TW200949439A - Cyclic compound, process for producing cyclic compound, photoresist base material comprising cyclic compound, photoresist composition, microprocessing method, semiconductor device, and apparatus - Google Patents

Abstract

A photoresist base material comprising a cyclic compound which is represented by any of formulae (A-1) to (A-3) and has an average degree of substitution with an acid-dissociable dissolution-inhibitive group of 55-90%. In the formulae, R's each is an acid-dissociable dissolution-inhibitive group or hydroxy.

Description

200949439 VI. Description of the invention: [Technical field to which the invention belongs]

The present invention relates to a photoresist substrate used in an electrical, electronic or optical field such as a semiconductor, and more particularly to a photoresist substrate for ultrafine processing. Further, the present invention relates to a novel cyclic compound, and more particularly to a radiation sensitive compound. Further, the present invention relates to a photoresist substrate used in an electrical, electronic or optical field such as a semiconductor, and more particularly to a photoresist substrate for ultrafine processing. [Prior Art] The use of ultra-violet light (Extreme Ultra Violet Light (hereinafter sometimes referred to as EUVL) or electron beam lithography can be used as a highly productive, high (four) degree micro-drawing method in the manufacture of semiconductors, etc. Therefore, in view of the high sensitivity and high-resolution photoresist used in the method, and the productivity and resolution of the fine pattern required, it is indispensable to improve the sensitivity of the photoresist. As a photoresist used for ultrafine processing by EUVL, for example, a method of using a chemically amplified positive resist having a higher photoacid generator concentration than other photoresist compounds has been proposed (for example, see Patent Document). However, the photoresist of the embodiment has a limitation of only 100 nm which is exemplified when the electron beam is used, from the viewpoint of line edge roughness. It is presumed that the main reason is that the aggregate of the polymer compound used as the substrate or the macromolecule of each of the polymerized molecules is large, and the line width and the surface: roughness thereof are affected. The present inventors have proposed a resorcinol calixarene compound (cah 139475.doc 200949439 resorcnnarene compound) as a high-sensitivity and high-resolution photoresist material (see Patent Documents 2 and 3). Further, Patent Document 4 discloses a resorcinol calixarene compound, but it is considered that the solubility of a part of the compounds is not sufficient, and only s has been used as a resist substrate for a known polymer. Additives are added instead of as a photoresist substrate. On the other hand, in the current semiconductor manufacturing step, since the photoresist substrate is dissolved in the solvent and then enters the film forming step, it is required that the photoresist substrate has a relatively high solubility in the coating solvent. Therefore, the present inventors have also proposed a resorcinol calixarene compound having improved solubility in a coating solvent (see Patent Document 5). Further, Non-Patent Document 1 discloses a compound in which: 'B' in the following formula (B_丨) and (B-4) is a fluorenyl group, a phenyl group or a 4-isopropylphenyl group, and all r are the first A cyclic compound of a dibutoxycarbonylmethoxy group, a third butoxycarbonyloxy group or an ethoxylated group. Further, it is disclosed that when the compound is used as a photoresist, it can be used as a dissolution inhibitor in a photoresist composition containing a known polymer substrate, and a half pitch of 4 〇 nm is performed. Micro processing. However, in the microfabrication, as the sensitivity, it is necessary to apply a very large energy of u 5 microcoulomb/cm 2 , and the performance as a photoresist substrate is insufficient. Patent Document 1: Patent Publication No. 2002-055457, Patent Document 2: Japanese Patent Laid-Open No. 2004-191913, Patent Document 3: Japanese Patent Laid-Open Publication No. 2005-075767, Patent Document 4: US Patent No. 60,935, Patent No. Document 5: Japanese Patent Laid-Open No. 2007-197389 Non-Patent Document 1: Chemistry of Materials, vol. 20, 341 to 356 (2008) 139475.doc 200949439 The above resorcinol calixarene compound does not satisfy the following two Conditions: Soluble in a solvent; when a photoresist film is produced by spin coating or the like, the solvent solution (generally 2.3 8 /β tetramethyl methoxide aqueous solution) has sufficient solubility resistance. The object of the present invention is to provide a photoresist substrate which is excellent in solubility in a coating solvent and has solubility resistance in a developer. Further, the present invention has been made in view of the above problems, and an object of the invention is to provide a photoresist substrate which is capable of performing fine addition of J1' and excellent in sensitivity.

SUMMARY OF THE INVENTION The present inventors have found that: the acid dissociation of the resorcinol calixarene compound, the acceptor ratio of the inhibitory group, that is, the average substitution rate of the acid dissociable dissolution inhibitory group is a specific value. The m solvent 'and has solubility resistance in a developing solution' to complete the present invention.匕 匕 匕 匕 发明 发明 发明 发明 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 发明 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The average substitution rate of the acid dissociable dissolution inhibiting group is a specific value, and it is soluble in a refrigerant, and has solubility resistance in a developing solution to complete the present invention. According to the invention, the following photoresist substrate, cyclic compound or the like can be provided. A photoresist substrate comprising a cyclic compound which is represented by any of the following (A-3), wherein a plurality of the formulas are acid groups, acid groups, acid groups, acid groups The average substitution rate of the dissociative dissolution inhibitory group is 55 to 90%, 139475.doc 200949439 [Chemical i]

