of materials in the prior art, these methods all have disadvantages. Accordingly, there remains a need in the semiconductor industry to: a) provide improved compositions and methods for reducing the dielectric constant of dielectric layers; b) provide improved properties such as thermal stability, glass transition temperature (Tg), modulus and hardness. Dielectric materials; c) making thermoset compounds and dielectric materials that can be solvated and spin-coated on wafers or laminates; and d) providing materials with said scalability.

The present invention advantageously provides such scalability so that semiconductor manufacturers can use the compositions of the present invention for the fabrication of a variety of microchips.

Summary of the invention

In response to the needs of the prior art and from a perspective different from the prior art, we have developed a composition comprising:

(a) dielectric material; and

(b) a porogen comprising at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substituent and at least two alkyl substituents on adjacent aromatic rings Bonds exist between substituents.

We have also found a composition comprising a cage structure with a dielectric constant of less than 2.7.

We have also discovered a composition comprising:

(a) a thermosetting component comprising:

(1) Optional at least one monomer of formula I:

and

(2) at least one oligomer or polymer of formula II,

wherein E is a clathrate; each Q is the same or different and is selected from hydrogen, aryl, branched aryl, and substituted aryl, wherein the substituents include hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl group, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl or carboxyl; _Gw is aryl or substituted aryl, wherein the substituent includes halogen and alkyl; h is 0-10; i is 0-10; j is 0-10; w is 0 or 1; and

(b) Porogens.

It can be understood that when w in the above formula II or the following formulas IV, VI, VII, VIII or IX is 0, two clathrate compounds are directly bonded. For each E to which at least one Q is attached, preferably no more than one Q to which E is attached is hydrogen, more preferably none of the Qs to which E is attached is hydrogen. When Q is a substituted aryl, then more preferably the aryl is substituted with alkenyl and alkynyl. Most preferred Q groups include (phenylethynyl)phenyl, bis(phenylethynyl)phenyl, phenylethynyl(phenylethynyl)phenyl and (phenylethynyl)phenylphenyl moieties. Preferred aryl groups as _Gw include phenyl, biphenyl and terphenyl. A more preferred _Gw group is phenyl. Preferably w is 1.

The invention also includes a method of using the composition described above. One method includes the steps of: decomposing the porogen; and volatilizing the decomposed porogen, thereby lowering the dielectric constant of the dielectric material. Another method includes the steps of: decomposing the porogen; and volatilizing the decomposed porogen, thereby forming pores in the dielectric material.

We have also developed a composition comprising:

(a) a compound having at least two functional groups, wherein the two functional groups may be the same or different, and at least one of the first functional group and the second functional group is selected from a silicon-containing group, a nitrogen-containing group, a carbon-oxygen bond-containing group , hydroxyl and carbon-carbon double bond groups; and

(b) A porogen comprising at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substituent and there is a bond between at least two alkyl substituents on adjacent aromatic rings .

Brief description of the drawings

Figures 1A-1F illustrate how to prepare _C10 adamantyl compositions for use as thermosetting components in the compositions of the present invention.

Figure 2 illustrates a method of preparing a _C14 adamantyl composition for use as a thermosetting component in the composition of the present invention.

Figures 3A to 3F illustrate another method of preparing a _C14 adamantyl composition useful as a thermosetting component in the compositions of the present invention.

Figure 4 shows the scanning electron micrographs of the cross-sections of the films of Examples 44-47 of the present invention.

Figure 5 shows the scanning electron micrographs of the surface of the films of Examples 44-47 of the present invention.

Figure 6 shows the thermal desorption mass spectra of Examples 46-49 of the present invention.

Detailed description of the invention

Compositions of thermosetting components and porogens associated therewith are claimed in our patent application 10/158548 filed concurrently with the present application.

Dielectric material

Known dielectric materials such as inorganic, organic or organic and inorganic hybrid materials can be used together with the porogens described below. Examples of these dielectric materials include phenylethynylated aromatic monomers or oligomers; fluorinated or non-fluorinated polyarylene ethers, as disclosed in commonly assigned U.S. Patent Nos. 5,986,045, 6,124,421, 6,291,628, and 6,303,733 bisbenzocyclobutene; and organosiloxanes, such as commonly assigned copending US patent application 10/078,919, filed February 19, 2002.

As used herein, the terms "cage structure", "cage molecule" and "cage compound" are used interchangeably and mean a molecule having at least 8 atoms arranged such that there is at least one bridge A bond covalently connects two or more atoms of a ring system. In other words, a cage structure, cage molecule or clathrate compound comprises a number of rings joined by covalently bonded atoms, wherein the structure, molecule or compound defines a space such that Points cannot leave without passing through the ring. The bridge and/or ring system may include one or more heteroatoms, may comprise an aromatic group, part of a cyclic or acyclic saturated hydrocarbon group, or a cyclic or acyclic unsaturated hydrocarbon group. Other cage structures may also include fullerenes and crown ethers with at least one bridge. For example, a C ₁₀ adamantane or a C ₁₄ adamantane is considered a cage structure, whereas a naphthalene or an aromatic spiro compound is not a cage structure by this definition because naphthalene or an aromatic spiro compound does not contain one or more Bridge bonds, therefore do not fall within the definition of clathrates above. The clathrate compound is preferably C ₁₀ adamantane and C ₁₄ adamantane, more preferably C ₁₀ adamantane.

As used herein, the term "bridgehead carbon" refers to any cage carbon that is bonded to three other carbons. Thus, for example, _C10 adamantane has 4 bridgehead carbons and _C14 adamantane has 8 bridgehead carbons.

Preferred dielectric materials are the thermoset compositions disclosed and claimed in our commonly assigned co-pending patent application 60/347195 filed January 8, 2002, 60/347195 filed concurrently with the present application. 384303 and P-106878 filed January 3, 2003. These patent applications are hereby incorporated by reference in their entirety.

Preferably the compositions of the present invention comprise: (a) at least one C ₁₀ adamantane monomer of formula III

and (b) at least one C ₁₀ adamantane oligomer or polymer of formula IV

or (a) at least one C _adamantane monomer of formula V

and (b) an oligomer or polymer of at least one C _adamantane monomer of formula VI

The definitions of Q, G _w , h, i, j and w are the same as above.

In the above formula IV, when h, i and j are all 0, the _C10 adamantane dimer is shown in the following formula VII:

Wherein Q and _Gw are as defined above. When w is 0 in Formula VII, examples of C ₁₀ adamantane dimers are listed in Table 2 below.

Table 2

When w is preferably 1 in formula VII, examples of preferred dimers are listed in Table 3 below.

table 3

In the above formula IV, when h is 1 and i and j are 0, the _C10 adamantane trimer is shown in the following formula VIII:

Wherein Q and _Gw are as defined above. When w is preferably 1 in formula VIII, examples of preferred trimers are listed in Table 4 below.

Table 4

Preferably, the composition of the invention comprises at least one oligomer or polymer of formula VI above, wherein Q, G, h, i, j and w are as defined above. When h, i and j are all 0 in the above formula VI, the _C14 adamantane dimer is shown in the following formula IX:

Wherein Q and _Gw are as defined above.

Preferably the thermosetting component (a) comprises: (1) a C ₁₀ adamantane monomer of formula XA

Formula XB

Formula XC

or XD

and (2) the C ₁₀ adamantane oligomer or polymer of formula XI

and preferably a C ₁₀ adamantane oligomer or polymer of the formula

Or (1) the C _adamantane monomer of formula XIIA

Formula XIIB

Formula XIIC

Formula XIID

and (2) C _adamantane oligomers or polymers of formula XIII

and preferably a C _adamantane oligomer or polymer of the formula,

wherein h is 0-10; i is 0-10; j is 0-10; in formulas XA, XB, XC, XD, XI, XIIA, XIIB, XIIC and XIID each _R is the same or different and is selected from hydrogen, Halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl ; in formulas XA, XB, XC, XD, XI, XIIA, XIIB, XIIC and XIID, each Y is the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl or halogen.

Formulas II, IV, VI, XI and XIII represent arbitrary or random structures in which any one unit of h, i and j may or may not be repeated multiple times before the other unit. Thus, the order of the units of formulas II, IV, VI, XI and XIII above is arbitrary or random.

In one embodiment, it is preferred that the thermosetting component comprises a C ₁₀ adamantane monomer of formulas XA, XB, XC and XD above and at least one C ₁₀ adamantane oligomer or polymer of XI above, wherein h, At least one of i and j is at least 1. Preferably, the thermosetting component comprises a _C14 adamantane monomer of the above formula XIIA, XIIB, XIIC or XIID and at least one _C14 adamantane oligomer or polymer of the above formula XIII, wherein h, i and j are at least One is at least 1.

A preferred thermosetting component comprises a C ₁₀ adamantane monomer of formula XA, XB, XC or XD above and a C ₁₀ adamantane oligomer or polymer of formula XIV below wherein R ₁ , Y and w are as defined above and h is 0 or 1.

The preferred _C10 adamantane oligomer or polymer structure is shown in the following formula:

A preferred thermosetting component comprises a _C14 adamantane monomer of formula XIIA, XIIB, XIIC or XIID above and a _C14 adamantane oligomer or polymer of formula XV below, wherein _R1 , Y and w are as defined above and h is 0 or 1.

Preferred C ₁₄ adamantane oligomer or polymer structure is shown in the following formula:

A preferred thermosetting component comprises a C ₁₀ adamantane monomer of formula XA, XB, XC or XD above and a C ₁₀ adamantane dimer of formula XVI below, wherein R ₁ , Y and w are as defined above.

A preferred _C10 adamantane dimer is represented by the following formula:

A preferred thermosetting component comprises a C ₁₄ adamantane monomer of formula XIIA, XIIB, XIIC or XIID above and a C ₁₄ adamantane dimer of formula XVII below, wherein R ₁ , Y and w are as defined above.

A preferred _C14 adamantane dimer is represented by the following formula:

It should be understood that the substitution patterns exemplified in Tables 2, 3 and 4 above may also occur in tetramers and higher oligomers.

A preferred thermosetting component comprises a C ₁₀ adamantane monomer of formula XA, XB, XC or XD above and a C ₁₀ adamantane trimer of formula XVIII below, wherein R ₁ , Y and w are as defined above.

A preferred _C10 adamantane trimer is represented by the following formula:

Preferred thermosetting components include a C ₁₄ adamantane monomer of formula XIIA, XIIB, XIIC or XIID above and a C ₁₄ adamantane trimer of formula XIX below.

The preferred _C14 adamantane trimer is shown in the following formula:

Preferably, the thermosetting component comprises a C ₁₀ adamantane monomer of formula XA, XB, XC or XD above, a C ₁₀ adamantane dimer of formula XVI above, and at least one C ₁₀ adamantane oligomer or polymer of formula XI above wherein at least one of h, i, and j is at least 1. Preferably, the thermosetting component comprises a _C14 adamantane monomer of formula XIIA, XIIB, XIIC or XIID above, a _C14 adamantane dimer of formula XVII above, and at least one _C14 adamantane oligomer or polymer of formula XIII above wherein at least one of h, i, and j is at least 1.

Preferred thermosetting components include C 10 adamantane monomers of formula XA, XB, XC or XD above, C ₁₀ adamantane dimers of formula XVI above, C ₁₀ adamantane trimers of formula XVIII above, and C ₁₀ adamantane trimers of formula XI above. At least one C ₁₀ adamantane oligomer or polymer wherein at least one of i and j is at least 1. Preferred thermosetting components include C adamantane monomers of formula XIIA, XIIB, XIIC or XIID above, C adamantane dimers of formula XVII above, C _adamantane trimers of formula XIX above, and C _adamantane trimers of formula XIII _above . at least one C _adamantane oligomer or polymer, wherein at least one of i and j is at least 1.

The thermosetting component includes a tetra-substituted C ₁₀ adamantane monomer of Formula XA or a tetra-substituted C ₁₄ adamantane monomer of Formula XIIA. A preferred monomer is a C ₁₀ adamantane monomer of formula XA. The C ₁₀ adamantane skeleton has substituted aryl groups at positions 1, 3, 5 and 7. The compound of formula XI is an oligomer or polymer formed by linking C ₁₀ adamantane monomers of formula XA through unsubstituted and/or substituted aryl units. The compound of formula XIII is an oligomer or polymer formed by linking C ₁₄ adamantane monomers of formula XIIA through unsubstituted and/or substituted aryl units. Generally, h, i and j are all numbers from 0-10, preferably 0-5, more preferably 0-2. Therefore, the simplest C ₁₀ adamantane oligomer is a dimer as shown in formula XVI above (h is 0, i is 0 and j is 0 in formula XI), in which two C ₁₀ adamantane skeletons are unsubstituted through or substituted aryl unit linkage. The simplest C ₁₄ adamantane oligomer is a dimer as shown in the above formula XVII (h is 0, i is 0 and j is 0 in formula XIII), wherein two C ₁₄ adamantane skeletons are unsubstituted or substituted The aryl units are linked.

In another embodiment, it is preferred that the thermosetting component of the present invention comprises at least one C ₁₀ adamantane oligomer or polymer of formula XI above, wherein h is 0-10, i is 0-10 and j is 0-10. 10. Preferably, the thermoset component of the present invention comprises at least one _C14 adamantane oligomer or polymer of formula XIII above, wherein h is 0-10, i is 0-10 and j is 0-10.

Preferably, the thermoset component of the present invention comprises at least one _C10 adamantane oligomer or polymer of formula XI above, wherein h is 0 or 1, i is 0 and j is 0. The C ₁₀ adamantane structure is shown in Formula XIV above.

Preferably, the thermoset component of the present invention comprises at least one _C14 adamantane oligomer or polymer of formula XIII above, wherein h is 0 or 1, i is 0 and j is 0. The C ₁₄ adamantane structure is shown in Formula XV above.

Preferably, the thermoset component of the present invention comprises at least one _C10 adamantane oligomer or polymer of formula XI above, wherein h is 0, i is 0 and j is 0. The C ₁₀ adamantane dimer is shown in Formula XVI above.

Preferably the thermosetting component comprises at least one _C14 adamantane oligomer or polymer of formula XIII above, wherein h is 0, i is 0 and j is 0. The C ₁₄ adamantane dimer is shown in formula XVII above.

Preferably the thermosetting component comprises at least one C ₁₀ adamantane oligomer or polymer of formula XI above, wherein h is 1, i is 0 and j is 0. The C ₁₀ adamantane trimer is shown in Formula XVIII above.

Preferably the thermosetting component (a) comprises at least one _C14 adamantane oligomer or polymer of formula XIII above, wherein h is 1, i is 0 and j is 0. The C ₁₄ adamantane trimer is shown in formula XIX above.

Preferably the thermosetting component comprises a mixture of at least one C ₁₀ adamantane oligomer or polymer of formula XI above, wherein h is 2, i is 0 and j is 0 (linear oligomer or polymer) and h is 0, i is 1 and j is 0 (branched oligomer or polymer). Thus, the composition comprises a mixture of linear C ₁₀ adamantane tetramers represented by the following formula XX, wherein R ₁ , Y and w are as defined above.

Preferably, the linear _C10 adamantane tetramer is a polymerizable body represented by the formula:

and a C ₁₀ adamantane branched tetramer of formula XXI as follows:

and a preferably branched _C10 adamantane tetramer represented by the formula:

Preferably the thermosetting component comprises at least one C _adamantane oligomer or polymer of formula XIII above, wherein h is 2, i is 0 and j is 0 (to give a linear oligomer or polymer) and h is 0, i is 1 and j is 0 (resulting in a branched oligomer or polymer). Therefore, the composition of the present invention includes a C ₁₄ adamantane linear tetramer represented by the following formula XXII, wherein R ₁ , Y and w are as defined above.

A preferred linear C ₁₄ adamantane tetramer is a C ₁₄ adamantane tetramer represented by the formula:

and a C _adamantane branched tetramer of formula XXIII as follows:

and a preferably branched C _adamantane tetramer represented by the formula:

Preferred thermoset components include the C ₁₀ adamantane dimer of formula XVI above and the C ₁₀ adamantane trimer of formula XVIII above. Preferred thermoset components include the _C14 adamantane dimer of formula XVII above and the _C14 adamantane trimer of formula XIX above.

Preferred thermoset components include a C ₁₀ adamantane dimer of formula XVI above and at least one C ₁₀ adamantane oligomer or polymer of formula XI above, wherein h is 0, i is at least 1 and j is 0. A preferred thermosetting component comprises a _C14 adamantane dimer of formula XVII above and at least one _C14 adamantane oligomer or polymer of formula XIII above, wherein h is 0, i is at least 1 and j is 0 and w is 0 or 1.

In the above two embodiments, for the above formulas I and II, it is preferred that the Q group includes aryl and aryl substituted by alkenyl and alkynyl, more preferably the Q group includes (phenylethynyl)phenyl, Bis(phenylethynyl)phenyl, phenylethynyl(phenylethynyl)phenyl and (phenylethynyl)phenylphenyl moieties. Preferred aryl groups for _Gw include phenyl, biphenyl and terphenyl. A more preferred _Gw group is phenyl.

In the above formulas XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, XIID, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII and XXIII, attached at _R1≡C Each _R group in the acetylene substituent on the benzene ring of the -type C ₁₀ adamantane ring or C ₁₄ adamantane ring is the same or different. _R is selected from hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxy Alkynyl, hydroxyl or carboxyl. Each R ₁ can be unbranched or branched and unsubstituted or substituted, and the substituents can be unbranched or branched. Preferred are alkyl, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyalkenyl and hydroxyalkynyl groups containing about 2 to 10 carbon atoms and aryl, aryl, and aryl groups containing about 6 to 18 carbon atoms. ethers and hydroxyaryls. If R ₁ represents aryl, it is preferred that R ₁ is phenyl. Preferably at least two R ₁ C≡C groups attached to the benzene ring are two different isomers. Examples of at least two different isomers include meta, para and ortho isomers. Preferably the at least two different isomers are meta and para isomers. The preferred monomer 1,3,5,7-tetrakis[3'/4'-(phenylethynyl)phenyl] _{C10adamantane} (shown in Figure 1D) has 5 isomeric forms: (1) for Position-, Para-position-, Para-position-, Para-position-; (2) Para-position-, Para-position-, Para-position-, Meta-position-; (3) Paraposition-, Paraposition-, Meta-position, Space Position-; (4) para-, meta-, meta-, meta-; (5) meta-, meta-, meta-, meta-.

Each Y on the benzene ring of the above formulas XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, XIID, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII and XXIII same or different and selected from hydrogen, alkyl, aryl, substituted aryl or halogen. When Y is an aryl group, examples of the aryl group include phenyl or biphenyl. Y is preferably selected from hydrogen, phenyl and biphenyl, more preferably hydrogen. It is preferred that at least two different isomers exist in at least one phenyl group between two bridgehead carbon atoms of the C ₁₀ adamantane or C ₁₄ adamantane. Examples of at least two different isomers include meta-, para- and ortho-isomers. Preferably at least two isomers are meta- and para-isomers. The most preferred dimer 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]C ₁₀ adamantane-7′-yl}benzene (shown in Figure 1F) has the following 14 isomers. Preferably, the phenyl group located between the two bridgehead carbon atoms of the C ₁₀ adamantane exists as meta- and para-isomers. For each of the previous two isomers, the R ₁ C≡C group on the phenyl group has the following 7 isomers: (1) para-, para-, para-, para-, Para-, para-; (2) para-, para-, para-, para-, para-, meta-; (3) para-, para-, para-, Para-, meta-, meta-; (4) para-, para-, para-, meta-, meta-, meta-; (5) para-, para-, Meta-, Meta-, Meta-, Meta-; (6) Para-, Meta-, Meta-, Meta-, Meta-, Meta-; and (7) Meta- , Meta-, Meta-, Meta-, Meta-, Meta-.

In addition to the branched C ₁₀ adamantane structure of the above formula XXI, it should be understood that when h is 0, i is 0 and j is 1, the above formula XI represents further branching into a branched chain structure as shown in the following formula XXIV, wherein R _1. Y and w are as defined above. It is understood that branching can go beyond the structure of Formula XXIV, as the branched C ₁₀ adamantane units of the structure of Formula XXIV can also be further branched.

