CN1102164C - Rapid hardening sol material - Google Patents
Rapid hardening sol material Download PDFInfo
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- CN1102164C CN1102164C CN 99109298 CN99109298A CN1102164C CN 1102164 C CN1102164 C CN 1102164C CN 99109298 CN99109298 CN 99109298 CN 99109298 A CN99109298 A CN 99109298A CN 1102164 C CN1102164 C CN 1102164C
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- acid
- sol material
- material according
- quickly hardening
- additive
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Abstract
本发明提供一种剂型溶胶材料，其是由下列成分经水解/缩合反应而成，包括：2-60重量份的硅醇盐；20-98重量份的醇；0.5-50重量份的水性介质；0.0001-10重量份的碱；0.001-30重量份的添加剂；以及，选择性地包括0.0001-10重量份的酸。依本发明的剂型溶胶溶液进行镀膜，可不经过老化过程直接进行固化，即可得到一无裂痕且具有孔隙的介电膜。The invention provides a dosage form sol material, which is formed by hydrolysis/condensation reaction of the following components, including: 2-60 parts by weight of silicon alkoxide; 20-98 parts by weight of alcohol; 0.5-50 parts by weight of aqueous medium ; 0.0001-10 parts by weight of a base; 0.001-30 parts by weight of an additive; and, optionally, 0.0001-10 parts by weight of an acid. Coating according to the dosage form sol solution of the present invention can be directly cured without aging process, and a dielectric film without cracks and with pores can be obtained.
Description
The present invention relates to a kind of formulation sol material, be specifically related to a kind of made quickly hardening sol material of colloidal sol synthesis method that utilizes, its applicable on the coating process to form the dielectric film of low-k (low k).
General plated film all must be through long gel and weathering process (a day～January) with the synthetic of material, and just can obtain in follow-up drying process not can contraction, warpage, cracked gel (gel); Perhaps behind the film gel formation again the surface to porous material carry out upgrading, to improve above-mentioned described problem.Generally behind synthetic colloidal sol (sol), the time of the leaving standstill frame strength that will increase the gel that forms of a specified duration more, and can resist the structure deteriorate phenomenon that causes because of capillary pressure in the drying process; In like manner, after the preliminary structure of gel forms, also can reach this kind effect in the mode of gel skeleton surfaction.In addition, convert to by colloidal sol and in fact implied the stability of plated film in the process of gel with material; That is material must satisfy long between its shelf lives under the obsolete situation, and in case be used for producing on the line demand that must change the finished product apace into.
United States Patent (USP) 4,652 has been described the method that a kind of dielectric film that designs porosity is made for No. 467: under a certain fixed alkoxide/pure ratio, adjust water-content, the pure salt concn that pH value (sour, alkali) and temperature obtain setting.And under 50 ℃ of states aging 6 days, grow to desired structure in order to polymer after, reduce the temperature to 15 ℃ or lower keeping the state of molecule in the colloidal sol, and then keep designed porosity.Carry out sintering, gel after plated film finishes again, obtain film.
United States Patent (USP) 5,525 has been inquired into for No. 643 and have been utilized acid to be catalyzer, with polydimethylsiloxane (polydimethylsiloxane; PDMS), tetraethoxysilane (tetraethoxylortho; Silicate; TEOS) and Union carbide A-162 (methyltriethoxysilane; MTEOS) condensation reaction of carrying out at random prepares aerogel (aerogel) or xerogel (xerogel), and is applied on the thermal insulation material.Be primarily aimed at PDMS to the ratio of TEOS/MTEOS, acid to the ratio of TEOS/MTEOS, water to the ratio of TEOS/MTEOS, the change that solvent is filled a prescription to the ratio of TEOS/MTEOS.But in that carry out must be through wearing out of not waiting in 24 hours～48 hours before dry.
United States Patent (USP) 5,565 discloses the xerogel (xerogel) that is equipped with high hole with chemical surface upgrading legal system No. 142.Its proposition can be under vacuum or under the subcritical pressure dry and obtain with supercutical fluid under the similar effect of exsiccant.Mainly be to utilize organism and hole surface reaction,, make when solvent evaporation not that the reason capillary pressure is excessive and cause colloidal sol to shrink to improve the contact angle of hole surface and solvent.Need to use two stage acid base catalysis in the preparation of Coating Materials: acid is in order to promote hydrolysis, and alkali is then in order to promote condensation; Afterwards, under 37 ℃, carry out wearing out in 24 hours, and behind gel formation, carry out surfaction.