[wherein v represents a hydrogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic nicotine group having a carbon number of 3 to 12, and carbon. The number is 3 to 12, an early cyclic cyclic aliphatic nicotyl group, a carbon number of 4 to a polycyclic cyclic aliphatic hydrocarbon group, a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group. And an aromatic group represented by the formula (A-4), a substituent represented by the formula (A-5), or a substituent formed by combining two or more of the substituents; [Chemical 2] —/Ύ (β)χ \=s/ (Α-4) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group, respectively, and χ represents an integer of 丨~5; when X is 2 or more, R may be the same or different) [Chemical 3]

4/-U-AT R2 y (A-5) p-tert-butylphenyl, naphthalene (wherein Ar represents a phenyl group, a stupid group, a group, or a formula (A-4) Group of groups; red substituted or unsubstituted carbon number is 1~20 R1, R2 is a hydrogen atom 139475.doc 200949439 linear aliphatic hydrocarbon group, substituted or unsubstituted carbon number is 3~丨2 a branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 2 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or A group consisting of two or more kinds of groups; y represents an integer of 1 to 4; when 丫 is 2 or more, R1 and R2 may be the same or different)].

2. The photoresist substrate of 1, wherein the acid dissociable dissolution inhibiting group is a group derived from the following formula (A-6) to (A-10), [Chemical 4]

(A-10)

(In the formulae (A-9) and (A-10), they may be the same or different). [Chem. 5] r represents the following - substituent; formula (Α-9) <

3. The photoresist substrate according to 2, wherein the cyclic compound is a compound represented by the following formula (A-11): wherein r is a substituent represented by the formula (A12) Or the average substitution rate of the substituent represented by the formula (A-12) is 60 to 90%, [Chem. 6]

A photoresist according to claim 2, wherein the cyclic compound is a compound represented by the following formula (A-13): wherein r is a substituent represented by the formula (A14) Or the average substitution rate of the substituent represented by the formula hydroxy (A-14) is 55 to 80%, [Chem. 7]

A photoresist composition comprising the photoresist substrate according to any one of 1 to 4 and a solvent. 139475.doc -8 - 200949439 6 · A microfabrication method 7. A semiconductor device. 'It uses a photoresist composition such as 5. This is made up of a semiconductor device such as 7 by a microfabrication method such as 6. A cyclic compound having a stereospecific configuration represented by one of the following formulas (B1) to (B6), wherein the ratio of the above cyclic compound to the total stereoisomer is 9 More than 〇 mol%, [化8] 〇

[In the formula, R is an acid-dissociating dissolution-inhibiting group or a meridine, respectively, and R is a hydroxyl group or an ether group, respectively. (_〇Ra: 5^ is a linear, monthly, aliphatic hydrocarbon group having a carbon number of 丨~cut, carbon number a branched aliphatic hydrocarbon group of 3 to 8, a monocyclic cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a polycyclic cyclic europene aliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, a naphthyl group, a linear aliphatic hydrocarbon group having a carbon number of 1 to 12, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a monocyclic cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms, carbon a number of ring-shaped rings of 4 to 10 139475.doc -9- 200949439 aliphatic hydrocarbon group, phenyl group, p-phenylphenyl group, p-tert-butylphenyl group, naphthyl group, the following formula (B -7) a substituent represented by a scent group of w, a substituent represented by the following formula (B-8), or a substituent formed by combining two or more of the φ + work s. (R)x (B-7) (in the formula, number) [Chem. 10] R is an acid dissociable dissolution inhibiting group or a hydroxyl group, and X represents an integer of 1 to 5

(B-8) (wherein Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the above formula (B-7); The hydrogen atom, the substituted or unsubstituted carbon number is a direct bond aliphatic hydrocarbon group, and the substituted or unsubstituted carbon number is 3 to have a branched m group hydrocarbon group, substituted or unsubstituted carbon number a cyclic aliphatic hydrocarbon group of 3 to 2 fluorene, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of the substituents; y is An integer of 1 to 4) R may be the same or different from each other, and R• may be the same or different from each other; wherein, in the above formula (BD and (B-4), R is a methyl group, a phenyl group or a 4 isopropyl group. Stupid base, and R is excluded from the following formula (B-9)] 139475.doc 200949439 [化li]

(B-9) 10. The cyclic compound according to 9, wherein the acid dissociable dissolution inhibiting group is selected from the above formula (Β-9) or the following formula (Β-10)~(Β-36) Group, [12]

[Chem. 13]

(Β-16) (Β-1 7) -3⁄4 -0-^ (B-l 8)- (Β-19) [Chem. 14]

(Β-2 0) (Β-21) 139475.doc -11 - 200949439

(B-2 3) (B-2 2)

-O 1-4Θ -03⁄4 (B-24) (B-25) [Chem. 15]

(B-30) (B-3 1) [Chem. 16]

(B-32) (B-33) (B-34)

O

(B-3 5) (B-36), 0-2) (wherein r represents the above formula (B-9) to (B-34), and the following formula (r- represented by the substituent) Either) -12· 139475.doc 200949439 [Chem. 17]