Preferably, the _C10 adamantane structure is shown in the following formula:

In addition to the branched _C14 adamantane structure of the above formula XXIII, it should be understood that when h is 0, i is 0 and j is 1, the above formula XIII represents further branching into a branched chain structure as shown in the following formula XXV. It is understood that branching can go beyond the structure of Formula XXV, as the branched C _adamantane units of the structure of Formula XXV can also be further branched.

Preferably, the _C14 adamantane structure is shown in the following formula:

In the thermosetting components, the monomer and oligomer or polymer content is determined by the gel permeation chromatography technique described below in the Analytical Test Methods section. The compositions of the present invention comprise: a C ₁₀ adamantane or a C ₁₄ adamantane monomer in an amount of about 30 to 70 area percent, more preferably about 40-60 area percent and most preferably about 45 to 55 area percent; and an oligomer or polymer in an amount of about 70-30 area%, more preferably about 60-40 area%, and most preferably about 55-45 area%. Most preferably the composition of the invention comprises: a monomer (1) in an amount of about 50 area %; and an oligomer or polymer (2) in an amount of about 50 area %.

In general, the ratio of the amount of C ₁₀ adamantane or C ₁₄ adamantane monomer (1) to oligomer or polymer (2) can be determined in an appropriate manner, such as by changing The molar ratio of the starting components is determined by adjusting the reaction conditions and by changing the ratio of non-solvent to solvent during the precipitation/isolation step.

Preferably the process for preparing the thermosetting component (a) comprises the following steps.

In step (A), C ₁₀ adamantane or C ₁₄ adamantane reacts with a halogenated benzene compound of formula XXVI to form a mixture,

wherein Y is selected from hydrogen, alkyl, aryl, substituted aryl or halogen and Y is halogen. When using a _C10 adamantane, the mixture comprises at _least one monomer of formula III above and at least one monomer of formula IV above The oligomer or polymer of wherein h is 0-10, i is 0-10, j is 0-10 and w is 0 or 1, Q is hydrogen or -C ₆ H ₃ Y ₁ Y, wherein Y ₁ and Y is as defined above. Preference is given to at least one oligomer or polymer of the formula:

Or when using C ₁₄ adamantane, the mixture includes at least one monomer of the above formula V and at least one oligomer or polymer of the above formula VI, wherein h is 0-10, i is 0-10, j is 0-10 and w is 0 or 1, Q is hydrogen or _-C6H5Y1Y , wherein _{Y1 and} Y are as defined above; and preferably at least _one oligomer or polymer of the formula

It will be appreciated by those skilled in the art that the reaction can take place at other bridgehead carbon atoms than those of the _C14 adamantane shown in Formulas X and XVI above.

In step (B), the mixture resulting from step (A) is reacted with a terminal alkynyl group of formula R ₁ C≡CH. Preferably the process of the invention forms compositions of formulas XA and XI or XIIA and XIII above.

In step (A), a C ₁₀ adamantane or a C ₁₄ adamantane is reacted with a halobenzene compound of formula XXVI. In addition to the halo group _Y1 and the aforementioned Y groups, the halobenzene compounds may also contain other substituents.

Preferably the halobenzene compound is selected from bromobenzene, dibromobenzene and iodobenzene. Preference is given to bromobenzene and/or dibromobenzene, more preferably bromobenzene.

The reaction of C ₁₀ adamantane or C ₁₄ adamantane with halobenzene compound (step (A)) is preferably carried out by Friedel-Crafts reaction in the presence of a Lewis acid catalyst. Although all common Lewis acid catalysts can be used, it is preferred that the Lewis acid catalyst used comprises at least one member selected from the group consisting of aluminum (III) chloride (AlCl ₃ ), aluminum (III) bromide (AlBr ₃ ) and aluminum (III) iodide ( AlI ₃ ) compounds. Among them, aluminum(III) chloride (AlCl ₃ ) is most preferred. Although the Lewis acid of aluminum(III) bromide is more acidic, it is generally not preferred for use due to its low sublimation temperature of only 90°C. Therefore, compared with aluminum(III) chloride, aluminum(III) bromide is more difficult to apply in large-scale industry.

In a more preferred aspect, the Friedel-Crafts reaction is carried out in the presence of a second catalyst component. The second catalyst component preferably comprises at least one compound selected from halogenated tertiary alkanes containing 4-20 carbon atoms, tertiary alkanols having 4-20 carbon atoms, secondary and tertiary alkanols having 4-20 carbon atoms Alkenes and halogenated tertiary alkylaryl compounds. Specifically, the second catalyst component includes at least one selected from the group consisting of 2-bromo-2-methylpropane (tert-butyl bromide), 2-chloro-2-methylpropane (tert-butyl chloride), 2- Methyl-2-propanol (tert-butyl alcohol), isobutylene, 2-bromopropane and tert-butylbromobenzene, most preferably 2-bromo-2-methylpropane (tert-butyl bromide). In general, compounds containing an alkyl group of 5 or more carbon atoms are less suitable because a solid component precipitates in the reaction solution at a later stage of the reaction.

Most preferably the Lewis acid catalyst is aluminum (III) chloride (AlCl ₃ ) and the second catalyst component is 2-bromo-2-methylpropane (tert-butyl bromide) or tert-butylbromobenzene.

The preferred procedure of the Friedel-Crafts reaction is by mixing C ₁₀ adamantane or C ₁₄ adamantane, a halogenated benzene compound (such as bromobenzene) and a Lewis acid catalyst (such as aluminum chloride) and heating at 30°C-50°C, preferably 35 ℃-45℃, especially heating at 40℃. At temperatures below 30 °C, the reaction does not go to completion, eg a higher proportion of trisubstituted _C10 adamantane forms will be produced. It will be appreciated that in principle higher temperatures (e.g. 60° C.) than the above mentioned temperatures can be used, but this will lead to undesired reactions which lead to the reduction of the non-halogenated aromatic starting material (e.g. benzene) in the reaction mixture of step (A). The proportion is higher. The second component of the catalyst system, such as tert-butyl bromide, is then added to the above reaction solution, usually for a duration of 5-10 hours, preferably 6-7 hours, and after the addition is complete, at the temperature range specified above The reaction mixture is mixed well, usually further mixed for 5-10 hours, preferably 7 hours.

Surprisingly, in addition to tetraphenyl compound monomers such as 1,3,5,7-tetrakis(3'/4'-bromophenyl) C ₁₀ adamantane, in the mixture obtained after step (A) also Found its oligomers or polymers. The amount ratio of the C ₁₀ adamantane monomer of formula III to the C ₁₀ adamantane oligomer or polymer of formula IV or the C ₁₄ adamantane monomer of formula V to the C ₁₄ adamantane oligomerization of formula VI was totally unexpected The molar ratio of the compound or polymer can be controlled by the amount of C ₁₀ adamantane or C ₁₄ adamantane, halobenzene compound (such as bromobenzene) and second catalyst component (such as tert-butyl bromide) used. Preferably, in the reaction mixture of step (A), C ₁₀ adamantane or C ₁₄ adamantane: halogenated benzene compound: the molar ratio of the second catalyst component is 1: (5-15): (2-10), more preferably 1:(8-12):(4-8).

In compounds of formula XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, XIID, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV and XXV, The position of the halogen substituent Y ₁ is not limited. Preferred mixtures include meta- and para-isomers, as opposed to all para-isomers, which advantageously result in enhanced solubility and good film properties. In the reaction mixture of step (A), besides monomers and oligomers or polymers, there will also be starting components and by-products such as non-perphenylated C ₁₀ adamantanes.

The mixture resulting from step (A) can optionally be worked up by methods known to the person skilled in the art. For example, it may be necessary to remove unreacted halobenzene compounds, such as bromobenzene, from the mixture in order to obtain products having a high proportion of compounds of formulas III, IV, V and VI which are available for further reaction. Any solvent or solvent mixture which is miscible with halobenzene compounds such as bromobenzene and which is suitable for the precipitation of compounds of formula III, IV, V and VI can be used for the isolation of these products. The mixture resulting from step (A) is preferably added, eg dropwise, to a non-polar solvent or solvent mixture, preferably using an aliphatic hydrocarbon having 7 to 20 carbon atoms or a mixture thereof, especially at least one selected from the group Sub: heptane fraction (boiling range: 93-99°C), octane fraction (boiling range: 98-110°C) and currently available from Honeywell International Inc., trade name Spezial Benzin 80-110°C (boiling range: 80-110°C petroleum ether) alkane mixture. The most preferred is Spezial Benzin 80-110°C (petroleum ether with a boiling range of 80-110°C). Preferably the weight ratio of organic mixture to non-polar solvent is about 1:2 to 1:20, more preferably about 1:5 to 1:13, most preferably about 1:7 to 1:11. Alternatively, polar solvents or solvent mixtures such as methanol or ethanol can be used in the workup of the mixture produced after step (A), but are less preferred since the precipitated product mixture is a rubbery composition.

We have found that the highest ratio of monomers produced in step (A) to dimers, trimers and oligomers in the reaction mixture occurs if the mixture of step (A) above is precipitated in certain solvents Significant change. This finding will well prompt one skilled in the art to adjust the process conditions to obtain the target ratio of monomers to dimers, trimers and oligomers. To reduce this ratio, preference is given to using solvents in which monomers and oligomers or polymers have different solubilities.

Preferred solvents to achieve this change in the ratio of monomers to dimers and trimers include Spezial Benzin 80-110°C (petroleum ether with a boiling range of 80-110°C), ligroine (boiling range of 90-110°C) and Heptane (boiling point 98°C). A more preferred solvent is Spezial Benzin. In particular, to achieve a monomer:(dimer+trimer+oligomer) variation of about 3:1 to about 1:1, the mixture of step (A) is precipitated from Spezial Benzin, or as To obtain a monomer:(dimer+trimer+oligomer) variation of about 3:1 to about 1.7-2.0:1.0, the reaction mixture of step (A) was precipitated from ligroine and heptane. We know that these apparent changes in peak distribution upon precipitation can be explained by monomer loss in the precipitation filtrate: 2/3 loss in SpezialBenzin and ≥1/3 loss in ligroine and heptane, which correspond to 50 and 25-33% of Monomer yield loss. To keep the monomer:(dimer+trimer+oligomer) ratio of 3:1 constant, the reaction mixture from step (A) was precipitated in methanol and no yield loss was observed . This was further confirmed by yield loss measurements in the filtrate and GPC analysis of the filtrate.

Like the synthetic method described by Ortiz, the Friedel-Crafts reaction performed according to the preferred aspect of step (A) in the method of the present invention starts directly with a _C10 adamantane coupled with a halobenzene compound. The method of the present invention is particularly advantageous compared to the prior synthesis of _e.g. The method does not require the preparation of tetrabromo-C ₁₀ adamantane first, thus simplifying the reaction steps. At the same time less undesirable benzene is formed.

Those skilled in the art know that, in addition to reacting _C10 adamantanes directly with halobenzene compounds (e.g. with the help of Friedel-Crafts reactions), it is also possible to introduce compounds of formulas III, IV, V and VI via a multistep synthesis. The halo group Y ₁ is, for example, coupled with a C ₁₀ adamantane and a phenyl compound (ie no halo group Y ₁ ), and then introduced into the Y ₁ group such as by addition reaction with W(Y ₁ ) ₂ (such as Br ₂ ). But this method is not preferred.

In step (B) of the preferred process, the mixture obtained after step (A) (optionally after work-up) is reacted with a terminal alkynyl group of the formula R ₁ C≡CH (R ₁ is as defined above).

In the formula R ₁ C≡CH, R ₁ is combined with R in the previously described C ₁₀ adamantane products of formulas XA, XB, XC, XD and XI and the C ₁₄ adamantane products of formulas XIIA, XIIB, XIIC or XIID and XIII ₁ is the same. Accordingly, it is most preferred to use ethynylbenzene (phenylacetylene) as the terminal alkynyl group for the reaction of step (B).

In step (B), to couple the terminal alkynyl group with the halophenyl group in the _C10 adamantane system, all conventional methods suitable for this purpose as described below can be used: Diederich, F., and Stang, PJ , (ed.) "Metal-Catalyzed Cross-Coupling Reactions", Wiley-VCH 1998 and March., J., "Advanced Organic Chemistry", Fourth Edition, John Wiley & Sons 1992, pp. 717/718.

When Y on the phenyl group is connected to two bridgehead carbons in the above formula XI or the above formula XIII, Y can react with phenylacetylene to form a terminal alkynyl group.

In a preferred aspect of the invention, the reaction of the mixture obtained after step (A) (optionally after work-up) with terminal alkynes is used in the so-called Sonogashira coupling (see Sonogashira; Tohda; Hagihara; Tetrahedron Lett. 1975, p. 4467 ) in the presence of a catalyst system. More preferably used catalyst systems comprise in any case at least one palladium-triarylphosphine complex of formula [Ar ₃ P] ₂ PdX ₂ (wherein Ar=aryl and X=halogen), copper halides such as CuI), base (such as trialkylamine), triarylphosphine and cosolvent. According to the invention, such preferred catalyst systems may consist of equal parts of the stated components. Preferably, the co-solvent includes at least one component selected from the group consisting of toluene, xylene, chlorobenzene, N,N-dimethylformamide and 1-methyl-2-pyrrolidone (N-methyl-pyrrolidone (NMP)). Most preferred are catalyst systems comprising the following components: bis-(triphenylphosphine)palladium(II) dichloride (ie [Ph ₃ P] ₂ PdCl ₂ ), triphenylphosphine (ie [Ph ₃ P]) , ketone iodide (I), triethylamine and toluene (as co-solvent).

A preferred procedure for the reaction of the mixture obtained in step (A) (and optional workup) with a terminal alkyne is to first mix the mixture with a base (e.g. triethylamine) and a cosolvent (e.g. toluene) and bring the mixture to room temperature Stir for several minutes; then add palladium-triphenylphosphine complex (such as Pd(PPh ₃ ) ₂ Cl ₂ ), triphenylphosphine (PPh ₃ ) and copper halide (such as ketone iodide (I)); The mixture is heated at 50°C-90°C (more preferably 80°C-85°C); then the terminal alkyne is added within the specified temperature range within 1-20 hours (more preferably 3 hours); after the addition is complete, the mixture is Heating at 75°C-85°C (more preferably 80°C) for at least 5-20 hours (more preferably 12 hours); then adding the solvent to the reaction solution and distilling under reduced pressure; preferably after filtering, the reaction solution is cooled to 20°C- 30° C. (more preferably 25° C.); finally, the reaction mixture of step (B) is treated by conventional methods well known to those skilled in the art, specifically to remove trace metals (such as palladium).

If precipitation of the step (B) mixture occurs in certain solvents, the maximum ratio of monomers to their dimers and trimers and oligomers in the reaction mixture produced in step (B) above will change.

Surprisingly, it was found that in the reaction step starting directly from _C10 adamantane, the ratio of _C10 adamantane, halobenzene compound and a second catalyst component such as tert-butyl bromide can be controlled Oligomer content or polymer content in the reaction product of step (A). Likewise, the benzene content of the reaction mixture of step (A) can be successfully controlled by such use of ratios. Due to the toxicity of benzene, this will be very important in an industrial scale synthesis. The content of oligomers or polymers is such that their secondary chemistry (secondary chemistry) is similar to that of monomers (such as 1,3,5,7-tetra-(3'/4'-bromophenyl) C ₁₀ adamantane) , ie the oligomers and polymers react with the terminal alkynes of step (B) as readily as the monomers.

In one embodiment, the thermosetting component is mixed with a porogen. The thermosetting component is used in an amount of about 50 to 90% by weight and the porogen is used in an amount of about 10 to 50% by weight. The thermosetting component and porogen may or may not react with each other. The tackifier is preferably added subsequently.

Preferably in another embodiment, the present invention comprises a composition comprising a porogen and a mixture comprising at least two different isomers of formula XXVII,

Wherein the definition of Q is the same as before. Preferred mixtures include at least two different isomers of formula XXVIII, formula XXIX, formula XXX:

Formula XXVII

Formula XXIX

Formula XXX

wherein each Y is the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl, or halogen and each _R is the same or different and is selected from hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl.

Preferred mixtures include at least two different isomers of formula XXXI

Wherein, the definition of each Q is the same as above. Preferably the mixture comprises at least two different isomers of formula XXXII, formula XXXIII, formula XXXIV,

Formula XXXII

Formula XXXIII

Formula XXXIV

Wherein Y and R ₁ are as defined above.

Tackifier:

As used herein, the term "tackifier" refers to any component added to a thermosetting component that increases its adhesion to a substrate as compared to the thermosetting component alone.

As used herein, the term "compound having at least two functional groups" refers to any compound having at least two functional groups and capable of interacting, reacting, or bonding as follows. Functional groups can react in a variety of ways, including undergoing addition reactions, nucleophilic and electrophilic substitution or elimination, free radical reactions, and more. Other reactions may also include non-covalent bond formation, such as the formation of van der Waals forces, electrostatic bonds, ionic bonds, and hydrogen bonds.

In one embodiment, the tackifier and porogen are mixed. The tackifier is used in an amount of about 3 to 18% by weight and the porogen is used in an amount of about 10 to 50% by weight, based on the composition comprising the tackifier, porogen and thermosetting compound. The thermosetting component and porogen may or may not react with each other. Preferably the thermosetting component is subsequently added in an amount of about 32 to 87% by weight.

We have found that tackifiers advantageously increase the compatibility of the porogen and thermoset components. While not wishing to be bound by theory, it is believed that the tackifier acts as an emulsifier, thus forming a homogeneous system.

Tackifiers are disclosed in our commonly assigned pending patent applications 60/350187, filed January 15, 2002, and 10/160773, filed May 30, 2002, the contents of which are incorporated by reference in their entirety incorporated into this article.

In the tackifier, preferably at least one of the first functional group and the second functional group is selected from silicon-containing groups, nitrogen-containing groups, carbon-oxygen bond-containing groups, hydroxyl groups, and carbon-carbon double bond-containing groups. Preferred silicon-containing groups are selected from Si-H, Si-O and Si-N; Nitrogen-containing groups are selected from such as C- _NH Or other secondary amines, tertiary amines, imines, amides and imides; Groups selected from =CO (carbonyl) such as ketones and aldehydes, esters, -COOH, alkoxyl groups of 1 to 5 carbon atoms, ethers, glycidyl ethers and epoxides; hydroxyl groups such as phenolic hydroxyl groups; carbon-carbon bis The bonding group is selected from allyl and vinyl. For semiconductor applications, more preferred functional groups include silicon-containing groups, carbon-oxygen bond-containing groups, hydroxyl groups, and vinyl groups.

Examples of preferred adhesion promoters with silicon-containing groups are silanes of formula XXXVI: (R ₂ ) _k (R ₃ ) _l Si(R ₄ ) _m (R ₅ ) _n , where R ₂ , R ₃ , R ₄ and _R independently represent hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl, wherein the substituent is amino or epoxide, saturated or unsaturated alkoxy, unsaturated or saturated carboxy or aryl ; at least two of R ₂ , R ₃ , R ₄ and R ₅ represent hydrogen, hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl or unsaturated carboxy; and k+l+m+n≦4. Examples include vinylsilanes such as H ₂ C=CHSi(CH ₃ ) ₂ H and H ₂ C=CHSi(R ₆ ) ₃ where R ₆ is CH ₃ O, C ₂ H ₅ O, AcO, H ₂ C=CH or H ₂ C=C(CH ₃ )O- or vinylbenzylsilane; formula H ₂ C=CHCH ₂ -Si(OC ₂ H ₅ ) ₃ and H ₂ C=CHCH ₂ -Si(H)(OCH ₃ ) Allylsilanes of ₂ ; glycidoxypropylsilanes such as (3-glycidoxypropyl)methyldiethoxysilane and (3-glycidoxypropyl)trimethoxysilane ; Methacryloxypropylsilane of the formula H ₂ C=(CH ₃ )COO(CH ₂ ) ₃ -Si(OR ₇ ) ₃ , wherein R ₇ is an alkyl group, preferably methyl or ethyl; aminopropyl Silane derivatives including H ₂ N(CH ₂ ) ₃ Si(OCH ₂ CH ₃ ) ₃ , H ₂ N(CH ₂ ) ₃ Si(OH) ₃ or H ₂ N(CH ₂ ) ₃ OC(CH ₃ ) ₂ CH=CHSi(OCH ₃ ) ₃ . The aforementioned silanes are commercially available from Gelest.