United States Patent (USP) 5,723, mention the method for improving porous material dielectric film surface properties No. 368: utilize halogen (fluorine) to remove the aqueous vapor on hole surface, make the neither hydrophilic also oleophylic not in surface, and improve the possibility that reduces specific inductivity because of hole absorption aqueous vapor.In the preparation of plated film, utilize fluorine-containing gas to carry out the sintering gel, to reach the purpose of surfaction.
By above explanation as can be known, present existing plated film needed 24 hours at least with its gel of material and digestion time or makes its skeleton structure firm through the low-grade fever state; Or behind gel formation, again porous material is carried out surfaction, just can obtain the microporous membrane of crackless different aperture degree after the drying.
In addition, commercial at present low-k material such as FOX-14 (Dow Corning company) and PAE-2 (Schamacher company) etc. all need 5 ℃ of preservations.
Main purpose of the present invention is to provide a kind of gel and digestion time extremely short; And in the colloidal sol building-up process, promptly carrying out the plated film material of upgrading, it can directly apply in the coating process, can obtain not having the microporous membrane of the different aperture degree of contraction, warpage, slight crack after the drying.
Another object of the present invention is to provide a kind of plated film material that can at room temperature preserve.
For reaching above-mentioned purpose, the invention provides a kind of formulation sol material, be to utilize additive to control the sol particle size, except that make the colloidal sol storage life itself enough long, gum deposit rapidly again in the system film, and reach the purpose of upgrading.
The present invention relates to a kind of quickly hardening sol material, it is to be formed through the hydrolyzing reaction by following ingredients, comprising: the silicon alkoxide of 2-60 weight part; The alcohol of 20-98 weight part; 0.5-50 the aqueous medium of weight part; 0.0001-10 the alkali of weight part; And the additive of 0.001-30 weight part; Described additive is selected from the compound with following structural: R '
nSi (OCH
3)
4-n, R '
nSi (OC
2H
5)
4-n, R ' COOH, R (OH)
mAnd R '
nSiCl
4-n, wherein R ' can be hydrogen, phenyl, C
1-C
20Alkyl, thiazolinyl, ester group or amino; R is phenyl, C
1-C
20Alkyl, thiazolinyl, ester group or amino, m are 1-3, and n is the integer of 0-3; Condition is the R ' described in the additive
nSi (OCH
3)
4-nAnd R '
nSi (OC
2H
5)
4-nStructurally different with above-mentioned silicon alkoxide, the R described in the additive (OH)
mStructurally different with above-mentioned alcohol and alkali.
Snap cure solvent material of the present invention also optionally further comprises the acid of 0.0001-10 weight part, and condition is that this acid is structurally different with the R ' COOH described in the additive.
The present invention is set out by the synthesis step of plated film with material with maximum different being in the present invention of known technology, utilize additive control granular size to prolong preservation period in the building-up process, and be able in coating process, obtain not having contraction after the drying, the microporous membrane of the different aperture degree of warpage, slight crack.
Enough long according to the resulting material of the present invention shelf lives, carry out plated film, the required time compole of gel and aging reaction is short, and dry back and can obtaining does not have the microporous membrane of the different aperture degree of contraction, warpage, slight crack; Thereby be applicable to general coating process in the present IC industry.
The present invention mainly utilizes the colloidal sol synthesis method to make the silicon-dioxide main body of different aperture degree size, with the material that provides different coating process to use.For further understanding content of the present invention, below will be illustrated one by one at each reacted constituent of above-mentioned sol material:
Silicon alkoxide used in the present invention is R
1 nSi (OR
2)
4-n, R wherein
1, R
2Can be identical or different, be hydrogen, C
1-C
4Alkyl, n are the integer of 0-3.Wherein, the most normal silicon alkoxide that uses is tetraethoxysilane (TEOS).In addition, employed alcohols can cooperate the kind of silicon alkoxide and use, and is generally methyl alcohol or ethanol or its mixture; And employed aqueous medium can be deionized water or distilled water.
The present invention utilizes basic catalyst, or optionally uses an acidic catalyst, adjusts the size that different pH values is controlled ultra tiny sol particles.According to the present invention, employed acid can be organic acid or mineral acid or its mixture, for example: hydrochloric acid, nitric acid, phosphoric acid, acetic acid etc.; Employed alkali can be organic bases or mineral alkali or its mixture, for example: ammonium hydroxide, quadrol etc.
The present invention is when colloidal sol is synthetic, and the additive that is added also can prolong preservation period, and have the effect of upgrading except the granular size of control sol particles, is different from the known technology and again porous material is carried out upgrading behind the film gel formation.