(M) (r-2) H, a photoresist substrate comprising a cyclic compound having a stereoscopic relative configuration represented by any one of the following formulas (B1) to (B-6), and the above The ratio of the cyclic compound to the total stereoisomer is 9 〇 mol% or more '[18]

[In the formula, R is an acid dissociative dissolution inhibitory group or a hydroxyl group, respectively, and R is a 35-group, a bond group (-〇Ra: Ra Oxygen Mountain slave, K is a slave number 丨~ cut straight chain aliphatic a hydrocarbon group, an aliphatic hydrocarbon group having a male chain of 3 to 8 carbon atoms, a monocyclic cyclic aliphatic hydrocarbon group having a carbon number of 3 to 8, and a polycyclic cyclic aliphatic group having a hard number of 4 to 1 Å. Hydrocarbyl, phenyl, naphthyl), _ } linear aliphatic ketone having an anisotropy of 1 to 12, a ruthenium having a carbon number of 3 to 12, a hydrazine, an aliphatic hydrocarbon group of a fork chain, and carbon a monocyclic cyclic aliphatic hydrocarbon group of 3 to 12, a polycyclic ring having a reversion of 4 to 1 139 139475.doc • 13- 200949439 aliphatic hydrocarbon group, stupid base, p-phenylphenyl group, p-type a tributylphenyl group, a naphthyl group, an aromatic group represented by the following formula (Β7), a substituent represented by the following formula (B-8), or a combination of two or more of the substituents a substituent; [Chem. 19] _/"Y(R)x (B-7) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group, and χ represents an integer of 5)

[Chem. 20]

(Β-8) (wherein Ar represents a phenyl group, a lean material | ^ an aromatic group represented by the basic group, a p-tert-butylphenyl group, a naphthyl group, and the above formula (B-7); R1, R2 a hydrogen atom, a substituted or unsubstituted carbon group having a carbon number of _ 〇, a substituted or unsubstituted carbon number of 3 to a branched aliphatic hydrocarbon group, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having a carbon number of 3 to 20, a substituted or unsubstituted aromatic group having a carbon number of 6 to 12, or a substituted A combination of two or more combinations of A and D bases, y is an integer of 1 to 4, and R' may be the same or different. Wherein the groups of the above-mentioned acid dissociative dissolution inhibiting group, R may be the same or different. 12. The photoresist substrate such as 11 is selected from the following (B-9) to (b_36) 139475.doc -14- 200949439 [化21]

Hai? ?«3 -〇 -C—O—j~~CH3 W3 Ο (B-9)

CHa

(B - 1 1) ‘CH3 -O-C-O'

(B-l 3) [Chem. 22]

(B-l 4) (B-l 5)

一〇—c —c—ο-H3C" (B-l 6) H2 —o-c- h3c- (B-l 7)-o-c2-o^ ❿ (B-l 8) (B-19) [Chem. 23]

H2 _〇-〇-O^i

P (B-23) -°3⁄4 (B —24) (B-25) -15- 139475.doc 200949439 [Chem. 24]

(B~26> (B-27)

(B_28) (B-2 9)

[Chem. 25]

(B-34) (wherein r represents each of the above formulas (B_9) to (b_34) and the substituents indicated below) J U-1), (r-2) [Chem. 26]

(M) (r-2) W is a photoresist substrate having a carbon number of 13. 1 or 12, a monocyclic cyclic aliphatic hydrocarbon group, a carbon number of 4, a polycyclic ring, 139,475. Doc •16 200949439 a hydrocarbon group, a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the above formula (B-7), and a substitution represented by the above formula (B-8) a substituent or a substituent composed of two or more of these groups. 14. The photoresist substrate according to 11, which is represented by the above formula (B1) or represented by R, wherein R is a group represented by the following formula (B-9), and R is a methyl group or a phenyl group, respectively. Or 4-isopropylphenyl, [Chem. 27]

CHa (B-9) 15_ - a photoresist composition containing, for example, a photoresist substrate according to any one of the above. 16. A microfabrication method using a photoresist composition such as 15 17. A semiconductor device produced by a microfabrication method such as 16. A device comprising a semiconductor device such as 17. 19. A method for producing a cyclic compound, such as a cyclic compound In the formula (B-1) to (B-3), the production method is a polyphenol compound selected from the group consisting of resorcin, pyrogallol, and 1,2,3,5·tetrahydrobenzene. An alcohol having a boiling point of 9 (rc or more) is added as a solvent to a mixture of a solid organic sulfonic acid as an acid catalyst, and then an aldehyde compound represented by the following formula (B-24) is added to prepare a reaction solution. 'The cyclization condensation reaction is carried out at a temperature of 90 ° C or more and 150 ° C or less to produce a cyclic compound represented by the following formulas (B-1') to (B-3'), and then the formula (Β) -Γ)~ at least one of the cyclic compounds represented by (B-3') 139475.doc •17· 200949439 Introduction of an acid dissociative dissolution inhibitory group via a base, [Chem. 28] R· -CHO (B-2 4)