Examples of preferred tackifiers having carbon-oxygen bond-containing groups are glycidyl ethers, including but not limited to 1,1,1-tris-(hydroxyphenyl)ethane tri-glycidyl ether available from TriQuest.

Examples of tackifiers preferably having a carbon-oxygen bond-containing group are unsaturated carboxylic acid esters having at least one carboxyl group. Examples include trifunctional methacrylates, trifunctional acrylates, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl methacrylate. The above products are all commercially available from Sartomer.

Examples of preferred tackifiers having vinyl groups are vinyl cyclic pyridine oligomers or polymers, wherein the cyclic group is pyridine, an aromatic compound or a heteroaromatic compound. Effective examples include, but are not limited to, 2-vinylpyridine and 4-vinylpyridine available from Reilly; vinylaromatics; and vinylheteroaromatics, including but not limited to vinylquinoline, vinylcarba Azole, Vinylimidazole and Vinyloxazole.

Examples of preferred silicon-group-containing adhesion promoters are the polycarbosilanes disclosed in our commonly assigned copending U.S. Patent Application Serial No. 09/471,299, filed December 23, 1999, the contents of which are incorporated by reference It is incorporated herein in its entirety. Polycarbosilane is shown in formula XXXVIX:

wherein R ₈ , R ₁₄ and R ₁₇ each represent a substituted or unsubstituted alkylene, cycloalkylene, 1,2-vinylene, allylylene or arylene; R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent hydrogen or organic groups including alkyl, alkylene, vinyl, cycloalkyl, allyl or aryl, and these groups can be branched or straight chain ; R ₁₃ represents organosilicon, silyl, siloxy or organic group; and p, q, r and s satisfy the condition [4≤p+q+r+s≤100,000], q, r and s can be All or 0 respectively. Organic groups can contain up to 18 carbon atoms, but generally contain about 1-10 carbon atoms. Useful alkyl groups include _-CH2- and -( _CH2 ) _t- , where t>1.

Preferred polycarbosilanes of the present invention include polydihydrocarbosilanes, wherein _R is a substituted or unsubstituted alkylene or phenyl group, _R is a hydrogen atom and there is no subsidiary group on the polycarbosilane chain; that is , q, r and s are all 0. Another preferred polycarbosilane group is one in which the R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ groups of formula XXXVII are substituted or unsubstituted alkenyl groups having 2-10 carbon atoms those groups. The alkenyl group may be vinyl, propenyl, allyl, butenyl or other unsaturated organic backbone groups having up to 10 carbon atoms. Alkenyl groups may be alkenyl in nature and include unsaturated alkenyl groups as side chains or substituents on other alkyl or unsaturated organic polymer backbones. Examples of these preferred polycarbosilanes include dihydro- or alkenyl-substituted polycarbosilanes such as polydihydrocarbosilane, polyallylhydrocarbosilane, and combinations of polydihydrocarbosilane and polyallylhydrocarbosilane. standard copolymer.

In a more preferred polycarbosilane, the R ₉ group of formula XXXVII is a hydrogen atom, R ₈ is a methylene group and the subsidiary groups q, r and s are 0. Other preferred polycarbosilane compounds of the present invention are polycarbosilanes of formula XXXVII, wherein R ₉ and R ₁₅ are hydrogen, R ₈ and R ₁₇ are methylene groups, R ₁₆ are alkenyl and subsidiary groups q and r is 0. The polycarbosilanes can be prepared by methods known in the art or supplied by polycarbosilane composition manufacturers. In the most preferred polycarbosilane, the R ₉ group of the formula XXXVII is a hydrogen atom; R ₈ is -CH ₂ -; q, r and s are 0 and p is 5-25. These most preferred polycarbosilanes are available from Starfire Systems, Inc. The specific examples of these most preferred polycarbosilanes are as follows:

polycarbosilane Weight average molecular weight (Mw) polydispersity  Peak Molecular Weight (Mp) 1 400-1,400 2-2.5 330-500 2 330 1.14 320 3 (10% allyl) 10,000-14,000 10.4-16 1160 4 (75% allyl) 2,400 3.7 410

As can be seen from Formula XXXVII, when r > 0, the polycarbosilanes used in the present invention may include oxidized groups in the form of siloxy groups. Thus, when r > 0, R ₁₃ represents a silicone, silyl, siloxy or organic group. It is understood that the oxidized form of polycarbosilane (r > 0) works very effectively and falls well within the scope of the present invention. It is also evident that r can be 0 independently of p, q and s, provided only that the p, q, r and s groups in the polycarbosilane of formula XXXVII satisfy [4<p+q+r+ s<100,000], and q and r can be 0 simultaneously or respectively.

Polycarbosilanes can be prepared from commercially available starting materials from a number of manufacturers using conventional polymerization methods. As an example of synthesizing polycarbosilane, the raw materials used can be obtained as follows: using commonly used organosilane compounds or polysilanes as raw materials, the corresponding polymer is produced by heating a mixture of polysilane and polyborosiloxane in an inert atmosphere , by heating polysilane and low molecular weight carbosilane mixture in an inert atmosphere to produce the corresponding polymer or by heating polysilane and low molecular weight carbosilane in an inert atmosphere in the presence of a catalyst (such as polyboron diphenylsiloxane) mixtures of carbosilanes to produce the corresponding polymers. Polycarbosilanes can also be synthesized by the Grignard reaction reported in US Patent No. 5,153,295, the contents of which are incorporated herein by reference.

Examples of preferred tackifiers with hydroxyl groups are phenolic resins or oligomers of formula XXXVIII: -[R ₁₈ C ₆ H ₂ (OH)(R ₁₉ )] _u -, where R ₁₈ is a substituted or unsubstituted alkylene R is _alkyl , alkylene, 1,2-vinylidene, cycloalkylene, allyl or aryl; and u = 3-100. Examples of useful alkyl groups include _-CH2- and d-( _CH2 )v-, where v>1. A particularly useful 1500 molecular weight phenolic resin oligomer is available from Schenectady International Inc.

Preferably, the tackifiers of the present invention are added at relatively low levels, with an effective amount of from about 0.5% to 20% by weight of the thermosetting composition (a) of the present invention, usually preferably in an amount of up to 20% by weight of the composition. About 5.0%.

By mixing the tackifier with the thermosetting component (a) and exposing the composition to a heat or high energy environment, the resulting composition has excellent adhesive properties, ensuring affinity of the entire polymer to any coating surface in contact. and sex. The tackifiers of the present invention also reduce streaking and improve tack and film uniformity. Indeed, streak reduction was also confirmed by visual inspection.

The compositions of the present invention may also include additional components such as additional tackifiers, antifoam agents, detergents, flame retardants, pigments, plasticizers, stabilizers and surfactants.

Pore former

As used herein, the term "pore" includes cavities and cells in a material and any other term having a space in a material that is occupied by a gas. Suitable gases include relatively pure gases and mixtures thereof. Typically distributed in the pores is air, primarily a mixture of nitrogen and oxygen, but may also be a pure gas such as nitrogen, helium, argon, carbon dioxide or carbon monoxide. The pores are generally spherical, but may also be or include columns, layers, discs, cavities with other shapes, or combinations of the aforementioned shapes, and these pores may be open or closed. As used herein, the term "porogen" refers to a material, including solid, liquid, or gaseous materials, that can be dissociated, degraded, depolymerized, or otherwise dissociated by radiation, heat, chemical, or moisture. The decomposed porogen can be removed from the partially or fully crosslinked matrix or can be expelled by volatilization or diffusion, thereby creating pores in the subsequently substantially fully cured matrix and thereby lowering the dielectric constant of the matrix. Pore formers include expendable polymers. Supercritical materials such as carbon dioxide can be used to remove porogens and break down porogen fragments. For the thermally decomposable porogen, a substance having a decomposition temperature lower than the glass transition temperature (Tg) of the dielectric material mixed therewith but higher than the solidification temperature of the dielectric material mixed therewith is preferred. Therefore, the dielectric material and the porogen are different materials. Preferably, the novel porogens of the present invention have a degradation or decomposition temperature of about 350°C or above. Preferably, the degraded or decomposed porogen volatilizes at a temperature above the solidification temperature of the material with which it is mixed and below the Tg of the material. Preferably, the degraded or decomposed porogen volatilizes at a temperature of about 280°C or above.

Although International Patent Publication WO 00/31183 points out that porogens can be added to thermosetting benzocyclobutene, polyarylene or thermosetting perfluoroethylene monomers to increase their porosity and thereby reduce the dielectric constant of the resin , but the publication points out that a porogen that works well in a certain matrix system does not mean that it can work in another matrix system.

Porogens comprising at least two fused aromatic rings each having at least one alkyl substituent on the fused aromatic rings and between at least two alkyl substituents on adjacent aromatic rings can be used in the present invention. key exists. Preferred porogens include unfunctionalized polyacenaphthylene homopolymers, functionalized polyacenaphthylene homopolymers, polyacenaphthylene copolymers described below, poly(2-vinylnaphthalene) and vinylanthracene, and blends thereof thing. Other useful porogens include C ₁₀ adamantane, C ₁₄ adamantane, fullerene, and polynorbornene. These porogens can be used in admixture with each other or with other porogen materials such as polycaprolactone, polystyrene and polyester. Useful blends include unfunctionalized polyacenaphthylene homopolymer and polycaprolactone. More preferred porogens are unfunctionalized polyacenaphthylene homopolymers, functionalized polyacenaphthylene homopolymers, polyacenaphthylene copolymers, and polynorbornene. Useful polyacenaphthylene homopolymers may preferably have a weight average molecular weight of from about 300 to 20,000, more preferably from about 300 to 10,000 and most preferably from about 1000 to about 7,000. Polyacenaphthene homopolymer can be obtained by polymerization of acenaphthene using the following initiators: 2,2'-azobisisobutyronitrile (AIBN), di-tert-butyl azodicarboxylate, diisopropyl azodicarboxylate, diisopropyl azodicarboxylate, Diethyl azodicarboxylate, dibenzyl azodicarboxylate, diphenyl azodicarboxylate, 1,1'-azobis(cyclohexanecarbonitrile), benzoyl peroxide (BpO), tert-butyl base peroxides and boron trifluoride ether. The chain end of the polyacenaphthylene homopolymer can have functional end groups, such as triple bonds or double bonds; Obtained by cationic polymerization quenched with hydroxyethyl acrylate.

European Patent Publication 315453 teaches that silica and certain metal oxides can react with carbon to give volatile suboxides and gaseous carbon oxides to form pores. The patent publication also indicates that the source of carbon includes any suitable organic polymer, including polyacenaphthene. However, this publication does not teach or suggest porogens that can be used with non-metallic materials or lower the dielectric constant of the substrate.

Useful polyacenaphthylene copolymers may be linear polymers, star polymers or hyperbranched polymers. The comonomer can have bulky side groups, resulting in a conformation of the copolymer similar to that of the polyacenaphthylene homopolymer, or can have non-bulky side groups, resulting in a conformation of the copolymer that is different from that of the polyacenaphthylene homopolymer. resemblance. Comonomers with bulky side groups include vinyl pivalate, tert-butyl acrylate, styrene, alpha-methylstyrene, tert-butylstyrene, 2-vinylnaphthalene, 5-vinyl-2- Norbornene, vinylcyclohexane, vinylcyclopentane, 9-vinylanthracene, 4-vinylbiphenyl, tetraphenylbutadiene, 1,2-stilbene, tert-butyl 1,2 - stilbene and indene; preferably vinyl pivalate. Hydrogenated polycarbosilanes can be used as a further comonomer or as a component of a copolymer with anthracene and at least one of the aforementioned comonomers. An example of a useful hydropolycarbosilane has 10-75% allyl groups. Comonomers with less bulky side groups include vinyl acetate; methyl acrylate; methyl methacrylate and vinyl ethers, preferably vinyl acetate.

Preferably, the comonomer is used in an amount of about 5 to 50 mole percent of the copolymer. These copolymers can be prepared by free-radical polymerization using initiators. Useful initiators preferably include 2,2'-azobisisobutyronitrile (AIBN), di-tert-butyl azodicarboxylate, diisopropyl azodicarboxylate, diethyl azodicarboxylate, azobis Dibenzyl formate, diphenyl azodicarboxylate, 1,1'-azobis(cyclohexanecarbonitrile), benzoyl peroxide (BPO), tert-butyl peroxide, more preferably AIBN. Copolymers can also be prepared by cationic polymerization using boron trifluoride ether as an initiator. Preferred copolymers have a molecular weight of from about 500 to 15,000.

The thermal properties of the copolymers formed of acenaphthene and comonomer are given in Table 5 below. In Table 5, BA represents butyl acrylate, VP represents vinyl pivalate, VA represents vinyl acetate, AIBN represents 2,2'-azobisisobutyronitrile, BF ₃ represents boron trifluoride·ethyl ether, DBADC means di-tert-butyl azodicarboxylate, W1 means the weight loss from room temperature to 250 °C, W2 means the weight loss at 250 °C for 10 minutes, W3 means the weight loss from 250 °C to 400 °C, W4 represents the weight loss at 400°C for 1 hour, and W5 represents the total weight loss.

table 5 comonomer Copolymer Initiator Comonomer% Initiator% solvent temperature(℃) time (hours) W1 W2 W3 W4 W5 mn mw BA 1 AIBN 11 1 Xylene 70 twenty four 14.63 1.02 33.14 30.44 79.23 4797 10552 BA 2 AIBN 20 1 Xylene 70 twenty four 1.47 0.98 37.92 35.55 75.92 4343 8103 BA 3 AIBN 30 1 Xylene 70 twenty four 13.41 1.6 36.48 27.55 79.04 4638 7826 BA 4 AIBN 50 1 Xylene 70 twenty four 10.01 2.96 46.92 26.51 86.40 3504 5489 BA 5 BF3 10 3 Xylene 5 2 11.93 0.58 40.06 29.33 81.90 1502 2421 VP 6 AIBN 10 1 Xylene 70 twenty four 16.22 0.41 37.8 34.72 89.15 5442 10007 VP 7 AIBN 16 1 THF 60 12 5.32 0.66 46.55 29.59 82.12 1598 2422 VP 8 AIBN 25 1 Xylene 70 twenty four 4.15 0.37 24.98 47.4 76.90 2657 8621 VP 9 AIBN 30 1 Xylene 70 twenty four 14.7 0.69 33.27 39.54 88.20 5342 9303 VP 10 AIBN 40 1 Xylene 70 twenty four 6.34 0.26 33.69 39.38 76.67 4612 7782 VP 11 AIBN 50 1 Xylene 70 twenty four 14.12 0.32 29.01 37.86 81.31 4037 6405 VP 12 BF3 10 1 Xylene 5 2 0.84 0 55.51 39.38 95.73 2078 3229 VP 13 BF3 10 3 Xylene 5 2 2.26 0.06 47.44 28.93 78.69 1786 2821 VP 14 BF3 25 1 Xylene 5 2 0.17 0 36.99 41.17 78.33 2381 3549 VP 15 BF3 25 3 Xylene 5 2 1.33 0.03 35.28 41.08 77.72 2108 3267 VP 16 BF3 40 1 Xylene 5 2 0.23 0.04 36.46 42.17 78.90 2659 3692 VP 17 BF3 40 3 Xylene 5 2 0.28 0.01 40.23 38.98 79.50 2270 3376 VA 18 AIBN 20 2 Xylene 70 twenty four 16.93 1.346 38.42 21.43 78.13 3404 7193 VA 19 AIBN 40 2 Xylene 70 twenty four 15.45 1.631 31.28 31.64 80.00 3109 6141

Known porogens such as linear polymers, star polymers, crosslinked polymer nanospheres, block copolymers and hyperbranched polymers can be used with the novel thermoset components of formula I or II above. Suitable linear polymers are polyethers such as polyethylene oxide and polypropylene oxide; polyacrylates such as polymethyl methacrylate; aliphatic polycarbonates such as polypropylene carbonate and polyethylene glycol Esters; Polyesters; Polysulfones; Polystyrenes, including monomers selected from the group consisting of halostyrenes and hydroxy-substituted styrenes; poly(alpha-methylstyrene), polylactides, and other vinyl polymers. Useful polyester porogens include polycaprolactone; polyethylene terephthalate; poly(oxyadipyloxy-1,4-phenylene); poly(oxyterephthaloyloxy phenylene-1,4-phenylene); poly(oxyadipyloxy-1,6-hexylene); polycarbonates, such as poly(hexanediol carbonate)diol having a molecular weight of about 500 to 2500 and polyethers such as bisphenol A-epichlorohydrin copolymers having a molecular weight of about 300 to 6,500. Suitably cross-linked insoluble nanoparticles (prepared according to nanoemulsion techniques) suitably comprise polystyrene or polymethylmethacrylate. Suitable block copolymers are styrene-α-methylstyrene copolymers, styrene-ethylene oxide copolymers, polyether lactones, polyester carbonates and polylactonides. Suitable hyperbranched polymers are hyperbranched polyesters, such as hyperbranched polycaprolactone, and polyethers, such as polyethylene oxide and polypropylene oxide. Another useful pore former is ethylene glycol-polycaprolactone, useful polymer blocks include polyvinylpyridine, hyperbranched polyvinylaromatic, polyacrylonitrile, polysiloxane, polycaprolactam , polyurethanes, polydienes (such as polybutadiene and polyisoprene), polyvinyl chloride, polyacetals, and amine-terminated alkylene oxides. Other useful thermoplastic materials include polyisoprene, polytetrahydrofuran, and polyethyloxazoline.

Hole forming :

The term "degradation" as used herein refers to the breaking of covalent bonds. This bond breaking can occur in various ways such as heterolysis and homolysis. Bond breaking does not have to be complete, ie not all breakable bonds have to be broken. Furthermore, some bonds may break faster than others in the breaking of bonds. For example, ester linkages are generally less stable than amide linkages and thus can be broken at a faster rate. Depending on the chemical composition of the degraded moiety, bond breaking also causes the resulting fragments to differ from each other.

In the pore-forming process of thermally degrading the porogen, thermal energy is applied to the porogen-containing material to substantially degrade or break down the porogen into its original components or monomers. The term "substantially degraded" as used herein preferably means that at least 80% by weight of the porogen degrades or decomposes. For the preferred thermoset compositions of formulas I and II above, porogens of the present invention having a degradation or decomposition temperature of about 350°C or above are particularly useful for such thermoset compositions having a Tg of about 400°C to 450°C. For the preferred polyacenaphthylene-based homopolymer or copolymer porogens, we found that the porogens degrade, decompose, or depolymerize into their original groups of acenaphthyl monomers and comonomers by using analytical techniques such as thermal desorption mass spectrometry. point.

Thermal energy is also applied to volatilize the substantially degraded or decomposed porogen from the thermosetting component matrix. Preferably the same thermal energy is used for the degradation and volatilization steps. As the amount of volatilized degraded porogen increases, the porosity of the resulting thermoset component increases. The preferred thermosetting components of Formulas I and II above have a Tg of about 400°C to 450°C, therefore, the substantially degraded porogens of the present invention have a volatilization temperature of about 280°C or higher, which is for the thermosetting components will be very useful.

Preferably the curing temperature for crosslinking the thermoset component will also substantially degrade the porogen and volatilize it from the thermoset matrix. Typical curing temperatures and conditions are described in the uses section below.

The resulting pores can be uniformly or randomly dispersed throughout the matrix. Preferably the pores are evenly dispersed throughout the matrix.

Alternatively, other methods or conditions in which the porogen is at least partially removed without detriment to the thermoset component may also be used. The porogen is preferably substantially removed. Common methods of removal include, but are not limited to, exposure to radiation, such as, but not limited to, electromagnetic radiation such as ultraviolet, X-ray, laser, or infrared radiation; mechanical energy such as ultrasound or physical pressure; or particle radiation such as gamma rays, alpha particles, neutral beamlets or electron beams.

Uses :

The term "layer" as used herein includes films and coatings.

As used herein, the term "low dielectric constant polymer" refers to an organic, organometallic or inorganic polymer having a dielectric constant of about 3.0 or less. Low dielectric materials are typically produced as thin layers with a thickness of 100 to 25,000 Angstroms, but are available as thick films, bulks, cylinders, spheres, etc.