According to the present invention, the concrete example of employed additive comprises: Union carbide A-162 (MTEOS), phenylformic acid, ethylene glycol, N-phenyl amino propyl trimethoxy silicane, phenylmethyldichloroislane or the like.
Colloidal sol according to the mentioned component gained is a formulation, can effectively control its preservation period, and can be directly used in the coating process, is suitable for the dielectric film with preparation low-k, high heat stability.For example, above-mentioned sol material can be coated with or impregnation method covers in the substrate, need directly not be cured through weathering process then, just can form a film with hole in substrate, and its porosity is between 5-80%.
Quickly hardening sol material of the present invention still can be applicable to fields such as optical thin film material, stupalith, thermal insulation material except can be applicable to the semiconductor dielectric layer material.
For above-mentioned and other purposes of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, be described in detail below:
Embodiment 1
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Nitric acid | Ammonium hydroxide | Additive * |
| wt％ | 9.3 | 83(6.1∶1) | 3 | 0.62 | 0.67 | 3.41 |
* Union carbide A-162 (MTEOS)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, reacts reaction is carried out fully, and last colloidal sol obtains not having contraction, the film of warpage, slight crack after spin coating process film forming drying.Measuring its specific refractory power through refractive index measuring instrument (nanospec 4000) is 1.155, substitution formula: Dk=1+6.33 (n-1) (n=specific refractory power), and getting Dk (dielectric coefficient) is 1.98.The Dk value of following examples all adopts above-mentioned instrument to measure specific refractory power substitution formula Dk=1+6.33 (n-1) and getting again if no special instructions.
Embodiment 2
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Nitric acid | Ammonium hydroxide | Additive * |
| wt％ | 9 | 88.3(3.6∶1) | 1.7 | 0.15 | 0.65 | 0.04 |
* phenylformic acid (C
6H
5COOH)
To go up the listed reactant of table and place in the reaction flask and be hydrolyzed/condensation reaction, and react reaction is carried out fully, colloidal sol obtains not having contraction, the film of warpage, slight crack after spin coating process film forming drying at last, and its Dk value is 3.08.
Embodiment 3
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Ammonium hydroxide | Additive * |
| wt％ | 10.5 | 86.4(14.6∶1) | 1.98 | 0.76 | 0.29 |
* phenylmethyldichloroislane (Si (C
6H
5) (CH
3) CL
2)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, reacts reaction is carried out fully, and last colloidal sol obtains not having contraction, the film of warpage, slight crack after spin coating process film forming drying, and its Dk value is 3.03.
Embodiment 4
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Nitric acid | Ammonium hydroxide | Additive * |
| wt％ | 8.7 | 88(3.1∶1) | 1.7 | 0.5 | 0.63 | 0.3 |
* N-phenyl amino propyl trimethoxy silicane (N-phenylaminopropyltrimethoxysilane)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, react reaction is carried out fully, last colloidal sol obtains not having contraction, the film of warpage, slight crack after spin coating process film forming drying, it is through ellipse minute instrument (Ellipsometer of J.A.Woollam company; Modle VB-200) recording porosity is 35%, the substitution formula: porosity %=1-(d/2.27) (d=density); D=(n-1)/0.202; Dk=1+6.33 (n-1), getting the Dk value is 2.88.
Embodiment 5
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Hydrochloric acid | Ammonium hydroxide | Additive * |
| wt％ | 10 | 82.3(13.4∶1) | 3.3 | 0.03 | 0.72 | 3.6 |
* Union carbide A-162 (MTEOS)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, reacts reaction is carried out fully, and last colloidal sol obtains not having contraction, the film of warpage, slight crack after spin coating process film forming drying, and its Dk value is 2.86.
Embodiment 6
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Nitric acid | Quadrol | Additive * |
| wt％ | 7.6 | 71.2(4.6∶1) | 16.7 | 1.2 | 0.5 | 2.8 |
* Union carbide A-162 (MTEOS)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, react reaction is carried out fully, last colloidal sol is after spin coating process film forming drying, obtain not having contraction, the film of warpage, slight crack, it is 18% that its ellipse minute instrument (modle VB-200) through J.A.Woollam company records porosity, substitution formula: porosity %=1-(d/2.27) (d=density); D=(n-1)/0.202; Dk=1+6.33 (n-1), getting the Dk value is 3.38.
Embodiment 7
| Composition | TEOS | Alcohols (methyl alcohol: ethanol) | Water | Acetic acid | Ammonium hydroxide | Additive * |
| wt％ | 10 | 81.3(22.8∶1) | 2.3 | 1.9 | 0.74 | 3.7 |
* Union carbide A-162 (MTEOS)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, reacts reaction is carried out fully, and last colloidal sol obtains not having contraction, the film of warpage, slight crack after spin coating process film forming drying, and its Dk value is 2.66.