(wherein R represents the same group as R represented by the claim 9). 20. A photoresist substrate comprising: a cyclic compound which is represented by any one of the following formula (C_1HC_3), wherein the plural (four) in the formula is an acid dissociable dissolution inhibiting group containing an alicyclic structure, respectively. Or a hydroxyl group, the average substitution rate of the above-mentioned acid dissociable dissolution inhibiting group is 2〇~6〇%, [Chem. 29]

Wherein R1 represents a hydrogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a number of a monocyclic cyclic aliphatic hydrocarbon group of 3 to 12, a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of fluorene, a phenyl group, a p-phenylphenyl group, a p-butylphenyl group, a naphthyl group, and a formula (C) -4) a substituent represented by the formula (c_5), 139475.doc -18- 200949439, a substituent, or a combination of two or more of the substituents; [Chem. 30] (C-4) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group each containing an alicyclic structure, and X represents an integer of 1 to 5; when 乂 is 2 or more, the ruler may be the same or different) 31]

(wherein Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (C-4); and R and R2 each independently represent a hydrogen atom; Or the unsubstituted carbon number is a linear aliphatic hydrocarbon group of 丨~汕, a substituted or unsubstituted branched aliphatic hydrocarbon group having a carbon number of 3 to 12, and the substituted or unsubstituted carbon number is a cyclic aliphatic hydrocarbon group of 3 to 2 fluorene, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups; y represents 1~ An integer of 4; when 丫 is 2 or more, Ri and R2 may be the same or different)]. A photoresist substrate according to 20, wherein said acid dissociable dissolution inhibiting group is selected from the group consisting of the following formulas (C-6) to (C-31), [Chem. 32]

(C-6) (C-7) 139475.doc -19- 200949439

(cl 0) (Cl 1) [Chem. 33] H2 min / -1 - OC - 0 - 0 - 7 - 〇 -C-0-7^" HaC-^, (Cl 2) (cl 3) °"5L〇i0 -o-c2-ojQ (Cl 4) (cl 5) h2

(C-I6) -o

P (C- 1 7) [Chem. 34]

(C-20) (C-2 1) (C-22) (C-2 3) 139475.doc 20- 200949439 [Chem. 35] (C-24) (C-2 5)

[化36]

(C-2 8) (C-2 9)

(C-30) (C-31) (wherein r represents any of the substituted embodiments represented by the above formulas (C-6) to (c-29)).

22. The photoresist substrate according to 21, wherein the cyclic compound is a compound represented by the following formula (C-33): HR is a substituent represented by the formula (C-34), respectively, a formula (C) .34) The average substitution rate of the substituents indicated is 35 to 50%, [Chem. 37]

(C-33) 139475.doc -21- (034} 200949439

23. The photoresist substrate according to 21, wherein the cyclic compound is a compound represented by the following formula (C-33): wherein R is a substituent represented by the formula (C-34') or The average substitution ratio of the substituent represented by the formula (C-34') is 20 to 60%, [Chem. 38]

A photoresist composition comprising the photoresist substrate according to any one of 2 to 23 and a solvent. 25. A microfabrication process using a photoresist composition such as 24.

26. A semiconductor device produced by a microfabrication method such as 25. 27. A device comprising a semiconductor device such as 26. According to the present invention, it is possible to provide a solvent which is easily soluble in a solvent and is spin-coated or the like: a photoresist film having a high solubility resistance in a developer (typically 2.38% tetrahydrocarbyl hydroxide solution) Photoresist substrate. The cyclic compound and the photoresist substrate of the present invention have a specific stereoscopic relative two-two in a developing solution (generally 2.38% gas oxidized tetramethylammonium water (IV), which is sufficiently high in calculus, and is easily soluble in the use of a photoresist. J39475.doc • 22· 200949439 in the medium. Further, according to the method for producing a cyclic inclusion of the present invention, a cyclic compound having a specific stereoscopic relative configuration can be produced. Therefore, the cyclic compound can be controlled. The stereoscopic relative configuration makes it possible to easily control the reactivity to the irradiated EUVL or the electron beam when used as a photoresist. As a result, the performance of the resist such as resolution or sensitivity can be greatly improved. The photoresist substrate of the first aspect of the present invention (hereinafter sometimes referred to as a first photoresist substrate) contains a cyclic compound which is represented by the following formula (A-1) to (A3). Any one of the formulas wherein the plurality of R in the formula is an acid dissociable dissolution inhibiting group or a hydroxyl group 'acid dissociable dissolution inhibiting group, respectively, has an average substitution ratio of 55 to 90%.