Combinations of thermosetting components, tackifiers, and porogens of the present invention can be used to lower the dielectric constant of materials. Preferably, the dielectric material has a dielectric constant k less than or equal to about 3.0, more preferably about 1.9 to 3.0. The dielectric material preferably has a glass transition temperature of at least about 350°C.

The layer of the combination of thermosetting component, adhesion promoter and porogen of the present invention can be formed by solution techniques such as spray coating, roll coating, dip coating, spin coating, flow coating or casting, preferably using spin coating in the field of microelectronics . The compositions of the invention are preferably dissolved in a solvent. Suitable solvents for these solutions of the compositions of the present invention include any suitably pure organic, organometallic or inorganic molecule or mixtures thereof which volatilize at a certain temperature. Suitable solvents include aprotic solvents: for example cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone and cyclooctanone; cyclic amides such as N-alkylpyrrolidones, wherein the alkyl group has 1 to 4 carbon atoms; and N - cyclohexylpyrrolidone and mixtures thereof. Various other organic solvents can be used as long as they facilitate the dissolution of the tackifier while effectively controlling the viscosity of the resulting solution (used as a coating solution). Various convenient measures such as stirring and/or heating can be used to assist dissolution. Other suitable solvents include methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, cyclomethicone, butyrolactone, gamma-butyrolactone, 2-heptanone, 3-ethoxypropionic acid Ethyl esters, polyethylene glycol [di]methyl ether, propylene glycol monomethyl ether acetate (PGMEA), and anisole, and hydrocarbon solvents such as 1,3,5-trimethylbenzene, xylene, toluene, and benzene. A preferred solvent is cyclohexanone. The layer thickness is generally about 0.1-15 microns. Dielectric interlayers used in microelectronics typically have a layer thickness of less than 2 microns.

The compositions of the present invention are useful in electronic devices, more particularly as interlayer dielectrics in interconnects associated with individual integrated circuit ("IC") blocks. The surface of an integrated circuit chip typically has multiple layers of the composition of the invention and multiple layers of metal conductors. Regions of the composition of the invention may also be included between discrete metal conductors or in regions of conductors in the same layer or level of integrated circuits.

In applying the polymers of the invention to various ICs, solutions of the compositions of the invention are applied to semiconductor wafers by conventional wet coating methods such as spin coating, other well known coating techniques such as spray coating, flow coating Or dip coating can also be used in specific examples. For example, a cyclohexanone solution of the composition of the present invention is spin-coated onto a substrate on which a conductive element is mounted, and then the coated substrate is subjected to heat treatment. Following a strict clean-handling protocol to prevent trace metal contamination in any conventional device with a non-metallic lining, an exemplary formulation of the composition of the invention dissolves the composition of the invention in a ring under ambient conditions. Prepared in hexanone solvent. The resulting solution preferably comprises about 70-98% by weight of the thermosetting component, about 2-30% by weight of the tackifier, about 5-25% by weight of the porogen, and about 75-95% by weight of the solvent, based on the total solution weight. .

The uses of the present invention are exemplified as follows. The application of the composition of the invention to form a layer on a planar or partial surface or substrate can be achieved by any conventional means, preferably said means being a spin-on applicator, since the composition used has a controlled viscosity suitable for such an applicator . The solvent can be evaporated by any suitable method, such as simple air drying in spin coating, exposure to ambient environment or heating to 350° C. on a hot plate to evaporate the solvent. The substrate has at least one layer of the preferred combination of thermosetting component, adhesion promoter and porogen of the present invention.

Substrates contemplated for use herein may comprise substantially any desired solid material. In particular, suitable substrate layers include films, glass, ceramics, plastics, metals or coated metals or composite materials. In a preferred embodiment, the substrate comprises: a silicon or gallium arsenide die or wafer surface; a package surface, such as a copper, silver, nickel or gold plated leadframe; a copper surface, such as a circuit board or package connection wire, via wall or hardener interfaces (“copper” includes bare copper and its oxides); polymer-based package or board interfaces such as polyimide-based flex packages, lead or other metal alloy solder ball surfaces, glass, and polymers. Useful substrates include silicon, silicon nitride, silicon oxide, silicon oxycarbide, silicon dioxide, silicon carbide, silicon oxynitride, titanium nitride, tantalum nitride, tungsten nitride, aluminum, copper, tantalum, silicone Oxane, silicone glass and fluorinated silicon glass. In other embodiments, the substrate includes common materials found in the packaging and circuit board industries, such as silicon, copper, glass and polymer industries. The compositions of the present invention are also useful as dielectric matrix materials for microchips, multichip modules, laminated wiring boards or printed wiring boards. The surface of a circuit board formed from the composition of the present invention has installed thereon a pattern for the various electrical conductor circuits. Circuit boards can include various reinforcement materials such as non-conductive woven fibers or glass wool. These circuit boards can be single-sided or double-sided.

Layers prepared from the compositions of the invention have low dielectric constants, high thermal stability, high mechanical strength and excellent adhesion to electronic substrate surfaces. Because of the molecularly dispersed distribution of adhesion promoters, these layers have demonstrated excellent adhesion to all attachment surfaces, _including underlying substrates, overlays or masking layers such as _SiO2 and _Si3N4 overlays. The application of these layers eliminates the need for additional processing steps using at least one primer coat to adhere the film to the substrate and/or covering surface.

After application of the composition of the present invention to the electro-topographic substrate, the coated structure is subjected to a bake and cure heat treatment at increasing temperatures ranging from about 50°C up to about 450°C to polymerize the coating. The curing temperature is at least about 300°C because low temperatures do not complete the reaction. It is generally preferred that curing be carried out at a temperature of from about 375°C to about 425°C. Curing can be carried out in a conventional curing chamber (such as an electric furnace, hot plate, etc.), and is usually carried out in an inert (non-oxidizing) atmosphere (nitrogen) inside the curing chamber. In addition to oven or hot plate curing, compositions of the present invention as described in commonly assigned patent publication PCT/US96/08678 and U.S. Patent Nos. Curing can also be effected by exposure to ultraviolet radiation, microwave radiation or electron beam radiation. In the practice of the present invention, any non-oxidizing or reducing atmosphere (such as processing gases such as argon, helium, hydrogen, and nitrogen) may be employed so long as these atmospheres are effective in curing the tackifier-modified thermosetting components of the present invention to obtain low-k dielectric layer.

It is hypothesized that the processing method of the low dielectric constant composition of the present invention will result in a homogeneous solution of the thermosetting component, tackifier, and porogen, but without being limited by such speculation. The preferred silane adhesion promoters will advantageously serve multiple functions in the low dielectric constant composition. For example, processing of the compositions of the present invention allows the preferred polycarbosilane adhesion promoter to interact with both the porogen and the unsaturated structure of the thermoset component. It is believed that the silane moieties of the preferred polycarbosilane adhesion promoters interact with the porogen and thermoset components. It is speculated that the polycarbosilane acts as a surfactant or emulsifier to uniformly disperse the porogen in the thermosetting component of the low dielectric composition. This is important in order to obtain a composition that produces a homogeneous film (or layer in which pores of very small size are uniformly dispersed). The silane moiety of the polycarbosilane also reacts with the surface of the substrate thereby creating an adhesive interface for chemical bonding of the primary thermosetting monomer precursor with silylene/silyl groups throughout the composition, Acts as a bonding source to anchor and stabilize any chemically bonded interfacial surfaces. The interaction between the different components and the reaction of the silane moieties can also occur during formulation and handling prior to layer formation. As already indicated, the dispersion of the silane functionality with the porogen and thermosetting components throughout the composition results in a uniform porosity of the resulting layer. The dispersion of the silane functional groups also results in excellent adhesion of the reactive groups and the layer to the underlying substrate surface as well as to overlying surface structures such as skin or masking layers. Important to the materials discovered in the present invention is the discovery that the preferred polycarbosilane adhesion promoters of formula XXXVII have active hydrogen substituted silicon on the polycarbosilane backbone structure. This feature of polycarbosilane allows it to: (1) uniformly mix with the pore forming agent to form a uniform composition; (2) react with the thermosetting component; (3) uniformly mix and disperse the pore forming agent in the thermosetting component, A homogeneous composition is obtained, resulting in a final porous layer with uniformly dispersed pores; and (4) resulting in a polycarbosilane-modified thermoset composition with enhanced viscosity.

As previously mentioned, the adhesion promoter modified thermosetting component (a) coating of the present invention can be interlayered and overlaid by other coatings such as other dielectric ( _SiO2 ) coatings, SiO ₂ modified ceramic oxide layer, silicon-containing coating, carbon-silicon coating, silicon-nitrogen coating, silicon-nitrogen-carbon coating, diamond-like carbon coating, titanium nitride coating, nitrogen Tantalum oxide coatings, tungsten nitride coatings, aluminum coatings, copper coatings, tantalum coatings, organosiloxane coatings, silicone glass coatings, and fluorinated silica glass coatings. Such multilayer coatings are described in US Patent No. 4,973,526 (herein incorporated by reference). At the same time, as fully demonstrated, the polycarbosilane-modified thermosetting component (a) of the present invention prepared in the process of the present invention is easy to form an interlayer interlayer between adjacent conductive lines on assembled electronic or semiconductor substrates. electrical layer.

The dielectric constant of the layer of the invention is preferably below 2.7, preferably below 2.5, more preferably below 2.2 and most preferably below 2.0.

For integrated circuit production, the films of the invention can be used in dual damascene (eg copper) processing and base metal (eg aluminum or aluminum/tungsten) processing. The compositions of the present invention can be used as etchstops, hardmasks, airline or passivation coatings for encapsulation of entire wafers. As noted by Michael E. Thomas in "Spin-On Stacked Films for Low koff Dielectrics", Solid State Technology (July 2001), which is hereby incorporated by reference in its entirety, the compositions of the present invention can be used in all suitable Used in press-spin laminated films as required. The layers may be laminated with other layers comprising organosiloxanes as described in commonly assigned US Patent 6,143,855 and pending US Serial No. 10/078919 (February 19, 2002); ^HOSP® products commercially available from Honeywell International Inc.; microporous silica, as described in commonly assigned U.S. Patent 6,372,666; commercially available ^NANOGLASS® E products from Honeywell International Inc.; organosilsesquioxanes, as described in commonly assigned U.S. Patent 6,372,666; as described in assigned WO 01/29052; and fluorosilsesquioxanes as described in commonly assigned WO 01/29141 (hereby incorporated by reference in its entirety).

Analytical test method :

¹ H NMR : A 2-5 mg sample of the starting material to be analyzed is placed in an NMR sample tube. Add approximately 0.7 mL of deuterated chloroform. Shake the mixture by hand to dissolve the ingredients. Samples were then analyzed by Varian 400MHz NMR.

Gel Permeation Chromatography (GPC) : Separation was performed using a Waters 2690 separation module with a Waters 996 diode array and a Waters 410 differential refractive index detector. Using chloroform at a flow rate of 1ml/min as the mobile phase, two PLgel 3μm Mixed-E 300×7.5mm columns were used for separation. A solution at a concentration of approximately 1 mg/ml was injected in a volume of 25 μl in duplicate. Good reproducibility was observed.

The columns were calibrated with various relatively monodisperse polystyrene standards ranging in molecular weight from 20,000 to 500. Using lower molecular weight standards, 9 different components could be resolved into 9 styrenes, ie, butyl-terminated styrene monomers to oligomers. The logarithm of the peak molecular weight of the standard corresponds to a third order polynomial of the elution time. The instrument broadening effect was evaluated by the ratio of half peak width to the average elution time of toluene.

Preparations 1 and 2 described below had a maximum absorbance at about 2 g 4 nm. The spectrum with absorption wavelength below about 300nm has a similar peak shape. Results shown here are absorbance at 254 nm. The peak was determined by the known molecular weight of the polystyrene eluting at the same time. These values should not be interpreted as the molecular weight of the oligomers from which 1 and 2 were made. The molecular weight of higher oligomers, trimers, dimers, oligomers and incomplete oligomers eluted sequentially over time can be measured.

The peaks for each component were broader than that observed for monodisperse material. The width is analyzed by half width (in minutes). In order to roughly illustrate the broadening effect of the instrument, the calculation is carried out according to the following formula:

Width _Correction = [Width _Observation2 - ^Width _Instrument2 ^{] 1/2}

where the width _instrument is the observed width of toluene corrected by the ratio of peak elution time to that of toluene. The peak width is converted to the molecular weight width through the calibration curve and compared with the peak molecular weight width. Since the molecular weight of styrene oligomers is proportional to the square of their size, the relative molecular weight breadth divided by 2 can be converted to the corresponding oligomer size breadth. This method can be used to account for differences in the molecular configuration of two substances.

¹³ C NMR : Initial measurements of T ₁ showed a maximum of 4 seconds, so set the cycle time as such to obtain quantitative results. All samples were dissolved in CDCl ₃ and scanned 4000 times cumulatively. The shifts assigned to the -C, -CH, _-CH2 , and _-CH3 groups, respectively, were determined by DEPT. DEPT clearly identified 41 ppm as _-CH2 , the group at position 3 adjacent to the unbranched (arm) carbon on the _C10 adamantane, and 30 ppm as -CH, the group at the unsubstituted position. The _-CH of the C ₁₀ adamantane adjacent to the linking branch occurs at 46–48 ppm. Similarly, the quaternary carbon at 35 ppm and _-CH3 at 31.5 ppm can be attributed to tert-butyl. In the region of aromatic character, the cluster of peaks between 120 and 123.5 clearly indicates unprotonated aromatics. Based on the chemical shifts, we assigned these carbons as bromoaryl carbons. Quaternary aromatics located in the 145-155 ppm range are considered to be aromatic ring carbons attached to aliphatic groups, which is the case for C ₁₀ adamantanes. There are also peaks at about 14, 23, 29 and 31.5 ppm in some spectra. These peaks are due to the heptane used to wash the samples. The relative amount of heptane varied widely between samples. We did not quantify the heptane as this is not critical to the final result.

NMR conditions:

Acquisition of high-resolution ¹³ C NMR spectra on a Varian Unity Inova 400

^13C frequency: 100.572MHz

· Gated ¹ H decoupling, using WALTZ modulation

Spectral width: 25kHz

• π/2 pulse of ¹³ C - 13 μs.

·Cycle time: 20 seconds

·#data point: 100032, 2 seconds to fetch data

0 to 131072 points, FT

1Hz exponential smoothing method

Liquid Chromatography-Mass Spectrometry (LC-MS) : Analysis was performed on a Finnigan/MAT TSQ7000 three-section quadrupole mass spectrometer system with an atmospheric pressure ionization (API) interface device using a Hewlett-Packard Series 1050 HPLC system as the chromatographic injector . For time-intensity chromatograms, both mass spec ion current and variable single-wavelength UV data are available.

Chromatography was performed on a Phenomenex Luna 5 micron phenyl-hexyl column (250 x 4.6 mm). The automatic injection sample is generally 5-20 microliters of tetrahydrofuran or non-tetrahydrofuran concentrated solution. A preferred analytical concentrated sample solution is prepared by dissolving approximately 5 mg of solid sample per mL of tetrahydrofuran and injecting 10 microliters. The mobile phase passed through the column was acetonitrile/water at a flow rate of 1.0 mL/min, starting with 70/30 for 1 minute and then ramping up to 100% acetonitrile at 10 minutes and continuing through 40 minutes.

In separation experiments, atmospheric pressure chemical ionization (APCI) mass spectrometry can simultaneously record cation ionization and anion ionization. For these final products, cationic APCI provides more information on the molecular structure of protonated pseudomolecular ions (including adducts with acetonitrile matrix). The APCI corona discharge is 5 microamperes, the cation ionization voltage is about 5 kV and the anion ionization voltage is about 4 kV. Keep the heated capillary line at 200 °C and the vaporization chamber at 400 °C. The ion detection system after quadrupole mass analysis was set at a switching dynode of 15kV and an electron multiplication voltage of 1500V. Mass spectra are typically recorded from about m/z 50 to 2000 a.m.u at 1.0 sec/scan for anion ionization and from about m/z 150 a.m.u for cation ionization. In separation cation experiments, the mass range was scanned to 2000 a.m.u in low mass adjustment/calibration mode and to 4000 a.m.u in high mass adjustment/calibration mode.

Differential Scanning Calorimetry (DSC) : The DSC measurement is carried out with a TAInstrumert 2920 differential scanning calorimeter connected to a controller and related software. The analysis was performed using a standard DSC chamber with a temperature range of 250°C - 725°C (inert atmosphere: 50ml/min nitrogen). Use liquid nitrogen as the cooling gas source. Small samples (10-12 mg) were carefully weighed using a Mettler Toledo analytical balance with an accuracy of ±0.0001 gram and placed in an automated DSC aluminum sample pan (Cat #990999-901). Samples were sealed by covering the pan with a lid that had been perforated in the middle to allow for venting. The sample was heated from 0°C to 450°C at a rate of 100°C/min (cycle 1) in nitrogen and then cooled to 0°C at a rate of 100°C/min. A second cycle was immediately performed, heating from 0°C to 450°C at a rate of 100°C/min (repeated cycle 1). The crosslinking temperature is determined by the first cycle.

FTIR analysis: FTIR spectra were acquired in transmission mode using a Nicolet Magna 550 FTIR spectrophotometer. Substrate background spectra were obtained from uncoated substrates. Thin film spectra were obtained with the substrate as the background. Then the thin film spectrum is analyzed for changes in peak position and intensity.

Dielectric constant: The dielectric constant is determined by coating a thin aluminum film on the cured layer, then performing a capacitance-voltage measurement at 1 MHz and calculating the k value from the layer thickness.

Glass Transition Temperature (Tg) : The glass transition temperature of a film is determined by measuring the film stress as a function of temperature. Film stress was measured with a KLA 3220 Flexus. Before thin film measurements, the uncoated wafers were annealed at 500°C for 60 min to avoid any errors due to stress relaxation of the wafer itself. The wafer is then coated with the material to be tested and processed according to all necessary processing steps. The wafer is then placed in a pressure gauge and the wafer bow is measured as a function of temperature. Based on known wafer thickness and film thickness, the instrument calculates a graph of stress versus temperature. The results are displayed graphically. To determine the Tg value, draw a horizontal tangent (0 slope value on the stress versus temperature graph). The Tg value is the intersection of the graph and the horizontal tangent.

It should be noted if the Tg value is determined after the first temperature cycle or the subsequent cycle using the highest temperature, since the method of measurement itself affects the Tg.

Isothermal Gravimetric Analysis (ITGA) Weight Loss: The total weight loss was determined by a TA Instruments 2950 Thermogravimetric Analyzer (TGA) used in connection with a TA Instruments Thermal Analysis Controller and associated software. A Platinel II thermocouple and a standard furnace with a temperature range of 25°C to 1000°C and a heating rate of 0.1°C to 100°C/min were used. A small sample (7-12 mg) was weighed with a TGA balance (resolution: 0.1 g; accuracy: to ±0.1%) and heated on a platinum pan. The sample was heated under nitrogen at a sweep rate of 100 ml/min (60 ml/min to the furnace and 40 ml/min to the balance). The sample was equilibrated under nitrogen at 20°C for 20 minutes, then the temperature was raised to 200°C at a rate of 10°C/min and maintained at 200°C for 10 minutes. The temperature was then raised to 425°C at a rate of 10°C/min and maintained at 425°C for 4 hours. Calculate the weight loss during 4 hours at 425°C.

Shrinkage : Film shrinkage is determined by measuring film thickness before and after processing. Shrinkage is expressed as a percentage of original film thickness. The shrinkage is positive if the film thickness decreases. The actual thickness is generally obtained by optical measurement with a JAWollam M-88 spectroscopic ellipsometer. The best-fit values of Psi and δ were calculated using the Cauchy model (for details on ellipsometry, see, eg, "Spectroscopic Ellipsometry and Reflectometry" by HG Thomkins and William A. McGahan, John Wiley and Sons, Inc., 1999).

Refractive Index : Refractive index was determined simultaneously with thickness measurements by a JA Woollam M-88 Spectroscopic Ellipsometer. Best-fit values of Psi and δ were calculated using the Cauchy model. Unless otherwise stated, the reported refractive index wavelength is 633 nm (for details on ellipsometry see, eg, "Spectroscopic Ellipsometry and Reflectometry" by HG Thomkins and William A. McGahan, John Wiley and Sons, Inc., 1999).