Embodiment 8
| Composition | TEOS | Alcohols (methyl alcohol) | Water | Ammonium hydroxide | Additive * |
| wt％ | 5.4 | 91 | 0.98 | 0.38 | 1.9 |
* Union carbide A-162 (MTEOS)
The reactant that last table is listed places in the reaction flask and is hydrolyzed/condensation reaction, react reaction is carried out fully, last colloidal sol is after spin coating process film forming drying, get the film of a no contraction, warpage, slight crack, it is 71% that its ellipse minute instrument (modle VB-200) through J.A.Woollam company records porosity, substitution formula: porosity %=1-(d/2.27) (d=density); D=(n-1)/0.202; Dk=1+6.33 (n-1), getting the Dk value is 1.81.
The present invention discloses above-mentioned preferred embodiment, and so it is not in order to qualification the present invention, any those skilled in the art, and without departing from the spirit of the invention, various changes and the retouching that may make all belong in the scope of the present invention.
Claims (13)
1. quickly hardening sol material, it is to be formed through the hydrolyzing reaction by following ingredients, comprising:
The silicon alkoxide of 2-60 weight part;
The alcohol of 20-98 weight part;
0.5-50 the aqueous medium of weight part;
0.0001-10 the alkali of weight part; And
0.001-30 the additive of weight part, it is selected from:
R '
nSi (OCH
3)
4-n, R '
nSi (OC
2H
5)
4-n, R ' COOH, R (OH)
mAnd R '
nSiCl
4-n, wherein R ' can be hydrogen, phenyl, C
1-C
20Alkyl, thiazolinyl, ester group or amino; R is phenyl, C
1-C
20Alkyl, thiazolinyl, ester group or amino, m are 1-3, and n is the integer of 0-3;
Condition is the R ' described in the additive
nSi (OCH
3)
4-nAnd R '
nSi (OC
2H
5)
4-nStructurally different with above-mentioned silicon alkoxide, the R described in the additive (OH)
mStructurally different with above-mentioned alcohol and alkali.
2. quickly hardening sol material according to claim 1, wherein said silicon alkoxide are R
1 nSi (OR
2)
4-n, R wherein
1, R
2Can be identical or different, be hydrogen, C
1-C
4Alkyl, n are the integer of 0-3.
3. quickly hardening sol material according to claim 2, wherein said silicon alkoxide are tetraethoxysilane.
4. quickly hardening sol material according to claim 1, wherein said alcohol be selected from methyl alcohol, ethanol, and composition thereof.
5. quickly hardening sol material according to claim 1, wherein said aqueous medium are deionized water.
6. quickly hardening sol material according to claim 1, wherein said aqueous medium are distilled water.
7. quickly hardening sol material according to claim 1, wherein said alkali is selected from organic bases and mineral alkali and composition thereof.
8. quickly hardening sol material according to claim 7, wherein said alkali is selected from oxyammonia and quadrol.
9. quickly hardening sol material according to claim 1, wherein said additive is selected from: Union carbide A-162, phenylformic acid, ethylene glycol, N-phenyl amino propyl trimethoxy silicane, phenylmethyldichloroislane.
10. quickly hardening sol material according to claim 1, it further comprises the acid of 0.0001-10 weight part, and condition is, and this acid is structurally different with the R ' COOH described in the additive, and wherein R ' definition is with claim 1.
11. quickly hardening sol material according to claim 10, wherein said acid are selected from organic acid, mineral acid or its mixture.
12. quickly hardening sol material according to claim 11, wherein said acid is selected from hydrochloric acid, nitric acid, phosphoric acid or acetic acid.
13. a microporous membrane, it is made by each described quickly hardening sol material among the claim 1-12, and porosity is 5-80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109298 CN1102164C (en) | 1999-06-28 | 1999-06-28 | Rapid hardening sol material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109298 CN1102164C (en) | 1999-06-28 | 1999-06-28 | Rapid hardening sol material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1279263A CN1279263A (en) | 2001-01-10 |
| CN1102164C true CN1102164C (en) | 2003-02-26 |
Family
ID=5273802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99109298 Expired - Lifetime CN1102164C (en) | 1999-06-28 | 1999-06-28 | Rapid hardening sol material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1102164C (en) |
-
1999
- 1999-06-28 CN CN 99109298 patent/CN1102164C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1279263A (en) | 2001-01-10 |
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