[In the formula, R' represents a hydrogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 2 carbon atoms, and carbon. a monocyclic cyclic aliphatic hydrocarbon group of 3 to 12, a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of 4 to 1 fluorene, a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, and a naphthalene a substituent represented by the formula (A-4), a substituent represented by the formula (a-5), or a combination of two or more of the substituents. 139475.doc-23-200949439 Substituent^ [化40]

(A-4) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group, respectively, and χ represents an integer of 丨~5. When X is 2 or more, R may be the same or different.) [Chem. 41]

(wherein Ar represents a stupid group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (A-4). R1 and R2 are each a hydrogen atom and are substituted. Or an unsubstituted carbon number of a straight-chain aliphatic hydrocarbon group having a carbon number of 3 to 12, a substituted or unsubstituted carbon number of 3 to 12, a substituted or unsubstituted carbon number a cyclic aliphatic hydrocarbon group of 3 to 2 fluorene, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups. An integer of ～4. When 7 is 2 or more, R1 and R2 may be the same or different.)] The "average substitution ratio" of the first aspect of the present invention is defined as follows. By subjecting a cyclic compound in which R is a hydroxyl group to an acid dissociable dissolution inhibiting group precursor by a conventionally known method, an acid dissociable dissolution inhibiting group initiator of a cyclic compound is produced, and according to the input ratio at this time, The reaction condition is selected to be selected from the group consisting of 〇~[the number of R in the cyclic compound] (8 in the case of the cyclic compound (A-1) and 12 in the case of the cyclic compound (A-2). Compound 139475.doc -24· 200949439 (Ad) is a mixture of a plurality of substitution number isomers in 16), the mixture having a fixed distribution. In the first aspect of the present invention, the average substitution ratio is calculated from the distribution according to the following formula, and is expressed as "average substitution ratio X percentage". , {(substituting the number of substitutional isomers of number 0) x〇+ (the amount of substitution number isomer of the substitution number) xl + (the amount of substitution number of substitution number 2) X2+ ... + (the number of substitutions of the number of substitutions in the number of R in the cyclic compound) χ [the number of the ruler in the cyclic compound]} - (all of the substitution isomers) The amount of the substance) = average substitution rate (percent) In general, the distribution shows a normal distribution, but due to the structure of the cyclic compound, or the combination of its stereoisomer and the acid dissociable dissolution inhibiting group precursor, There are combinations that are easy to react, combinations that are difficult to react, and situations that deviate from the normal distribution. Further, a specific distribution can be formed by a combination of the raw materials used and reaction conditions. Furthermore, the amount of each of the substituent isomers can be separated and identified by liquid chromatography/mass spectrometry (hereinafter referred to as LC/MS (Liquid chromatography-mass spectrometry)). The peak area ratio of each substituent isomer measured by a liquid chromatograph (hereinafter referred to as Lc) was determined. • The above average substitution rate can be arbitrarily adjusted according to the reaction conditions. For example, the amount of acid added to the acid dissociation inhibition inhibitor precursor is increased to dissociate the acid! - the amount of the condensing agent added by the condensation of the raw dissolution inhibiting group precursor, the reaction time, and the k-nan reaction temperature, thereby increasing the average substitution ratio; reducing the input amount of the y-acid dissolving dissolution-inhibiting precursor, reducing The amount of the condensing agent added by condensing the acid 139475.doc •25·200949439 dissociative dissolution inhibiting group precursor shortens the reaction time and lowers the reaction temperature, thereby lowering the average substitution ratio. The cyclic compound having an average substitution ratio of 55 to 90% is easily dissolved in a solvent for producing a photoresist composition, and when a photoresist film is formed by spin coating or the like, in a developing solution (generally 2.38% tetramethylammonium hydroxide) The solubility resistance in the aqueous ammonium solution is sufficiently high' and thus can be preferably used as a photoresist substrate.

The acid dissociable dissolution inhibiting group represented by the formula (A_i2) when the photoresist substrate is a cyclic compound of the general formula (An) and the cleavage is an acid dissociable dissolution inhibiting group or a hydroxyl group represented by the formula (A 12), respectively. The average substitution ratio is 6 〇 to 75 5%. When a small amount of the acid dissociable dissolution inhibiting group is removed during exposure, the solubility in the developer can be greatly improved, and as a result, the sensitivity as a photoresist can be improved. On the other hand, when the average substitution ratio is 75 to 9 %, the fine pattern formed is insoluble in the (four) developing solution, so that the smoothness of the surface of the side wall of the desired fine pattern is less likely to occur, and the height of the wall portion is lowered. 5 is better in terms of resolution. That is, the best range for the disclosed light-resistance sensitivity, the emphasis resolution, or the balance between the two is different.

However, if the average substitution ratio is 55 to 90%, it is shown that the sensitivity and the resolution are both practically problem-free, and it is preferably 60 to 9 Å/0. ^ In the same manner as above, ^ is a general formula (the cyclic compound of (7), the substituent represented by the formula (Α·14) or the base group, the formula represented by the formula (A"#) = base = average The substitution rate is 55, a percentage, and the sensitivity of the photoresist a nr is 7G to 8G percent, which is better in terms of resolution. When the photoresist substrate is used, if the early 払 + average substitution rate is 55 to 90 %, it shows that the sensitivity and resolution are both practical and problem-free performance, preferably 139475.doc •26- 200949439 55~80% 〇

In the first aspect of the present invention, the ## human t cyclic compound (hereinafter sometimes referred to as the first cyclic compound) is greatly affected by the action of the acid, and the solubility in the shoulder liquid is relatively It is good to contain an alkali soluble group. Examples of the soluble group include a thiol group, a benzyl group, a benzene (tetra), a benzyl group, a hexafluoroisopropanol group KC(CF3)20H] and the like. Preferred are a phenyl group, a carboxyl group, and a hexafluoroisopropanyl group, and more preferably a phenol group or a carboxyl group. The acid dissociable dissolution inhibiting group is a substituent which substitutes the hydrogen atom of OH in the above-mentioned alkali-soluble group, and preferably _c(Rm)(u(Rih), -C(R14a)(R15a)(〇 R16a), _CO_〇c(Riia)(Ri2a)(R]3a) Here, Rna-Rua independently represents a substituted or unsubstituted alkyl group, a % alkyl group, an alkenyl group, an arylalkyl group or an aromatic group. R14a&R.sup.sup. independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group, denotes a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aryl group. , R! la

R 12a

R 13a may also be bonded to form two of the rings, or two of R14a, R15a, and Rl6a.