Modulus and Hardness : Modulus and hardness were determined by instrumented indentation testing using a MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, TN). Specifically, a continuous stiffness measurement method is used, which ensures accurate, continuous determination of modulus and hardness, rather than discrete values determined from unloading curves. The system is calibrated with fused silica gel with a nominal modulus of 72+-3.5GPa. The obtained fused silica gel has an average modulus between 500 and 1000 nm indentation depth. For films, modulus and hardness values can be obtained from the minimum of the modulus versus depth curve, which is typically 5 to 15% of the film thickness.

Tape test : The tape test is carried out according to the method of ASTM D3359-95. Draw a grid on the dielectric layer as follows. Tape experiments were performed on grids taped as follows: (1) A piece of adhesive tape (preferably Scotch brand #3m600-1/2 x 1296) was placed over the layer of the invention and pressed down for good contact; And (2) the tape is then quickly and smoothly pulled up 180° from the surface of the layer. The samples were considered pass if the layers on the wafer remained intact, and failed if some or all of the film was pulled up with the tape.

Bolt Pull Test : Epoxy-coated bolts were bolted to the surface of a wafer with a layer of the invention. A ceramic support plate was placed on the backside of the wafer to prevent substrate bowing and to avoid excessive stress concentrations at the stud edges. The bolts are then pulled through the test equipment in a direction perpendicular to the wafer surface using standard pulling procedure procedures. Record the point where the applied stress disappears and the location of the interface.

Solvent Compatibility : Solvent compatibility was determined by measuring film thickness, refractive index, FTIR spectra, and dielectric constant before and after solvent treatment. For compatible solvents, no significant changes should be observed.

Average pore size tester : The N ₂ isotherm of the porous sample is tested on the Micromeretics ASAP2000 automatic nitrogen isothermal adsorption tester, using UHP (Ultra High Purity Industrial Gas) N ₂ , the sample is loaded into a liquid nitrogen bath placed at 77°K in the sample tube.

To prepare the samples, the material was first deposited on a silicon wafer using standard processing conditions. Three wafers with a film thickness of approximately 6000 Å were prepared for each sample. The film was then scraped off the wafer with a thin blade to obtain a powder sample. These powder samples were pre-dried in an oven at 180°C, then weighed, and the powder was carefully poured into 10mm inner diameter sample tubes, followed by degassing at 180°C, 0.01 Torr for >3 hours.

Adsorption and desorption of nitrogen attachment were then measured automatically, with an equilibration interval of 5 s unless analysis indicated that a longer time was required. The time required to measure the isotherm curve is related to the mass of the sample, the pore volume of the sample, the number of data points tested, the equilibration interval, and the P/Po tolerance (P is the actual pressure of the sample in the sample tube, Po is the ambient pressure outside the instrument ) is proportional to. The instrument measures the nitrogen isotherm curve and draws the nitrogen removal-P/Po curve.

Using the BET theory (S.Brunauer, PH Emmett, E.Teller disclosed in J.AM.Chem.Soc., 60,309-319 (1938) used Brunauer, Emmett, Teller method in solid surface multilayer gas adsorption ), the linear portion of R ² >0.9999 was fitted using the BET equation, and the apparent BET surface area was calculated from the low P/Po region of the nitrogen adsorption isotherm.

The pore volume was calculated from the nitrogen adsorption volume at a relative pressure value of P/Po typically ~0.95 (in the flat region of the isotherm, at which point condensation has been completed), assuming that at this P/Po the density of the adsorbed nitrogen is the same as Liquid nitrogen is the same, and all holes are filled with condensed nitrogen.

Using the BJH theory (E.P.Barret, L.G.Joyner and P.P.Halenda; J.AM.Chem.Soc, 73, 373-380 (1951), using the Kelvin equation, the pore size distribution is calculated from the nitrogen isotherm), the adsorption line of the nitrogen isotherm Calculate the pore size distribution. This approach uses the Kelvin equation, which describes the suppression dependence of curvature on vapor pressure, and the Halsey equation, which describes the nitrogen monolayer thickness as a function of P/Po, and relates the volume of condensed nitrogen to P/Po The relationship of is converted to pore volume in a specific pore size range.

The average columnar pore diameter D is the diameter of the column, and its apparent BET surface area Sa (m ² /g) and pore volume Vp (cc/g) are the same as those of the sample, so D (nm) = 4000Vp/Sa.

Thermal desorption mass spectrometry : Thermal desorption mass spectrometry (TDMS) measures the thermal stability of materials by heat-treating the material and analyzing the desorbed substances.

TDMS tests were performed in a high vacuum system equipped with a wafer heater and a mass spectrometer in close proximity to the front surface of the wafer. Heat lamps are used to heat the backside of the wafer. The die temperature is measured by a thermocouple that is in contact with the front surface of the die. Heater lamps and thermocouples are connected to a programmable temperature controller that performs several temperature ramp and soak cycles. The mass spectrometer used was Hiden Analytical HAL IV RCRGA 301. Both the mass spectrometer and the temperature controller are connected with a computer, and the computer reads out and records the mass spectrometer and corresponding temperature signals at different times.

For TDMS analysis, the material is first deposited as a thin film on an 8-inch wafer using standard processing methods. Then place the wafer in the TDMS vacuum system, and use a pump to evacuate the system to a pressure lower than 1e-7 Torr. Start the temperature ramp using the temperature controller. Use a computer to record the temperature and mass spectrometer signal. For a typical ramp rate of 10°C/min, a full mass scan and a temperature measurement are recorded every 20 seconds. The mass spectrum at a given time and the temperature at a given time can be analyzed after the test is completed.

Example

Contrast A

We measured the dielectric constant of a composition similar to Example 5 of our International Patent Publication WO 01/78110 and found it to be 2.7.

Contrast B:

Although WO 00/31183 states that polybutadiene can be used as a porogen, we have tried to use polybutadiene as a porogen in a method similar to our pending U.S. patent application serial number filed on January 15, 2002. In the composition of the inventive examples 4-7 of 60/350187, it was found that regardless of the molecular weight of the polybutadiene, the refractive index of the composition does not change (as shown in Table 6 below), therefore, it is impossible to obtain a low dielectric constant s material.

Table 6 Pore former Pore former% Tackifier% solvent Refractive index Polybutadiene (Mw1800) 35 6.7 Xylene 1.629 Phenyl-terminated polybutadiene (Mw1000) 35 6.7 Cyclohexanone 1.623 Indene-benzofuran copolymer (Mw735) 35 6.7 Cyclohexanone 1.602 Indene-benzofuran copolymer (Mw735) 35 6.7 Xylene 1.607 Indene-benzofuran copolymer (Mw1090) 35 6.7 Cyclohexanone 1.600 Indene-benzofuran copolymer (Mw1090) 35 6.7 Xylene 1.595

preparation:

Preparation 1 - Preparation of thermosetting component (a)

(referred to here as "P1")

Step (a): Preparation of 1,3,5,7-tetrakis(3′/4′-bromophenyl)C ₁₀ adamantane (as shown in Figure 1A), 1,3/4-bis[1′,3 ',5'-tris(3"/4"-bromophenyl)C ₁₀ adamantan-7'-yl]benzene (as shown in Figure 1C) and at least 1,3-bis{3'/4'-[ 1″, 3″, 5″-tris(3/4-bromophenyl)C ₁₀ adamantane-7″-yl]phenyl}-5,7-bis-(3″″/4″″- Bromophenyl) C ₁₀ adamantane (as shown in Figure 1C) mixture (collectively referred to as "P1 step (a) product").

C ₁₀ adamantane (200 g), bromobenzene (1550 mL) and aluminum trichloride (50 g) were added to the first reactor. The reaction mixture was heated to 40°C with a constant temperature water bath. Tert-butyl bromide (1206 g) was slowly added to the reaction mixture over 4-6 hours. The reaction mixture was stirred overnight at 40 °C.

1000 ml of aqueous hydrogen chloride solution (5% by weight) was added to the second reactor. The reactants in the first reactor were gradually poured into the second reactor while maintaining the temperature of the reaction mixture at 25-35°C by an external ice bath. The organic phase (dark brown, bottom layer) was separated and washed with water (1000 mL). About 1700 ml of organic phase remained.

20.4 liters of petroleum ether (mainly isooctane with a boiling range of 80°C-110°C) was added to the third reactor. The reactants in the second reactor were slowly poured into the third reactor over 1 hour. The resulting mixture was stirred for at least 1 hour. The precipitate was filtered and the filter cake was washed twice with 300 ml of the aforementioned petroleum ether. The washed filter cake was dried overnight at a pressure of 40 mbar at 45°C. The dry weight of the product obtained in the P1 step (a) was 407 grams. This reaction is shown in Figures 1A to 1C below. Figure 1A shows the resulting monomer. Figure 1B shows the general formula of the resulting dimers and higher order products and Figure 1C shows the specific dimers and trimers that are obtained, which are included within the structure of Figure 1B.

Products were identified using analytical techniques including LC-MS, ^NMR13C and GPC. LC-MS indicated that the product was a complex mixture of star compound monomers and oligomers with a C ₁₀ adamantane core. The determined structures are listed in the table below (Ad = C ₁₀ adamantane; Ph = C ₆ H ₅ ; Br = bromine; t-Bu = -C(CH ₃ ) ₃ ):

HPLC-MS analysis of IE1 step (a) product

NMR ¹³ C analyzes the attribution of the following peaks: ¹³ C NMR peak position, ppm structure 153.6, 151.8, 151.1, 148.3, 147.6 Bonded to the quaternary carbon of _C10 adamantane 136.0, 134.5, 134.2, 133.1, 131.6, 131.1, 130.2, 130.0, 129.6, 129.3, 128.5, 126.9, 123.8 Aromatic CH 123.1, 123.0, 122.9, 122.6, 121.4, 121.1, 120.3 Aromatic C-Br 47.7 Three CH ₂ of trisubstituted C ₁₀ adamantane 46.8 CH ₂ of tetrasubstituted C ₁₀ adamantane 41.0 _CH2 of a _C10 adamantane adjacent to an unsubstituted _C10 adamantane position 39.3, 39.0, 38.9, 38.4, 38.1 Quaternary (aliphatic) carbon of C ₁₀ adamantane 35.2 quaternary (aliphatic) carbon of tert-butyl 31.4 tert-butyl CH ₃ 30 CH of trisubstituted C ₁₀ adamantane

GPC analysis results:

-1,3,5,7-Tetrakis(3'/4'-bromophenyl) C ₁₀ adamantane (as shown in Figure 3A) has a peak molecular weight of about 360;

-1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl) C ₁₀ adamantane-7′-yl]benzene (as shown in Figure 3C) The molecular weight is about 620;

-1,3-bis{3′/4′-[1″,3″,5″-tris(3/4-bromophenyl)C ₁₀ adamantane-7″-yl]phenyl}-5 , the peak molecular weight of 7-bis(3″″/4″″-bromophenyl) C ₁₀ adamantane (as shown in FIG. 3C ) is about 900 (shoulder peak).

Step (b): Preparation of 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]C ₁₀ adamantane (as shown in Figure 1D), 1,3/4-bis{ 1′,3′ 5′-tris[3″/4″-(phenylethynyl)phenyl]C ₁₀ adamantane 7′-yl}benzene (as shown in Figure 1F) and at least 1,3-bis{3 ′/4′-[1″, 3″, 5″-tri[3/4-(phenylethynyl)phenyl]C ₁₀ adamantane-7″-yl]phenyl}-5,7-bis A mixture of [3""/4""-(phenylethynyl)phenyl]C ₁₀ adamantanes (as shown in Figure 1F) (collectively referred to as "P1 step (b) products").

Under nitrogen protection, toluene (1500 ml), triethylamine (4000 ml) and the product prepared in step (a) of P1 above (1000 g, dry weight) were added to the first reactor. The mixture was heated to 80°C, bis-(triphenylphosphine)palladium(II) dichloride (ie [Ph ₃ P] ₂ PdCl ₂ ) (7.5 g) and triphenylphosphine (ie [Ph ₃ P ]) (15 grams). After 10 minutes, copper (I) iodide (7.5 g) was added.

A solution of phenylacetylene (750 grams) was added to the first reactor over 3 hours. The reaction mixture was stirred at 80°C for 12 hours to ensure completion of the reaction. Toluene (4750 mL) was added. The solvent was distilled off under reduced pressure at the highest internal vessel temperature and the reaction mixture was cooled to about 50°C. Triethylammonium bromide (about 1600 mL) was filtered off. The filter cake was washed 3 times with 500 ml of toluene. The organic phase was washed with 1750 ml of HCl (10% by weight) and then with water (2000 ml).

Water (1000 mL), ethylenediaminetetraacetic acid (EDTA) (100 g) and dimethylglyoxime (20 g) were added to the washed organic phase. About 150 mL of _MH4OH (25% by weight) solution was added to bring the pH to 9. The reaction mixture was stirred for 1 hour. The organic phase was separated and washed with water (1000 mL). Azeotropic drying was performed through a Dean-Stark trap until the moisture ceased to evaporate. A filter dolomite (100 g) (trade name Tonsil) was added. The mixture was heated at 100°C for 30 minutes. The dolomite was filtered off with a fine filter cloth and the residue was washed with toluene (200 ml). Silica (100 g) was added. The reaction mixture was stirred for 30 minutes. The silica was filtered off with a fine-mesh filter cloth and the residue was washed with toluene (200 ml). 2500 ml of ammonia solution (20% by weight) and 12.5 g of N-acetylcysteine were added. The phases were separated. The organic phase was washed with 1000 ml of HCl (10% by weight) and then twice with 1000 ml of water. Toluene was distilled off under reduced pressure at a pressure of about 120 mbar. The internal temperature of the reactor did not exceed about 70°C. The residue was a dark brown viscous oil (1500-1700 mL). To the hot reaction in the reactor was added isobutyl acetate (2500 mL), resulting in a dark brown solution (4250 mL).

17000 ml of petroleum ether (mainly isooctane with a boiling range of 80°C-110°C) was added to the second reactor. The contents of the first reactor were added to the second reactor over 1 hour and stirred overnight. The precipitate was filtered and washed 4 times with 500 ml of the aforementioned petroleum ether. The product was dried under reduced pressure at 45°C for 4 hours and at 80°C for 5 hours. P1 step (B) yields 850-900 grams of product. This reaction is shown in Figures 1D to 1F below. Figure 1D shows the resulting monomer. Figure IE shows the general formulas of the resulting dimers and higher order products, while Figure IF shows the specific dimers and trimers that are obtained, included in the structure of Figure IF.

Products were identified using analytical techniques including LC-MS, ^NMR1H , ^NMR13C , GPC and FTIR.

LC-MS analysis indicated that the product was a complex mixture of star compound monomers and oligomers with a C ₁₀ adamantane core. The determined structures are listed in the table below (Ad = clathrate C ₁₀ adamantane; T is tolanyl-PhC≡CC ₆ H ₄ -; t-Bu = -C(CH ₃ ) ₃ ):

# M+ peak Inferred structure 1 ^a 664 AdT ₃ H ^2a 840 AdT ₄ ^3a 720 Ad(H)T ₃ (t-Bu) 4 ^{a, b} 896 _AdT4 (t-Bu) 5 ^{a, b} 1326 Ad ₂ T ₆ 6a ^,b 1402 Ad ₂ T ₆ (C ₆ H ₄ )

^a All of these general structures were observed for analogs with MW ± 100 a.u. (plus or minus PhC≡C-group)

^b These structures are all observed analogues without the tolanyl branch (-176a.u.)

¹ H NMR identified aromatic protons (6.9-8 ppm, 2.80±0.2H) and caged _C10 adamantane protons (1.7-2.7 ppm, 1±0.2H).

¹³ C NMR analyzes the attribution of the following peaks: 13CNMR peak position, ppm structure 151.3, 151, 150, 149.9, 149.8, 149.3, 149.2 Connect the quaternary carbon on the C ₁₀ adamantane ring 132-131, 128.5, 125.3, 125.2 CH aromatic carbon 129.6-129.1 Aromatic ring carbon 123.7-122.9, 121.8, 121.1, 120.9 quaternary carbon attached to acetylene 93.6 quaternary acetylene carbon (on disubstituted ring) 90.7, 90.3, 90.1, 89.7, 89.5, 89.4, 89.1, 88.8, 88.7 quaternary acetylene carbon 47.5, 46.7 _CH2 of tetrasubstituted _C10 adamantane 47.1 _CH3 of tetrasubstituted _C10 adamantane 41 _CH2 of trisubstituted _C10 adamantane 39.6 _CH3 of trisubstituted _C10 adamantane 39.5, 39.2-39.0, 38.6, 38.2, 35 Quaternary carbon of tetrasubstituted C ₁₀ adamantane 32 CH ₃ of the tert-butyl group on the aromatic ring 30 CH of trisubstituted C ₁₀ adamantane

GPC analysis results:

-1,3,5,7-Tetrakis[3'/4'-(phenylethynyl)phenyl]C ₁₀ adamantane (as shown in Figure 3D) has a peak molecular weight of about 744;

-1,3/4-bis{1′,3′,5′-tri[3″/4″-(phenylethynyl)phenyl]C ₁₀ adamantane-7′-yl}benzene (as shown in Figure 3F Shown) the peak molecular weight is about 1300;

-1,3-bis-{3′/4′-[1″,3″,5″-tri[3/4-(phenylethynyl)phenyl]C ₁₀ adamantane-7″-yl] The peak molecular weight of phenyl}-5,7-bis(3″″/4″″-(phenylethynyl)phenyl]C ₁₀ adamantane (shown in FIG. 3F ) is about 1680 (shoulder peak).

According to the GPC results, the ratio of monomers and small molecules to oligomers was 50±5%.

FTIR results are as follows: Peak position cm ^-1 (peak intensity) structure 3050 (weak) Aromatic CH 2930 (weak) Aliphatic CH on _C10 adamantane 2200 (very weak) Acetylene 1600 (very strong) Aromatic C=C 1500(Strong) 1450 (medium) 1350 (medium)

Preparation 2 - Preparation of thermosetting components

(referred to here as "P2")

Step (a): Preparation of 1,3,5,7-tetrakis(3′/4′-bromophenyl)C ₁₀ adamantane (as shown in Figure 1A), 1,3/4-bis[1′,3 ',5'-tris(3"/4"-bromophenyl)C ₁₀ adamantan-7'-yl]benzene (as shown in Figure 1C) and at least 1,3-bis{3'/4'-[ 1″, 3″, 5″-tris(3/4-bromophenyl)C ₁₀ adamantane-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromo phenyl) C ₁₀ adamantanes (as shown in Figure 1C) (collectively referred to as "P2 step (a) products").

1,4-Dibromobenzene (587.4 grams) and aluminum trichloride (27.7 grams) were charged to the first reactor. The reaction mixture was heated to 90°C by means of a constant temperature water bath and maintained at this temperature without stirring for 1 hour, and then stirred for another 1 hour. The reaction mixture was cooled to 50 °C. C ₁₀ adamantane (113.1 g) was added to the cooled reaction mixture. Tert-butylbromobenzene (796.3 g) was added to the reaction mixture over 4 hours. The reaction mixture was stirred for an additional 12 hours.

HCl solution (566 mL, 10% by weight in water) was added to the second reactor. The contents of the first reactor were transferred to the second reactor at 50°C, maintaining the mixture temperature at 25-35°C by an external ice bath. The reactant was a light brown suspension. The lower organic phase was dark brown and was separated from the reaction mixture. The separated organic phase was washed with water (380 mL). After washing, about 800 ml of organic phase remained.

Heptane (5600 mL) was charged to the third reactor. The reactants in the second reactor were slowly added to the third reactor over 1 hour. The suspension was stirred for at least 4 hours and the precipitate was filtered off. The filter cake was washed twice with 300 ml of heptane. 526.9 g (wet weight) and 470.1 g (dry weight) of the product of P2 step (a) were obtained.