The alkyl group, the cycloalkyl group and the aryl group in R1 la to Rl 6a may further contain a group as a substituent: a cycloalkyl group, a hydroxyl group, an alkoxy group, a pendant oxy group, an alkylcarbonyl group, an alkyloxy group. Carbonyl, alkylcarbonyloxy 'alkylaminocarbonyl, alkylcarbonylamino, fen-based, alkylsulfonyl, alkylsulfonylamino, alkylamine-based, amine-based It is true that the base, the atom, and the base are.

The aryl group or the alkenyl group in R11a to Rna and Rl6a may further contain a group as a substituent: an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a pendant oxy group, an alkylcarbonyl group, an alkyloxycarbonyl group, Alkylcarbonyloxy, alkylaminocarbonyl, alkylcarbonyl-27- 139475.doc 200949439 Amino, alkylsulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino It is a thiol group, an amino group, a sulfhydryl group, a cyano group, and the like.

The alkyl, cycloalkyl, alkenyl or aralkyl groups of Rna~R!6a may also have an ether group, a thioether group, a carbonyl group, an ester group, a decylamino group, a urethane group, a urea in the chain, respectively. Base, sulfonyl, fluorenyl. The acid dissociable dissolution inhibiting group is preferably a total carbon number of 4 or more, more preferably 6 or more, more preferably 8 or more.

Further, the acidolysis (tetra) dissolution inhibiting base towel preferably contains an alicyclic structure or an aromatic ring structure. Examples of the alicyclic structure include a cyclopentane residue, a cyclohexane residue, a norbornane residue, and an adamantane residue. Examples of the aromatic ring structure include a benzene residue, a naphthalene residue, and an anthracene residue. The alicyclic structure and the aromatic ring structure may have a substituent at any position. Table 4 (4) Dissociates the (d) decomposing group. However, the first aspect of the present invention is not limited thereto. [化42]

(A-6)

(Ar7) (Λ.)

(Α-9)

(Α-10) 139475.doc -28- 200949439 (In the formula (A 9) (A 10), 'Γ represents any of the following substituents. The formula (human _9) r may be the same or different.) 43]

In the above formulae (A-1) to (A-3), R is preferably a linear aliphatic group having a carbon number of kb: a kk group and a branched aliphatic group having a carbon number of 3 to 12. a hydrocarbon group, a phenyl group, a naphthyl group, an aromatic group represented by the formula (A-4), or a substituent represented by the formula (A-5), more preferably a linear aliphatic hydrocarbon group having a carbon number of 1 to 4, A branched aliphatic hydrocarbon group having a carbon number of 3 to 4 or a phenyl group. In the above formula (A-4), a preferred acid dissociable dissolution inhibiting group of R is the same as those of the formulae (A-1) to (A-3). X is preferably an integer. In the above formula (A-5), Ar is preferably a phenyl group or a naphthyl group. Ri and R2 are preferably a hydrogen atom, a methyl group or an ethyl group. y is preferably an integer of 1 to 2. The preferred cyclic compound used in the first resist substrate of the present invention is represented by the following formula (A-11): wherein R is a substituent represented by the formula (A-i2) or a hydroxyl group, and the formula (A) -12) The cyclic group compound having an average substitution ratio of 60 to 90% represented by the substituent. [化44]

139475.doc -29- 200949439

Further, a preferred cyclic compound to be used in the first resist substrate of the present invention is represented by the following formula (A-13): wherein R is a substituent represented by the formula (A-14) or a hydroxyl group, respectively. The average substitution rate of the substituent represented by (A-14) is 55 to 80% by weight of the cyclic compound. [化45]