Products were identified using analytical techniques including LC-MS, ^NMR13C and GPC. LC-MS analysis results indicated that the product was a complex mixture of star compound monomers and oligomers with a C ₁₀ adamantane nucleus. The determined structures are listed in the table below (Ad = C ₁₀ adamantane; Ph = C ₆ H ₅ ; Br = bromine; t-Bu = -C(CH ₃ ) ₃ ):

HPLC-MS analysis of IE2 step (a) product

NMR ¹³ C analyzes the attribution of the following peaks: ¹³ C NMR peak position, ppm structure 153.6, 151.8, 151.1, 148.3, 147.6 Bonded to quaternary carbon of _C10 adamantane 136.0, 134.5, 134.2, 133.1, 131.6, 131.1, 130.2, 130.0, 129.6, 129.3, 128.5, 126.9, 123.8 Aromatic CH 123.1, 123.0, 122.9, 122.6, 121.4, 121.1, 120.3 Aromatic C-Br 47.7 Three CH ₂ of trisubstituted C ₁₀ adamantane 46.8 CH ₂ of tetrasubstituted C ₁₀ adamantane 41.0 _CH2 of a _C10 adamantane adjacent to an unsubstituted _C10 adamantane position 39.3, 39.0, 38.9, 38.4, 38.1 Quaternary (aliphatic) carbon of C ₁₀ adamantane 35.2 quaternary (aliphatic) carbon of tert-butyl 31.4 tert-butyl CH ₃ 30 CH of trisubstituted C ₁₀ adamantane

GPC analysis results:

-1,3,5,7-Tetrakis(3'/4'-bromophenyl) C ₁₀ adamantane (as shown in Figure 3A) has a peak molecular weight of about 360;

-1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl) C ₁₀ adamantane-7′-yl]benzene (as shown in Figure 3C) The molecular weight is about 570;

-1,3-bis(3′/4′-[1″,3″,5″-tris(3″/4-bromophenyl)C ₁₀ adamantane-7″-yl]phenyl}-5 , the peak molecular weight of 7-bis(3″″/4″″-bromophenyl) C ₁₀ adamantane (as shown in FIG. 3C ) is about 860 (shoulder peak).

Step (b): Preparation of 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]C ₁₀ adamantane (as shown in Figure 1D), 1,3/4-bis{ 1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]C ₁₀ adamantane-7′-yl}benzene (as shown in Figure 1F) and at least 1,3-bis {3′/4′-[1″, 3″, 5″-tri[3/4-(phenylethynyl)phenyl]C ₁₀ adamantane-7″-yl]phenyl}-5,7 - Mixtures of bis[3""/4""-(phenylethynyl)phenyl]C ₁₀ adamantanes (as shown in Figure 1F) (collectively referred to as "P2 step (b) products").

Under nitrogen protection, toluene (698 ml), triethylamine (1860 ml) and the product of P2 step (a) prepared above (465 g, dry weight) were added to the first reactor. The mixture was heated to 80°C. Palladium-triphenylphosphine complex (ie [Ph(PPh ₃ ) ₂ Cl ₂ ) (4.2 g) was added to the reaction mixture. After waiting 10 minutes, triphenylphosphine (ie, _PPh3 ) (8.4 g) was added to the reaction mixture. After waiting another 10 minutes, copper (I) iodide (4.2 g) was added to the reaction mixture.

Phenylacetylene solution (348.8 g) was added to the reaction mixture over 3 hours. The reaction mixture was stirred at 80 °C for 12 hours to ensure completion of the reaction. Toluene (2209 mL) was added to the reaction mixture, which was then distilled under reduced pressure at maximum reactor temperature. The reaction mixture was cooled to about 50°C, and triethylammonium bromide was filtered off. The filter cake was washed twice with 250 ml of toluene. The organic phase was washed with HCl (10 wt%) (500 mL) and water (500 mL).

Water (500 mL), EDTA (18.6 g) and dimethylglyoxime (3.7 g) were added to the organic phase. _NH4OH (25% by weight) (about 93 mL) was added to maintain pH=9. The reaction mixture was stirred for 1 hour. The organic phase is separated from the insoluble material and the palladium complex-containing emulsion. The separated organic phase was washed with water (500 mL). The washed organic phase was azeotropically dried through a Dean-Stark trap until the water evaporated. A filter agent dolomite (trade name Tonsil) (50 g) was added and the reaction mixture was heated at 100° C. for 30 minutes. The dolomite was filtered out with a filter cloth having fine pores, and the organic matter was washed with toluene (200 ml). Silica (50 g) was added and the reaction mixture was stirred for 30 minutes. Silica was filtered out with a filter cloth having fine pores, and the organic matter was washed with toluene (200 ml). Aqueous NH ₃ (20% by weight) (250 mL) and N-acetylcysteine (12.5 g) were added. The phases were separated. The organic phase was washed with HCl (10% by weight) (500 mL). The organic matter was washed twice with 500 ml of water. Toluene was distilled off under reduced pressure at a pressure of about 120 mbar. The reactor temperature does not exceed 70°C. A dark brown viscous oil (ca. 500-700 mL) remained. To the hot mass in the reactor was added isobutyl acetate (1162 mL), resulting in a dark brown solution (ca. 1780 mL).

Heptane (7120 mL) was charged to the second reactor. The reactants in the first reactor were added to the second reactor over 1 hour. The precipitate was stirred for at least 3 hours and filtered. The product was washed 4 times with 250 ml of heptane. The product was dried under reduced pressure at 40 mbar pressure at 80°C. 700 g (wet weight) or 419 g (dry weight) of the product of P2 step (b) were obtained.

Products were identified using analytical techniques including LC-MS, ^NMR1H , ^NMR13C , GPC and FTIR.

LC-MS analysis results indicated that the product was a complex mixture of star compound monomers and oligomers with a C ₁₀ adamantane nucleus. The determined structures are listed in the following table (Ad = clathrate C ₁₀ adamantane; T is tolanyl-PhC≡CC ₆ H ₄ -; t-Bu = -C(CH ₃ ) ₃ ):

# M+ peak Inferred structure 1 ^a 664 AdT ₃ H ^2a 840 AdT ₄ ^3a 720 Ad(H)T ₃ (t-Bu) 4 ^{a, b} 896 _AdT4 (t-Bu) 5 ^{a, b} 1326 Ad2T ₆ 6a ^,b 1402 Ad ₂ T ₆ (C ₆ H ₄ )

^a All of these general structures are observed for analogs with MW ± 100 a.u. (plus or minus PhC≡C-group)

^b These structures are all observed analogues without the tolanyl branch (-176a.u.)

¹ H NMR identified aromatic protons (6.9-8 ppm, 2.80±0.2H) and caged _C10 adamantane protons (1.7-2.7 ppm, 1±0.2H).

¹³ C NMR analyzes the attribution of the following peaks: ¹³ C NMR peak position, ppm structure 151.3, 151, 150, 149.9, 149.8, 149.3, 149.2 Quaternary aromatic carbon attached to the _C10 adamantane ring 132-131, 128.5, 125.3, 125.2 CH aromatic carbon 129.6-129.1 Aromatic ring carbon 123.7-122.9, 121.8, 121.1, 120.9 quaternary carbon attached to acetylene 93.6 quaternary acetylene carbon (on disubstituted ring) 90.7, 90.3, 90.1, 89.7, 89.5, 89.4, 89.1, 88.8, 88.7 quaternary acetylene carbon 47.5, 46.7 _CH2 of tetrasubstituted _C10 adamantane 47.1 _CH3 of tetrasubstituted _C10 adamantane 41 _CH2 of trisubstituted _C10 adamantane 39.6 _CH3 of trisubstituted _C10 adamantane 39.5, 39.2-39.0, 38.6, 38.2, 35 Quaternary carbon of tetrasubstituted C ₁₀ adamantane 32 CH ₃ of the tert-butyl group on the aromatic ring 30 CH of trisubstituted C ₁₀ adamantane

GPC analysis results:

-1,3,5,7-Tetrakis[3'/4'-(phenylethynyl)phenyl]C ₁₀ adamantane (as shown in Figure 3D) has a peak molecular weight of about 763;

-1,3/4-bis{1′,3′,5′-tri[3″/4″-(phenylethynyl)phenyl]C ₁₀ adamantane-7′-yl}benzene (as shown in Figure 3F Shown) the peak molecular weight is about 1330;

-1,3-bis-{3′/4′-[1″,3″,5″-tri[3/4-(phenylethynyl)phenyl]C ₁₀ adamantane-7″-yl] The peak molecular weight of phenyl}-5,7-bis(3″″/4″″-(phenylethynyl)phenyl]C ₁₀ adamantane (shown in FIG. 3F ) is about 1520 (shoulder peak).

According to the GPC results, the ratio of monomers and small molecules to oligomers was 50±5%.

FTIR results are as follows:

Peak position cm ^-1 (peak intensity) structure 3050 (weak) Aromatic C-H 2930 (weak) Aliphatic CH on _C10 adamantane 2200 (very weak) Acetylene 1600 (very strong) Aromatic C=C 1500(strong) 1450 (medium) 1350 (medium)

preparation 3

The solvent pairs 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]C ₁₀ adamantane (as shown in Figure 1D) and 1,3/4-bis{1′,3 ',5'-tris[3"/4"-phenylethynyl)phenyl]C ₁₀ adamantane-7'-yl}benzene (as shown in Figure 1F) and at least 1,3-bis{3'/4 ′-[1″, 3″, 5″-tri[3/4-(phenylethynyl)phenyl]C ₁₀ adamantane-7″-yl]phenyl}-5,7-bis[3″ Effect of "/4""-(phenylethynyl)phenyl]C ₁₀ adamantane (as shown in Figure 1F) ratio.

850 ml of the product of step (a) of P1 was divided into four equal portions and precipitated in petroleum ether, ligroine, heptane and methanol respectively. Each aliquot produced a precipitate in 2520 ml of solvent, vacuum filtered (Büchner funnel, diameter 185 mm), washed twice with 150 ml of solvent on the filter, and then dried in a vacuum oven at about 20° C. for 2 hours at 40° C. Dry overnight and at 70-80°C to constant weight.

Precipitation in hydrocarbon solvents yields a very dispersed light gray powder, which can be dried directly. Precipitation in methanol gave a dark brown granular solid (particle size about 1 mm) which dried at 20°C to form a tar. The product required further drying.

The reaction mixture was analyzed by GPC during the reaction and before precipitation. All filtrates and final solids were analyzed by GPC and the results are listed in Table 7. In Table 7, PPT means precipitation, the monomer is 1,3,5,7-tetra(3'/4'-bromophenyl) C ₁₀ adamantane (as shown in Figure 1A); the dimer is 1,3 /4-bis[1′,3′,5′-tri(3″/4″-bromophenyl) C ₁₀ adamantane-7′-yl]benzene (as shown in Figure 1C); the trimer is 1 , 3-bis{3′4′-[1″,3″,5″-tris(3/4-bromophenyl)C ₁₀ adamantane-7″-yl]phenyl}-5,7- Bis(3""/4""-bromophenyl) C ₁₀ adamantane (as shown in Figure 1C).

Table 7 Pre-precipitation peak ratio [monomer: (dimer + trimer)] PPT solvent Peak ratio after precipitation [monomer: (dimer + trimer)] 75.0:25.0 petroleum ether 52.5:47.4 75.0:25.0 Ligroine 64.0:36.0 75.0:25.0 Heptane 66.2:33.8 75.0:25.0 Methanol 75.0:25.0

Summarizing these results, the monomer:(dimer+trimer) peak ratio in the reaction mixture was about 3:1. The product lost in the precipitation filtrate in the hydrocarbon solvent was predominantly (>90%) monomer, while the loss in the wash filtrate was negligible. No product was formed in the filtrate precipitated in methanol. After precipitation the monomer:(dimer+trimer) ratio increases (1:1 to 3:1) and the monomer loss in the filtrate decreases in the following order (56% to 0%): petroleum ether , Ligroine, Heptane and Methanol.

Preparation 4 - Preparation of Thermosetting Components

1,3/4-Bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl] _C10adamantan -7′-yl}benzene in the product mixture of preparation 1 (as shown in Figure 1F) were separated using preparative liquid chromatography (PLC). PLC is similar to the HPLC method described above, except that larger columns are used to separate larger quantities of mixtures (from a few grams to hundreds of grams).

Preparation 5 - Preparation of Thermosetting Components

1,3-Bis{3′/4′-[1″,3″,5″-tris[3/4-(phenylethynyl)phenyl] _{C10adamantane} -7 in preparation 1 product mixture ″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl] _{C10adamantane} (as shown in Figure 1F) using a preparative liquid chromatograph (PLC) separate.

Preparation 6 - Preparation of Thermosetting Components

Oligomers or polymers of C adamantane monomers of formula XIIA, XIIB, XIIC or XIID and C _adamantane monomers of formula XIII, XV, XXII and XXV are prepared by the _following method. As shown in Figure 2, bromine and Lewis acid catalysts were used to convert _C14 adamantanes to brominated _C14 adamantane products. The _C14 adamantane bromide product is then reacted with bromobenzene in the presence of a Lewis acid catalyst to generate bromobenzene _C14 adamantane. This bromophenylated _C14 adamantane is then reacted with a terminal alkyne in the presence of the catalyst system used in the so-called Sonogashira coupling reaction. The products of each step were worked up according to the method described in our pending patent application PCT/US01/22204 filed on October 17, 2001.

Preparation 7 - Preparation of thermosetting component (a)

Oligomers or polymers of C adamantane monomers of formula XIIA, XIIB, XIIC or XIID and C _adamantane monomers of formula XIII, XVI, XXII and XXV are prepared by the _following method. As shown in Figures 1A to 1F, _C14 adamantane was converted to the bromobenzylation composition of _C14 adamantane by a synthetic method similar to that described for Preparations 1 and 2. In FIGS. 1A to 1F , a _C14 adamantane is reacted with a substituted halobenzene compound in the presence of the Lewis acid catalyst described in Preparations 1 and 2 and/or the second catalyst component described in Preparation 2. Workup of the reaction mixture yields a mixture of monomers, dimers, trimers and higher oligomers. In FIGS. 1D to 1F , the bromobenzylated _C14 adamantane mixture is then reacted with terminal alkynes in the presence of a catalyst to produce alkyne-substituted _C14 adamantane compositions of the present invention.

Invention Example 1-Containing the preparation of the porogen of the copolymer of acenaphthylene and vinyl pivalate:

A porogen comprising a copolymer of acenaphthene and vinyl pivalate was prepared as follows. Add 20g of industrial grade acenaphthene (75% purity, equivalent to 0.986mol of pure acenaphthene), 3.1579g (0.0246mol) of vinyl pivalate, 0.5673g (2.464mmol) of azodicarboxylic acid into a 250ml flask equipped with a mechanical stirrer Di-tert-butyl ester and 95ml xylene. The mixture was stirred at room temperature for 10 minutes to obtain a homogeneous solution. The reaction solution was then degassed under reduced pressure for 5 minutes, purging with nitrogen. Repeat this process 3 times. The reaction mixture was heated at 140°C under nitrogen atmosphere for 6 hours. The solution was cooled to room temperature and added dropwise to 237 ml of ethanol. The mixture was further stirred at room temperature for 20 minutes. The precipitate formed was collected by filtration and dried in vacuo. The properties of the resulting copolymer are given in Table 5 above (copolymer 18). Other porogens comprising copolymers of acenaphthene and vinyl pivalate were prepared in a similar manner, but varying the percentage of comonomer used, type of initiator, percentage used, reaction time and temperature as shown in Table 5 above.

Inventive Example 2 - Preparation of porogen comprising acenaphthylene and tert-butyl acrylate copolymer:

A porogen comprising acenaphthene and tert-butyl acrylate copolymer was prepared as follows. Add 20 grams of industrial grade acenaphthene (75% purity, equivalent to 0.0986mol pure acenaphthene), 2.5263g (0.01971mol) tert-butyl acrylate, 0.3884g (2.365mmol) 2,2' in a 250ml flask equipped with a mechanical stirrer - azobisisobutyronitrile and 92ml xylene. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes, purging with nitrogen. Repeat this process 3 times. The reaction mixture was then heated at 70° C. under nitrogen for 24 hours. The solution was cooled to room temperature and added dropwise to 230ml of ethanol. The mixture was further stirred at room temperature for 20 min. The precipitate formed was collected by filtration and dried in vacuo. The properties of the resulting copolymer are given in Table 5 above (copolymer 2). Other porogens comprising copolymers of acenaphthene and tert-butyl acrylate were prepared in a similar manner, but varying the percentages of comonomer used, type of initiator, percentages used, reaction time and temperature as shown in Table 5 above.

Inventive Example 3 - Preparation of porogen comprising acenaphthylene and vinyl acetate copolymer:

A porogen comprising acenaphthene and vinyl acetate copolymer was prepared as follows. Add 20 grams of industrial grade acenaphthene (75% purity, equivalent to 0.986mol pure acenaphthene), 1.6969g (0.01971mol) vinyl acetate, 0.3884g (2.365mmol) 2,2'- Azobisisobutyronitrile and 88ml xylene. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes, purging with nitrogen. Repeat this process 3 times. The reaction mixture was then heated at 70° C. under nitrogen for 24 hours. The solution was cooled to room temperature and added dropwise to 220ml of ethanol. The mixture was further stirred at room temperature for 20 minutes. The precipitate formed was collected by filtration and dried in vacuo. The properties of the resulting copolymer are given in Table 5 above (copolymer 18). Other porogens comprising copolymers of acenaphthene and vinyl acetate were prepared in a similar manner, but varying the percentages of comonomers used; the properties of the resulting copolymers are given in Table 5 above (their polymer 19).

Invention Example 4 - Preparation of porogen comprising polyacenaphthylene homopolymer:

Polymers of acenaphthene were prepared as follows. Into a 250 ml flask equipped with a mechanical stirrer was added 30 g of technical grade acenaphthene (75% purity, equivalent to 0.148 mol of pure acenaphthene), 0.3404 g of di-tert-butyl azodicarboxylate (1.478 mmol) and 121 ml of xylene. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes, purging with nitrogen. Repeat this process 3 times. The reaction mixture was heated at 140°C under nitrogen atmosphere for 6 hours. The solution was cooled to room temperature and added dropwise to 303 ml of ethanol. The mixture was further stirred at room temperature for 20 minutes. The precipitate formed was collected by filtration and dried in vacuo. The resulting homopolymer properties are given in Table 5 below (Homopolymer 1), where DBADC stands for di-tert-butyl azodicarboxylate and PDI stands for polydispersity (Mw/Mn). Other porogens comprising polyacenaphthylene homopolymers were prepared in a similar manner, but the initiator type, percentage, reaction time and temperature were changed as shown in Table 8. In Table 8, AIBN represents 2,2'-azobisiso Nitrile.

Table 8 homopolymer Initiator type Initiator% solvent temperature(℃) time (hours) mn mw PDI 1 DBADC 1% Xylene 140 6 3260 14469 4.44 2 DBADC 2% Xylene 140 6 2712 11299 4.17 3 DBADC 3% Xylene 140 6 3764 14221 3.78 4 DBADC 4% Xylene 140 6 3283 8411 2.56 5 DBADC 6% Xylene 140 6 2541 7559 2.97 6 DBADC 8% Xylene 140 6 2260 6826 3.02 7 DBADC 12% Xylene 140 6 2049 5805 2.83 8 DBADC 16% Xylene 140 6 2082 5309 2.55 9 DBADC 20% Xylene 140 6 1772 4619 2.61 10 DBADC 30% Xylene 140 6 1761 3664 2.08 11 AIBN 2% Xylene 70 twenty four 3404 7193 2.11 12 AIBN 2% Xylene 70 twenty four 3109 6141 1.98 13 AIBN 2% Xylene 70 twenty four 3500 7295 2.08 14 AIBN 2% Xylene 70 twenty four 3689 6165 1.67

Inventive Example 5 - Composition Comprising Polyacenaphthylene Homopolymer, Thermoset Component and Polycarbosilane Preparation and Invention Example 6 - Preparation of Compositions Comprising Polyacenaphthylene Homopolymer and Thermosetting Components

For Inventive Example 5, commercial polyacenaphthene homopolymer (25 g, used as a pore former); polycarbosilane (Ch ₂ SiH ₂ ) _q , where q is 20-30 (1.57 g) (provided by Starfire Systems, Inc , used as a tackifier) and xylene (334 g) were weighed and added to a plastic bottle. Add a stir bar to the bottle. The bottle was tightly sealed and stirring started. The solution was stirred at room temperature for 24 hours. The solution was poured into a pre-weighed 2-neck bottle with a stir bar containing the thermoset component (22.43 g) similar to Preparation 1 or 2 above. The bottle was washed with xylene (approximately 111 g) and the resulting xylene solution was added to the 2-neck bottle until the total weight of the reaction mixture reached 500 g. Clamp the flask and connect it to a water condenser and turn on circulating water.

The system was flushed with nitrogen (strong nitrogen flow) from the top (inlet) to the side neck (outlet) of the condenser for 30 minutes. The nitrogen inlet at the top of the condenser was replaced with an inlet-outlet and the side neck was sealed with a plug. The slight nitrogen stream was continued. Lower the flask into an oil bath (preheated to 145°C and stir at a constant rate) and submerge the entire flask in the oil bath. The stir bar in the reaction flask was stirred and the reaction mixture was boiled and refluxed for 15.5 hours. Discontinue heating and stirring. The flask was taken out from the oil bath and allowed to stand to cool to room temperature. Remove the stir bar using the magnetic strip and begin solvent displacement with cyclohexanone.

Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to be about 60 to 90 g. Then 500 grams of cyclohexanone were added to the flask. Most of the xylene was removed again by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to be about 60 to 90 g. This operation was repeated twice until all xylene was replaced with cyclohexanone. The solution was then diluted with cyclohexanone to obtain a 20% solids solution. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps. The final composition contained 20% solids, of which 6.7% by weight polycarbosilane, 50% by weight polyacenaphthylene homopolymer, and the remainder being the thermoset component.

Inventive Example 6 The method of Inventive Example 5 was repeated except that no tackifier was added, so that the composition contained 50% by weight polyacenaphthylene homopolymer and the remainder was thermosetting components. Inventive Examples 7-10 - Preparation of Compositions Comprising Polyacenaphthylene Homopolymer, Thermosetting Component and Polycarbosilane

Inventive Example 7 Repeat the method of Inventive Example 5, except that polycarbosilane (CH ₂ SiH ₂ ) _q , wherein q is 20-30 (provided by Starfire Systems, Inc) is used in an amount of 2.68 g. The final composition contained 20% solids, of which 12% by weight polycarbosilane, 50% by weight polyacenaphthylene homopolymer, and the remainder being the thermoset component. Invention Examples 8-10 Repeat the method of Invention Example 7, except that the percentage content of polyacenaphthylene homopolymer is changed according to Table 9 below.

Table 9 Embodiment of the invention Polyacenaphthene Homopolymer % by weight 8 35 9 20 10 10

Inventive Examples 11-17 - Compositions Comprising Polyacenaphthylene Homopolymer, Thermosetting Compound and Polycarbosilane preparation of

The method of Inventive Example 5 was repeated, except that polycarbosilane (CH ₂ SiH ₂ ) _q , wherein q was 20-30 (provided by Starfire Systems, Inc) was used in an amount of 1.92 g. Change the percentage of polyacenaphthylene homopolymer according to Table 10 below.

Table 10 Embodiment of the invention Polyacenaphthene Homopolymer % by weight 11 28 12 26.8 13 27.2 14 26.5 15 25.4 16 38.3 17 30.1

Inventive Examples 18-21 - Compositions Comprising Polyacenaphthylene Homopolymer, Thermoset Component and Polycarbosilane preparation of

Inventive Example 7 was repeated except that the amount of polyacenaphthylene homopolymer used was 25% by weight and the type of polyacenaphthylene homopolymer used is described in Table 11 below.

Table 11 Embodiment of the invention Polyacenaphthene homopolymer 18 Homopolymer 1 of Table 4 19 Homopolymer 2 of Table 4 20 Homopolymer 3 of Table 4 twenty one Homopolymer 4 of Table 5

Inventive Examples 22-23 - Comprising Polyacenaphthylene Homopolymer, Thermoset Component and Ortho-Cresol Novolac Preparation of resin blend compositions

For Inventive Example 22, to a 65-mL plastic bottle equipped with a magnetic stirring bar was added a thermosetting component similar to Preparation 1 or 2 above (4.17 g), o-cresol novolac resin (0.125 g, as a tackifier agent), polyacenaphthylene (1.074g, as a pore former) and cyclohexanone (24.46g). The mixture was stirred at room temperature for 2 hours, then the resulting homogeneous solution was filtered through a 0.1 μm filter. Inventive Example 23 The method of Inventive Example 22 was repeated except that 6% by weight of o-cresol type novolac phenolic resin was used.

Inventive Examples 24-30 - Combinations Comprising Polyacenaphthene Copolymer, Thermosetting Compound and Polycarbosilane preparation

For inventive example 24, polyacenaphthylene copolymer (4.48 g, copolymer 13 of Table 2, as a pore forming agent) was added to a plastic bottle equipped with a magnetic stirring bar; polycarbosilane (CH ₂ SiH ₂ ) _q , where q is 20-30 (0.48g, as tackifier) and xylene (59.4g). The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 100 ml three-neck flask. A thermosetting component similar to Preparation 1 or 2 above (4.00 g) and an additional 19.8 g of xylene were added. The solution was purged with nitrogen for 5 minutes and heated at 145°C for 15.5 hours. Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to about 10 to 12 g. Then 100 grams of cyclohexanone was added to the flask. Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to about 10 to 12 g. This operation was repeated two more times to ensure that all xylene had been converted to cyclohexanone. The solution was then diluted with cyclohexanone to give a solution at 18% solids concentration. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps. The final composition contained 18% solids, of which 12% by weight polycarbosilane, 50% by weight polyacenaphthylene homopolymer, and the remainder being the thermoset component.

Inventive Examples 25 to 30 Inventive Example 24 was repeated except that the porogens of Table 12 below were used.

Table 12 Embodiment of the invention Copolymers of Table 2 twenty four 7 25 11 26 9 27 6 28 4 29 3 30 1

Inventive Examples 31-32 - Compositions comprising polycaprolactone, thermosetting compound and polycarbosilane preparation of

For Inventive Example 31, the solvent used was xylene. Add polycaprolactone (4.48g, as a pore forming agent) to _a plastic bottle _equipped with a magnetic stirring bar _; ) and xylene (59.4 g). The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250ml three-neck bottle. A thermosetting component similar to Preparation 1 or 2 above (4.00 g) and an additional 19.8 g of xylene were added. The solution was purged with nitrogen for 5 minutes and heated at 145°C for 15.5 hours. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps. The final composition contained 10% solids, of which 12% by weight polycarbosilane, 50% by weight polyacenaphthylene homopolymer, and the remainder being the thermoset component.

For Inventive Example 32, the solvent used was cyclohexanone. Add polycaprolactone (4.48g, as a pore forming agent) to _a plastic bottle _equipped with a magnetic stirring bar _; ) and xylene (59.4 g). The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250ml three-neck bottle. A thermosetting component similar to Preparation 1 or 2 above (4.00 g) and an additional 19.8 g of xylene were added. The solution was purged with nitrogen for 5 minutes and heated at 145°C for 15.5 hours. Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to about 10 to 12 g. Then 100 grams of cyclohexanone was added to the flask. Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to about 10 to 12 g. This operation was repeated two more times to ensure that all xylene had been converted to cyclohexanone. The solution was then diluted with cyclohexanone to give a solution at 18% solids concentration. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps. The final composition contained 18% solids, of which 12% by weight polycarbosilane, 50% by weight polyacenaphthylene homopolymer, and the remainder being the thermoset component.

Inventive Examples 33-35 - Containing Polycaprolactone, Thermosetting Compound and Ortho-Cresol Novolac Preparation of resin blend compositions

To a plastic bottle equipped with a magnetic stirring bar was added a thermosetting component (4.00 g) similar to Preparation 1 or 2 above, o-cresol type novolac resin (0.12 g, molecular weight 1760, supplied by Schenectady International Inc, as a tackifier agent), polycaprolactone (2.53 g, as a pore former) and 37.66 g of cyclohexanone. The solution was stirred at room temperature for 2 hours. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps. The final composition contained 15% solids, of which 3% by weight o-cresol novolak (calculated on the thermoset component), 35% by weight polycaprolactone (calculated on the total solids) and the remainder being the thermoset component .

According to the conditions given in Table 13, repeat the above steps.

Table 13 Embodiment of the invention o-cresol type novolac resin % by weight 33 3.4 34 6.9 35 12.2

Inventive Examples 36-37 - Comprising Polyacenaphthene Homopolymer, Polycaprolactone, Thermosetting Compound and Polycarbon Preparation of blend compositions of silanes

For Inventive Example 36, the solvent used was xylene. Add polycaprolactone (4.48g) and commercial polyacenaphthylene homopolymer (0.7906g, as a pore-forming agent) to a plastic bottle equipped with a magnetic stirring bar; polycarbosilane (CH ₂ SiH ₂ ) _q , where q is 20-30 (0.48 g, supplied by Starfire Systems, Inc. as a tackifier) and xylene (64.74 g). The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250ml three-neck bottle. A thermosetting component similar to Preparation 1 or 2 above (4.00 g) and an additional 21.58 g of xylene were added. The solution was purged with nitrogen for 5 minutes and heated at 145°C for 15.5 hours. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps. The final composition contained 16.5% solids, of which 12% by weight polycarbosilane (based on the weight of the thermoset component), 15% by weight polyacenaphthene (based on the weight of the thermoset component), and the remainder being the thermoset component.

For Inventive Example 37, the solvent used was cyclohexanone. Add polycaprolactone (4.48g) and commercial polyacenaphthylene homopolymer (0.7906g, as a pore-forming agent) to a plastic bottle equipped with a magnetic stirring bar; polycarbosilane (CH ₂ SiH ₂ ) _q , where q is 20-30 (0.48 g, as tackifier) and xylene (64.74 g g). The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250ml three-neck bottle. A thermosetting component similar to Preparation 1 or 2 above (4.00 g) and an additional 21.58 g of xylene were added. The solution was purged with nitrogen for 5 minutes and heated at 145°C for 15.5 hours. Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to about 10 to 12 g. Then 100 grams of cyclohexanone was added to the flask. Most of the xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture was weighed to about 10 to 12 g. This operation was repeated two more times to ensure that all xylene was converted to cyclohexanone. The solution was then diluted with cyclohexanone to give a solution at 18% solids concentration. The solution was slowly filtered through a 0.1 μm teflon filter at a rate of less than 20 psig. Repeat the preceding steps.

Inventive Examples 38-41 - Preparation of Compositions Comprising Blends of Polyacenaphthene Homopolymer, Polycaprolactone, Thermosetting Compound and Polycarbosilane

Inventive Examples 38 and 40 The method of Inventive Example 37 was repeated except that the amount of polycarbosilane used was changed according to Table 14. Inventive Examples 39 and 41 The method of Inventive Example 36 was repeated except that the amount of polycarbosilane used was changed according to Table 14. In Table 14, PAN means polyacenaphthylene homopolymer, PCL means polycaprolactone, and PCS means polycarbosilane.

Table 14 Embodiment of the invention PAN% in porogen blend PCL % in porogen blend PCS% solvent 38 15 50 6.7 Cyclohexanone 39 15 50 6.7 Xylene 40 15 50 3 Cyclohexanone 41 15 50 3 Xylene

Inventive Example 42-Preparation of the Film of Inventive Example 5

The composition of Inventive Example 5 was applied to a substrate under conventional coating conditions known to those skilled in the art. Under the protection of nitrogen (<50 ppm oxygen), the obtained spin-coating compositions were dried at 125° C., 250° C. and 300° C. for 1 minute, respectively. Furnace solidification conditions are nitrogen (26 liters/minute) protection, starting from 250 ° C, heating at 5 ° K per minute, and 60 minutes at 400 ° C. The curing temperature ranges from 350°C to 450°C. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the above-mentioned test method, and the properties of the analyzed layers are given in Table 15.

Table 15 parameter Invention Example 42 curing conditions 400℃/2 hours membrane thickness 0.3-1.2μm Refractive index n (after drying) 1.6600 Refractive index n (after curing) 1.3600 Thickness (after drying, nm) 2885.00 Thickness (after curing, nm) 2874.00 Shrinkage % (drying to curing) -0.30 Dielectric constant (room temperature) 1.93 Dielectric constant (outgassed) 1.901 Modulus (Gpa) 2.26±0.59(1.2μm) Hardness (Gpa) 0.16±0.05(1.2μm) Glass transition temperature (°C) >410 (the first cycle) Average peak pore size 20nm Average pore size 4.1nm Pore volume (cm ³ /g) 0.557 film quality good tape test qualified Stability at 425°C 4.5%

Inventive Example 43-Preparation of the Film of Inventive Example 6

The composition of Inventive Example 6 was applied to a substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the above test methods, and the properties of the analyzed layers are given in Table 16.

Table 16 parameter Invention Example 43 Refractive index n (after drying) 1.6600 Refractive index n (after curing) 1.4150 N ² 2.00 Thickness (after drying, nm) 2740.74 Thickness (after curing, nm) 2450.00 Shrinkage % (drying to curing) -10.61 film quality Cloudy (indicating phase separation)

The results for Inventive Example 43 show the benefit of the presence of tackifier in Inventive Example 42.

Inventive Examples 44-47 - Preparation of Films of Inventive Examples 7-10

Each of the compositions of Inventive Examples 7-10 was applied to the substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the above test methods, and the properties of the analyzed layers are given in Table 17.

Figures 4 and 5 present the results of scanning electron microscopy (SEM). Figure 4 shows a cross-section of the film and Figure 5 shows the surface of the film. It can be seen from SEM that with the increase of the amount of porogen, fine pores can be observed or seen on the surface of the film. Therefore, the surface appears to have lower porosity as the amount of porogen decreases. At the same time, it can be seen from the SEM cross-sectional view that the average pore diameter increases with the increase of the amount of porogen. The TDMS curve of Figure 6 shows that the porogen begins to decompose at about 380°C.

Table 17 parameter Invention Example 44 Invention Example 45 Invention Example 46 Invention Example 47 Pore former content 50% 35% 20% 10% Tackifier 12% 12% 12% 12% curing conditions 400℃/1h 400℃/1h 400℃/1h 400℃/1h membrane thickness 0.3-1.2μm 0.3-1.2μm 0.3-1.2μm 0.3-1.2μm Refractive index (RI)n (after curing) 1.39 1.50 1.56 1.59 (RI)(RI) 1.93 2.25 2.44 2.54 Shrinkage % (drying to curing) 11.7 10.5 6.4 4.1 Dielectric constant (room temperature) 2.07 2.30 2.54 2.75 Dielectric constant (outgassed) 2.03 2.24 2.46 2.66 Modulus (Gpa) 2.40±0.121(1.2μm) 2.60±0.118(1.2μm) 4.80±0.152(1.2μm) 5.13±0.192(1.2μm) Hardness (Gpa) 0.12±0.018(1.2μm) 0.24±0.043(1.2μm) 0.33±0.025(1.2μm) 0.32±0.037(1.2μm) Average peak pore size 12.0nm 9.0nm 5.0nm 3.0nm Average pore size 5.1nm 4.0nm 2.8nm 2.7nm Pore volume (cm ³ /g) 0.669 0.511 0.315 0.233 Porosity larger hole big hole mostly microporous microporous Estimated porosity (%) 41 34 twenty four 19 Surface area (m ² /g) 521 511 450 341 tape test pass, dry/wet pass, dry/wet pass, dry/wet pass, dry/wet Stability at 425°C 5.45% 5.07% 4.30% 4.07%

These results indicate that the dielectric constant decreases with subsequent increase in porogen addition.

Preparation of thin films of inventive examples 48-54-inventive examples 11-17 and comparative example C

The various compositions of Inventive Examples 11-17 were applied to the substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. Comparative Example C was prepared in a manner similar to our inventive examples in US Serial No. 60/350,187 filed January 15, 2002, and thus contained no porogen. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the above test methods, and the properties of the analyzed layers are given in Table 18.

Table 18 Inventive Examples or Comparative Examples Refractive index (after drying) Refractive index (after curing) Thickness () (after drying) Thickness () (after curing) Shrinkage % (after drying and curing) Dielectric constant k (room temperature) Dielectric constant k (outgassed) -Δk% 48 1.661 1.529 8518.23 8067.62 -5.29 2.48 2.18 -12.10 49 1.657 1.532 8057.8 7541.79 -6.40 2.51 2.42 -3.59 50 1.661 1.499 7225.37 7093.32 -1.83 2.54 2.44 -3.94 51 1.658 1.521 8659.18 8510.56 -1.72 2.51 2.43 -3.19 52 1.657 1.510 8025.79 7952.16 -0.92 2.53 2.43 -3.95 53 1.659 1.500 8633.55 7815.56 -9.47 2.42 2.33 -3.72 54 1.661 1.504 8899.51 8605.25 -3.31 2.42 2.35 -2.89 C 1.677 1.617 3152.00 3252.00 3.17 2.69 2.62 -2.60 Embodiment of the invention Surface area (m ² /g) Pore volume (cm ³ /g) Average columnar pore diameter (nm) Approximate BJH peak pore diameter (nm) 48 559.00 0.427 3.10 10.00 49 568.00 0.410 2.90 10.00 50 564.00 0.436 3.10 10.00 51 443.00 0.306 2.80 8.00 52 543.00 0.425 3.10 10.00 53 612.00 0.491 3.20 8.00 54 574.00 0.461 3.20 8.00

Preparation of Films of Inventive Examples 55-58 - Inventive Examples 18-21 and Comparative Example D

The various compositions of Inventive Examples 18-21 were applied to the substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. Comparative Example D was prepared in a manner similar to our inventive examples in US Serial No. 60/350,187, filed January 15, 2002, and thus did not contain any porogen. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the above-mentioned test method, and the properties of the analyzed layers are given in Table 19 below, wherein RI represents the refractive index.

Table 19 Inventive Examples or Comparative Examples Refractive index (after drying) Refractive index (after curing) (RI)(RI) Thickness () (after drying) Thickness () (after curing) Shrinkage % (after drying and curing) 55 1.655 1.548 2.395 6800.55 6916.90 1.71 56 1.657 1.543 2.381 6814.10 6885.99 1.06 57 1.657 1.549 2.400 6792.82 6871.42 1.16 58 1.655 1.567 2.456 7520.50 7394.75 -1.67 D. 1.677 1.617 2.615 3152.00 3252.00 3.17 Embodiment of the invention Surface area (m ² /g) Pore volume (cm ³ /g) Average columnar pore diameter (nm) Approximate BJH peak pore diameter (nm) 57 476 0.31 2.60 16.00 56 464 0.307 2.60 14.00 57 468 0.297 2.50 20.00 58 429 0.275 2.60 20.00

Inventive Examples 59-66 - Preparation of Films of Inventive Examples 24-30

The various compositions of Inventive Examples 24-30 were applied to a substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the test methods described above, and the properties of the analyzed layers are given in Table 20 below.

The results obtained indicate that compositions comprising porogens of acenaphthene and vinyl pivalate copolymers have lower dielectric constants than compositions comprising porogens of acenaphthene and tert-butyl acrylate copolymers.

Table 20 Embodiment of the invention Starting Compositions: Inventive Examples Refractive index (after curing) Shrinkage % (after drying and curing) Refractive index ² Dielectric constant k (room temperature) Dielectric constant k (outgassed) Δk% Surface area (m ² /g) Pore volume (cm ³ /g) Average columnar pore diameter (nm) Approximate BJH peak pore diameter (nm) 59 26 1.45 16.36 2.10 2.13 2.09 1.88 594 0.651 4.4 11.0 60 27 1.41 11.26 1.99 2.1 2.06 1.90 622 0.698 4.5 14.0 61 28 1.41 8.28 1.99 2.11 2.07 1.90 600 0.697 4.6 12.0 62 29 1.41 9.15 2.00 2.09 2.05 1.91 614 0.696 4.5 11.0 63 30 1.40 5.7 1.95 2.06 2.02 1.94 577 0.738 5.1 16.0 64 31 1.54 25.16 2.36 2.48 2.42 2.42 581 0.389 2.7 no peak 65 32 1.48 17.11 2.18 2.33 2.28 2.15 612 0.504 3.3 7.0 66 33 1.44 12.96 2.07 2.19 2.14 2.28 649 0.631 3.9 9.0

Inventive Examples 67-68 - Preparation of Films of Inventive Examples 31-32

The various compositions of Inventive Examples 31-32 were applied to the substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The obtained layers were analyzed according to the above-mentioned test method, and the properties of the analyzed layers are given in Table 21 below, wherein NM represents not measured, and RI represents the refractive index.