The above cyclic compound can be used as a resist substrate which is used for ultrafine processing by a lithography method such as far ultraviolet light or electron beam. P The photoresist composition of the first aspect of the present invention (hereinafter sometimes referred to as a first photoresist composition) contains the above-mentioned photoresist substrate and a solvent. The compounding amount of the cyclic compound is 50 to 99.9% by weight in the solvent removal, and more preferably, when the compound is used as a photoresist substrate, it is possible to better detract from the effects of the present invention in all of the compositions. More preferably, it is 75 to 95% by weight as the first photoresist composition of the present invention. The ring shape may be used singly or in combination of two or more. ° will be ring-shaped, or in the no-listing: enumeration: ethylene glycol monoterpene ether acetate, alcohol monoalkyl ether acetate; ethylene dihydro glycol monoalkyl ether; The solvent to be used, for example, can absorb 6 oxime, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ketone, etc. (PGMea, 139475.doc) 200949439 propylene glycol monomethyl ether acetate); propylene glycol monoethyl ether acetate; propylene glycol monomethyl ether; propylene glycol monomethyl ether propylene glycol monoethyl ether and other propylene glycol monoalkyl ethers; Ethyl esters such as esters, ethyl lactate (EL, ethyl • lactate); aliphatic carboxylic acids such as methyl acetate, ethyl acetate, propyl acetate, ethyl acetate, butyl acrylate, and ethyl propionate Esters; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate; toluene, Aromatic hydrocarbons such as toluene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; , Dioxane and other cyclic burning trip class; γ_ butyrolactone and lactones, and not particularly limited. These solvents may be used singly or in combination of two or more. The amount of the component other than the solvent, i.e., the photoresist solid content, in the composition is preferably an amount suitable for forming the film thickness of the desired photoresist layer. Specifically, it is generally 50% by weight based on the total weight of the photoresist composition, and can be specified together with the type of the substrate or solvent to be used, or the film thickness of the desired photoresist layer. The solvent is preferably formulated in an amount of from 50 to 99.9% by weight in the total composition. When the molecule of the substrate contains a chromophore which is active against EUV and/or electron beams and exhibits the ability to act as a photoresist alone, the present invention In the second photoresist composition, it is not necessary to add an additive in particular, but when it is necessary to enhance the performance (sensitivity) as a photoresist, a photochromic generator (PAG) is generally used as a chromophore as needed. The acid generation #1 is not particularly limited, and (4) is proposed as an acid generator for chemically amplified photoresist. As the acid generator, a rust (tetra) acid such as m(tetra) is known to be produced 139475.doc 31 200949439, sulphur Acid generators, diazonium-based acid generators such as dialkyl or bisarylsulfonyldiazomethanes, poly(bissulfonyl)diazostanes, nitrobenzylsulfonates Acid generator, iminosulfonate acid generator, two More like those based acid generator as bin salt-based acid generator, an acid may be exemplified by the following formula generating agent (b_0) represented by the.

[Chem. 46] R53-S

(b-O)

Wherein R51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R52 is a hydrogen atom, a hydroxyl group, a dentate atom, a straight chain or a branched chain. An alkyl group, a linear or branched dentate alkyl group, or a linear or branched alkoxy group; and R53 is an aryl group which may have a substituent; In the formula (b-O), R represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.

As the above linear or branched alkyl group, it is preferred that the carbon number is b..., more preferably, the carbon number is b, and most preferably the carbon number is b. Preferably, the number of carbon atoms is 4 to 12, and the carbon number is 5 to 1 Å, and preferably the carbon number is 6 to 10. As the above-mentioned fluorinated alkyl group, it is preferred that the carbon number is (4), more preferably the hindrance number is VIII, and most preferably the carbon number is 卜, ... the vaporization rate of the fluorinated alkyl group (substituted fluorine atom) The ratio of the number to the number of all hydrogen atoms in the yard base is preferably from 10 to 100%, more preferably from 5 to 1%, especially with 139475.doc • 32·200949439 It is preferred to replace all of the halogen atoms to increase the acid strength. R51 is preferably a linear alkyl group or a fluorinated alkyl group. R52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched alkyl group, or a linear or branched alkoxy group. In the case of 52 t R, 'as a halogen atom, a fluorine atom, a bromine atom, a chlorine atom, a hard atom or the like is preferable. A fluorine atom is preferred. In 52 R, the alkyl group is linear or branched, and the carbon number thereof is preferably 丨 5 or 5, more preferably 1 to 4, most preferably 2. In 5 2 t R, the halogenated alkyl group is a group in which a part or all of hydrogen atoms in the alkyl group are substituted by a dentate atom. The alkyl group here can be enumerated as described above

5 2 I R The "alkyl group" is the same. The halogen atom to be substituted may be the same as the halogen atom described in the above "dentin atom". In the halogenated group, it is preferable that 5 to 丨〇〇% of the total number of hydrogen atoms are substituted by a halogen atom φ. More preferably, all are substituted. 52 | In R, the alkoxy group is a straight bond or a branched chain, and the carbon number thereof is preferably from 1 to 5 Å, more preferably from 1 to 4 Å, most preferably from 丨 to 3. Among these, R52 is preferably a hydrogen atom. R is an aryl group which may have a substituent, and the structure of the basic ring (parent ring) after removing a substituent may, for example, be a naphthyl group, a phenyl group, a fluorenyl group or the like, and may be exposed to the effects of the present invention or an ArF excimer laser or the like. From the viewpoint of light absorption, a phenyl group is preferred. The substituent may, for example, be a hydroxyl group or a lower alkyl group (linear or branched 139475.doc-33-200949439, preferably having a carbon number of 5 or less, particularly preferably Yin-based). As the aryl group of R53, it is more preferred to have no substituent. u" is an integer of 1 to 3, preferably 2 or 3, as a preferred example of the chemical spur of the acid represented by the formula (d).