Change the amount of pore forming agent and repeat the above steps. The results in Table 22 indicate that porogens with certain thermal stability can be selected to achieve certain desired dielectric constants. In Table 22, RI represents a refractive index.

Table 21

Table 18

Inventive Examples or Comparative Examples Refractive index (after drying) Refractive index (after curing) (RI)(RI) Thickness () (after drying) Thickness () (after curing) Shrinkage % (after drying and curing) 67 1.581 1.570 2.466 10819 6275.94 -41.99 68 NM 1.571 2.468 N M NM NM Embodiment of the invention Surface area (m ² /g) Pore volume (cm ³ /g) Average columnar pore diameter (nm) Approximate BJH peak pore diameter (nm) 67 462 0.25 2.2 Very small 4nm peak 68 99 0.089 3.6 NM

Table 22 Pore former% mw Refractive index (after curing) (RI)(RI) Thickness Change % Dielectric constant k (outgassed) 0 - 1.613 2.60 4 2.65 27 3000 1.543 2.41 -12 2.49 27 1250 1.568 2.46 -16 - 27 530 1.594 2.54 -19 2.58 35 3000 1.495 2.28 -17 2.44 35 1250 1.556 2.42 -twenty two 2.40 50 300 1.465 2.15 -31 2.27 50 1250 1.497 2.24 -33 2.24

Preparation of Films of Inventive Examples 69-71 - Inventive Examples 33-35 and Comparative Example E

The various compositions of Inventive Examples 33-35 were applied to the substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. Comparative Example E was prepared in a manner similar to our inventive example in US Serial No. 60/350,187, filed January 15, 2002, and thus contained no porogen of the present invention. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The resulting layers were analyzed according to the above test methods, and the properties of the analyzed layers are given in Table 23 below.

Table 23 nature Embodiment 69 of the present invention Example 70 of the present invention Embodiment 71 of the present invention Comparative Example E Refractive index (after curing) 1.542 1.540 1.528 1.623 Shrinkage % (before curing) 16.5 20.4 12.3 5.6 k (room temperature) 2.58 2.58 2.48 2.73 k (degassed) 2.54 2.54 2.43 2.70 Δk% 1.42 1.51 2.09 1.17 Average pore size (nm) 15 15 33 15 Pore volume (cm ³ /g) 0.323 0.364 0.392 0.257

Preparation of Films of Inventive Examples 72-77 - Inventive Examples 38-41 and Comparative Example F

The various compositions of Inventive Examples 38-41 were applied to the substrate under conventional coating conditions known to those skilled in the art, and the drying and curing conditions of Inventive Example 42 were used. Comparative Example F was prepared in a manner similar to our inventive examples in US Serial No. 60/350,187, filed January 15, 2002, and thus did not contain the porogen of the present invention. In each composition, the porogen decomposes and the decomposed porogen volatilizes to form pores in the composition. The resulting layers were analyzed according to the test methods described above, and the properties of the analyzed layers are given in Table 24 below, where NM means not measured and RI means refractive index.

Table 24 Inventive Examples or Comparative Examples Refractive index (after drying) Refractive index (after curing) (RI)(RI) Thickness () (after drying) Thickness () (after curing) Shrinkage % (after drying and curing) Dielectric constant k (room temperature) Dielectric constant k (outgassed) -Δk% 72 1.592 1.549 2.400 10000.36 5980.85 -40.19 2.75 2.61 -5.09 73 N M 1.545 2.387 N M N M N M N M 2.62 -3.16 74 1.595 1.565 2.450 7815.35 4632.49 -40.73 2.78 2.66 -4.32 75 1.601 1.561 2.435 2927.49 1757.16 -39.98 2.76 2.65 -3.99 76 1.603 1.524 2.322 2781.52 1798.23 -35.35 2.53 2.45 -3.16 77 1.603 1.523 2.320 2752.07 1787.38 -35.05 2.60 2.51 -3.46 f 1.677 1.617 - 3152.00 3252.00 3.17 2.69 2.62 -2.60 Embodiment of the invention Surface area (m ² /g) Pore volume (cm ³ /g) Average columnar pore diameter (nm) Approximate BJH peak pore diameter (nm) 72 507 0.2683 2.1 5nm small peak 73 483 0.23 1.9 20nm broad peak 74 486 0.238 2.0 17nm very small peak 75 482 0.251 2.1 18nm very small peak 76 570 0.394 2.8 8nm small peak 77 550 0.371 2.7 7nm small peak

Invention Example 78

The 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]C ₁₀ adamantane-7′-yl} isolated from Preparation 4 Benzene (shown in Figure 1F) is mixed with adhesion promoters and porogens, then dissolved in a solvent, spin-coated onto silicon wafers, and then dried to cure to form a film for use in microchips or multi-chip assemblies.

Invention Example 79

The 1,3-bis{3′/4′-[1″,3″,5″-tris[3/4-(phenylethynyl)phenyl]C ₁₀ adamantane isolated from Preparation 5- 7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl] _{C10adamantane} (shown in Figure 1F) mixed with tackifier and pore former , then dissolved in a solvent, spin-coated on a silicon wafer, and then dried until solidified to form a film, which can be used in microchips or multi-chip assemblies.

Claims (61)

1. A composition comprising: (a) dielectric materials; and (b) a porogen comprising at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substituent and at least two of the alkyl substituents on adjacent aromatic rings A bond exists between the alkyl substituents. 2. The composition of claim 1, wherein said porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymers, functionalized polyacenaphthylene homopolymers, polyacenaphthylene copolymers, poly(2-vinylnaphthalene) and Vinyl anthracene and their blends with each other. 3. The composition of claim 2, wherein said porogen is said polyacenaphthene copolymer prepared from acenaphthene and a monomer selected from the group consisting of vinyl pivalate, tert-butyl acrylate, styrene, α- Methylstyrene, tert-butylstyrene, 2-vinylnaphthalene, 5-vinyl-2-norbornene, vinylcyclohexanone, vinylcyclopentane, 9-vinylanthracene, 4-vinyl Biphenyl, tetraphenylbutadiene, 1,2-stilbene, tert-butyl 1,2-stilbene, indene, allyl-substituted hydropolycarbosilane, vinyl acetate, methyl acrylate, methyl methyl acrylate and vinyl ether. 4. The composition of claim 2, wherein the porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymers, functionalized polyacenaphthylene homopolymers, polyacenaphthylene copolymers, and unfunctionalized polyacenaphthylene homopolymers. A blend of poly(caprolactone) and poly(caprolactone). 5. The composition of claim 2 or 3, wherein the dielectric material is an organic dielectric material. 6. The composition of claim 5, wherein the dielectric material is a phenylethynylated aromatic monomer or oligomer. 7. The composition of claim 5, wherein the organic dielectric material is a clathrate, preferably a _C10 adamantane. 8. A spin coating precursor comprising the composition of claim 5. 9. A thermoset substrate prepared from the spin-on precursor of claim 8. 10. A layer comprising the thermoset matrix of claim 9. 11. The layer of claim 10, wherein the thermoset matrix is cured. 12. A method of using the composition of claim 5. 13. The method of claim 12, said method comprising the steps of: decomposing the porogen; and The decomposed porogen is volatilized, thereby lowering the dielectric constant of the dielectric material. 14. The method of claim 12, said method comprising the steps of: decomposing the porogen; and The decomposed porogen is volatilized, thereby forming pores in the dielectric material. 15. The method of claim 13, wherein said step of decomposing said porogen comprises curing by means of a furnace, a hot plate, electron beam radiation, microwave radiation, or ultraviolet radiation. 16. The method of claim 14, wherein said step of decomposing said porogen comprises curing by means of a furnace, a hot plate, electron beam radiation, microwave radiation, or ultraviolet radiation. 17. A composition comprising a cage structure having a dielectric constant of less than 2.7. 18. The composition of claim 17, wherein the cage structure is _C10 adamantane. 19. A spin-on-coating precursor comprising the composition of claim 18. 20. A thermoset substrate prepared from the spin-on precursor of claim 19. 21. A layer comprising the thermoset matrix of claim 20. 22. The layer of claim 21, wherein said thermoset matrix is cured. 23. A composition comprising: (a) a thermosetting component comprising: (1) optionally at least one monomer of formula I and (2) at least one oligomer or polymer of formula II Wherein said E is a clathrate compound; each said Q is the same or different and is selected from hydrogen, aryl, branched aryl and substituted aryl, wherein said substituents include hydrogen, halogen, alkyl, aryl, Substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl; said G _is aryl Or substituted aryl, wherein said substituent includes halogen and alkyl; said h is 0-10; i is 0-10; j is 0-10; w is 0 or 1; (b) Porogens. 24. The composition of claim 23, wherein said porogen comprises a material having a decomposition temperature below the glass transition temperature of said thermosetting component (a) and above the curing temperature of said thermosetting component (a). 25. The composition of claim 24, wherein said porogen comprises at least two fused aromatic rings, wherein each of said fused aromatic rings has at least one alkyl substituent, and at least one alkyl substituent on adjacent aromatic rings A bond exists between two of said alkyl substituents. 26. The composition of claim 24, wherein said porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthene copolymer, polynorbornene, polycaprolactone , poly(2-vinylnaphthalene), vinylanthracene, polystyrene, polystyrene derivatives, polysiloxane, polyester, polyether, polyacrylate, aliphatic polycarbonate, polysulfone, polycross Esters and their blends. 27. The composition of claim 26, wherein said porogen is said acenaphthene copolymer prepared from acenaphthene and a monomer selected from the group consisting of vinyl pivalate, tert-butyl acrylate, styrene, alpha-formaldehyde Styrene, tert-butylstyrene, 2-vinylnaphthalene, 5-vinyl-2-norbornene, vinylcyclohexanone, vinylcyclopentane, 9-vinylanthracene, 4-vinylbis Benzene, tetraphenylbutadiene, stilbene, tert-butyl stilbene, indene, allyl substituted hydropolycarbosilane, vinyl acetate, methyl acrylate, methyl Methyl acrylate and vinyl ether. 28. The composition of claim 24, wherein the porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymers, functionalized polyacenaphthylene homopolymers, polyacenaphthylene copolymers, polynorbornenes, and polycaprolactones . 29. The composition of claim 26 comprising (1) at least one C ₁₀ adamantane monomer of formula III and (2) at least one C ₁₀ adamantane oligomer or polymer of formula IV Or (1) at least one C ₁₄ adamantane monomer of formula V

and (2) at least one C _adamantane oligomer or polymer of formula VI 30. The composition of claim 29, wherein said at least one oligomer or polymer (2) is a C ₁₀ adamantane dimer of formula VII

31. The composition of claim 29, wherein said at least one oligomer or polymer (2) is a _C10 adamantane trimer of the following formula VIII 32. The composition of claim 26, wherein said thermosetting component (a) comprises (1) a _C10 adamantane monomer of the formula: Formula XA

Formula XB Formula XC

or XD and (2) the C _adamantane oligomer or polymer of formula XI Or (1) C of the following formulas ₁₄ adamantane monomers: Formula XIIA

Formula XIIB

Formula XIIC or Formula XIID and (2) C _adamantane oligomers or polymers of formula XIII, Wherein said h is 0-10; said i is 0-10; said j is 0-10; said R ₁ are each the same or different and selected from hydrogen, halogen, alkyl, aryl, substituted aryl, Heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl; said Y are each the same or different and are selected from hydrogen , alkyl, aryl, substituted aryl or halogen. 33. The composition of claim 32, wherein said monomer is present. 34. The composition of claim 32 or 33, wherein said R ₁ is aryl or substituted aryl and said Y is hydrogen, phenyl or biphenyl. 35. The composition of claim 34, wherein said (2) C ₁₀ adamantane oligomer or polymer is a dimer of formula XVI

Or the (2) C ₁₄ adamantane oligomer or polymer is a dimer of formula XVII

36. The composition of claim 34, wherein said (2) C ₁₀ adamantane oligomer or polymer is a trimer of formula XVIII

Or the (2) C ₁₄ adamantane oligomer or polymer is a trimer of formula XIX

37. The composition of claim 34, wherein said thermosetting component (a), said oligomer or polymer (2) comprises a C ₁₀ adamantane dimer of formula XVI and a C ₁₀ adamantane tris of formula XVIII polymer mixture Formula XVI

Formula XVIII or a mixture of a C _adamantane dimer of formula XVII and a C _adamantane trimer of formula XIX Formula XVII Formula XIX

38. The composition of claim 37, wherein said thermosetting component (a), said monomer (1) and said oligomer or polymer (2) are _C10 adamantyl monomers. 39. The composition of claim 38, wherein at least two of said R ₁ C≡C groups on said phenyl are two different isomers and two of said C ₁₀ adamantane monomers are two different isomers. There are two different isomers of at least one of the phenyl groups between the bridgehead carbon atoms. 40. The composition of claim 39, wherein said at least two isomers are meta and para isomers. 41. The composition of claim 34, said composition also comprising (c) a tackifier, said tackifier comprising a compound having at least a bifunctional group, wherein said bifunctional groups may be the same or different, and said bifunctional group The first functional group is capable of interacting with said thermosetting component (a) and the second functional group is capable of interacting with the substrate on which said composition is applied. 42. The composition of claim 41, wherein the tackifier is selected from the group consisting of: Silanes of formula XXXVI: (R ₂ ) _k (R ₃ ) _l Si(R ₄ ) _m (R ₅ ) _n , wherein R ₂ , R ₃ , R ₄ and R ₅ each independently represent hydrogen, hydroxyl, unsaturated or saturated Alkyl, substituted or unsubstituted alkyl, wherein the substituent is amino or epoxy, unsaturated or saturated alkoxy, unsaturated or saturated carboxy, or aryl, the R ₂ , R ₃ , R ₄ and R At least two of ₅ represent hydrogen, hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl or unsaturated carboxyl, and k+l+m+n≤4; Polycarbosilanes of formula XXXVII:

Wherein R ₈ , R ₁₄ and R ₁₇ each independently represent a substituted or unsubstituted alkylene group, cycloalkylene group, 1,2-vinylene group, allyl group or arylene group; R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, or an organic group of alkyl, alkylene, vinyl, cycloalkyl, allyl or aryl, and these groups can be linear or branched ; R ₁₃ represents organosilicon, silyl, siloxy or organic group; and p, q, r and s satisfy the condition [4≤p+q+r+s≤100,000], and q, r and s Can be all or 0 respectively; Glycidyl ethers or unsaturated carboxylic acid esters having at least one carboxyl group; Vinyl cyclic oligomers or polymers, wherein the cyclic group is vinyl, aromatic or heteroaromatic; and Phenolic resins or oligomers of formula XXXVIII: -[R ₁₈ C ₆ H ₂ (OH)(R ₁₉ )] _u -, wherein R ₁₈ is substituted or unsubstituted alkylene, cycloalkylene, vinyl, alkenyl Propyl or aryl, R ₁₉ is alkyl, alkylene, 1,2-vinylene, cycloalkylene, allylylene or aryl, and u=3-100. 43. The composition of claim 42, wherein said tackifier (c) is said phenolic resin or oligomer. 44. A spin coating precursor comprising the composition of claim 41 and a solvent, preferably cyclohexanone. 45. A thermoset substrate prepared from the spin-on precursor of claim 44. 46. A layer comprising the thermoset matrix of claim 45. 47. The layer of claim 46, wherein said thermoset matrix is cured. 48. The layer of claim 46, wherein said layer has a dielectric constant of less than 2.7, preferably less than 2.5, more preferably less than 2.2 and most preferably less than 2.0. 49. The layer of claim 46, wherein the layer has an average pore size of less than 20 nanometers. 50. A substrate having at least one said layer of claim 46 thereon. 51. A microchip comprising the substrate of claim 50. 52. A composition comprising: (a) a compound having at least two functional groups, wherein the two functional groups may be the same or different, and at least one of the first functional group and the second functional group is selected from a silicon-containing group, a nitrogen-containing group, a carbon-oxygen bond groups, hydroxyl groups, and groups containing carbon-carbon double bonds; and (b) A porogen comprising at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substituent and between at least two of the alkyl substituents on adjacent aromatic rings key exists. 53. The composition of claim 52, wherein the porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymers, functionalized polyacenaphthylene homopolymers, polyacenaphthylene copolymers, poly(2-vinylnaphthalene), Vinyl anthracene and their blends with each other. 54. The composition of claim 53, wherein said porogen is said polyacenaphthene copolymer prepared from acenaphthene and a monomer selected from the group consisting of vinyl pivalate, tert-butyl acrylate, styrene, alpha- Methylstyrene, tert-butylstyrene, 2-vinylnaphthalene, 5-vinyl-2-norbornene, vinylcyclohexanone, vinylcyclopentane, 9-vinylanthracene, 4-vinyl Biphenyl, tetraphenylbutadiene, 1,2-stilbene, tert-butyl 1,2-stilbene, indene, allyl-substituted hydropolycarbosilane, vinyl acetate, methyl acrylate, methyl methyl acrylate and vinyl ether. 55. The composition of claim 54, wherein the tackifier is selected from the group consisting of: Silanes of formula XXXVI: (R ₂ ) _k (R ₃ ) _l Si(R ₄ ) _m (R ₅ ) _m , wherein R ₂ , R ₃ , R ₄ and R ₅ each independently represent hydrogen, hydroxyl, unsaturated or saturated Alkyl, substituted or unsubstituted alkyl, wherein the substituent is amino or epoxy, unsaturated or saturated alkoxy, unsaturated or saturated carboxy or aryl, the R ₂ , R ₃ , R ₄ and R ₅ At least two of them represent hydrogen, hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl or unsaturated carboxyl, and k+l+m+n≤4; Polycarbosilanes of formula XXXVII:

Wherein R ₈ , R ₁₄ and R ₁₇ independently represent substituted or unsubstituted alkylene, cycloalkylene, 1,2-vinylene, allyl or arylene; R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, or an organic group of alkyl, alkylene, vinyl, cycloalkyl, allyl or aryl, and these groups can be linear or branched ; R ₁₃ represents organosilicon, silyl, siloxy or organic group; and p, q, r and s satisfy the condition [4≤p+q+r+s≤100,000], and q, r and s Can be all or 0 respectively; Glycidyl ethers or unsaturated carboxylic acid esters having at least one carboxyl group; Vinyl cyclic oligomers or polymers, wherein the cyclic group is vinyl, aromatic or heteroaromatic; and Phenolic resins or oligomers of formula XXXVIII: -[R ₁₈ C ₆ H ₂ (OH)(R ₁₉ )] _u -, wherein R ₁₈ is substituted or unsubstituted alkylene, cycloalkylene, vinyl, alkenyl Propyl or aryl, R ₁₉ is alkyl, alkylene, 1,2-vinylene, cycloalkylene, allylylene or aryl, and u=3-100. 56. The composition of claim 55, wherein said tackifier (c) is said phenolic resin or oligomer. 57. The composition of claim 55, wherein said compound (a) and said porogen (b) interact. 58. The composition of claim 55, further comprising a dielectric material. 59. A composition comprising: (a) a thermosetting component comprising a mixture of at least two different isomers of formula XXVII Wherein said E is a clathrate compound; each said Q is the same or different and is selected from hydrogen, aryl, branched aryl and substituted aryl, wherein said substituents include hydrogen, halogen, alkyl, aryl, Substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl; said G _is aryl Or substituted aryl, wherein said substituent includes halogen and alkyl; said h is 0-10; i is 0-10; j is 0-10; w is 0 or 1; and (b) Porogens. 60. The composition of claim 59, wherein said mixture comprises at least two different isomers of formula XXVIII, formula XXIX or formula XXX: Formula XXVII

Formula XXIX

Formula XXX

Wherein each said Y is the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl or halogen and each of said _R is the same or different and is selected from hydrogen, halogen, alkyl, aryl, substituted aryl radical, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl. 61. The composition of claim 59, wherein said mixture comprises at least two different isomers of formula XXXI, formula XXXII, formula XXXIII or formula XXXIV Formula XXXI

Formula XXXII

Formula XXXIII

Formula XXXIV Wherein each said Y is the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl or halogen and each of said _R is the same or different and is selected from hydrogen, halogen, alkyl, aryl, substituted aryl radical, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl.

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