[化47J

An acid generator represented by the formula (b, 〇) can be used. The other hydrazine-based acid generator which is an acid generator represented by the formula (b-Ο), for example, may be exemplified by the following formula (bl) or 〇>-2). Compound. [化48]

SOj~ ···()}—1) V / R4 SO^•...(b-2) ^9475.(100 • 34- 200949439 aryl or topographical; R4" The unsubstituted alkyl group m has at least one surface 〒 bond = shape, and the courtyard group or gasification represents an aryl group.] Table W group 'H5 and R6 at least one aryl group independently represent a substituted or unsubstituted square group. Or alkyl. R"~R3", _ ^ ❿ aryl. w, m / - means that substituted or unsubstituted aryl is preferably two or more substituted or unsubstituted:. The square base is preferably R"~R, which is substituted or unsubstituted. The aryl group:: aryl group is not particularly limited, and may be, for example, a part of a wind atom having a carbon number of 6 to 2 Å or All of them may be substituted by a decyl group, an alkoxy group, a ruthenium atom or the like. The aryl group may be a compound which is inexpensive, and the carbon is preferably a phenyl group or a phenyl group. Specifically, as the substituent of the above aryl group (IV), the leuco group is preferably a methyl group, an ethyl 'propyl group, and a n-butyl group is a butyl group 1. The substitution of the above aryl group Base alkoxy group, preferably The alkoxy group having a carbon number of w is preferably a methoxy group or an ethoxy group. As the halogen atom of the substituent of the above aryl group, it is preferred that the gas R"~~ group is not particularly limited, for example, The resolution of 1 is preferable, and the carbon number is 丨~5. Specifically, the methyl surface is exemplified by a quinone having a carbon number of a linear shape, a branched chain, or a ring. Base, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, diyl, hexyl, cyclohexyl, decyl, fluorenyl, etc., excellent in resolution, in addition J29475.doc -35- 200949439 In terms of cheap synthesis, it is better to mention ridicule. Among these, the best is that R1''~R3" are stupid. R4" means a linear, branched or cyclic alkyl group or The above-mentioned linear or branched alkyl group is preferably a carbon (four) wo, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 丨~4. The ring group represented by the above, wherein the carbon number is 4 to 15, more preferably the carbon number is (4), and most preferably the carbon number is 6 to 10. Base, better The carbon number is 丨~1〇, more preferably the carbon number is 1~8, and the most preferred carbon number is w. Further, the fluorination rate of the fluorinated alkyl group (the ratio of fluorine atoms in the alkyl group) It is preferably 1 〇 to 1% by weight, more preferably 50 to 100%. 'The addition of all hydrogen atoms with a fluorine atom can enhance the acid strength. Therefore, as R4, the best one is linear. Or a cyclic alkyl group or a fluorinated alkyl group. In the formula (b-2), R5 and R6 each independently represent a substituted or unsubstituted aryl group or an alkyl group. At least one of R5" and R6" Substituted or unsubstituted aryl. Preferably, R5" and R6" are substituted or unsubstituted aryl groups. The substituted or unsubstituted aryl group of R5 to R6 may be the same as the substituted or unsubstituted aryl group of R1'' to R3'. The alkyl group of R5'' to R6" may be the same as the alkyl group of R]"~R3". The most preferred of these are R5'~R6, both of which are phenyl groups. R4 " in the formula (b-2) is the same as the above formula (b), and the rust salt-based acid generator represented by the formulas (b-1) and (b-2) Specific examples, 139475.doc -36- 200949439 may be exemplified by triphenylsulfonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis(4-t-butylphenyl)phosphonium trifluoromethanesulfonic acid. Salt or nonafluorobutanesulfonate, triphenylsulfonium triflate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, tris(4-methylphenyl)phosphonium trifluoromethanesulfonate Acid salt, heptafluoropropane sulfonate or nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate 'Trifluoromethane sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, diphenyl monomethyl hydrazine trifluoromethane hydrochloride, heptafluoropropionate Or nonafluorobutyrate, (4-mercaptobenzophenone), a stupid base of tri-I-propionate, heptafluoropropionate or nine-gas butyl acid salt (4-methoxyl) Phenyl)diphenylphosphonium triflate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, three (4- Trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, diphenyl(indole-(4-methoxy)naphthyl)nickel trifluoromethanesulfonate Acid salt, heptafluoropropane sulfonate or nonafluorobutane sulfonate, etc., can also be used to change the anion portion of the sulfonium salt to mesylate, n-propane sulfonate, n-butane sulfonate, An anthracene salt of n-octane sulfonate. Alternatively, it may be used in the above formula (b-Ι) or (b-2) to replace the anion moiety with the following formula (b-3) or (b- 4) A rust salt-based acid generator (the cation portion is the same as (b-Ι) or (b-2)) as the anion portion shown.

[wherein, X" represents an alkyl group having at least one hydrogen atom substituted by a fluorine atom and having a carbon number of 2 to 6, and Υ" and Ζ" each independently represent at least one hydrogen atom by a fluorine atom 139475.doc • 37· 200949439 Substituting an alkyl group having a carbon number of 1 to 10.] X" is a linear or branched exudyl group in which at least one hydrogen atom is replaced by a fluorine atom. The carbon number of the alkylene group is 2 to 6, Preferably, the carbon number is 3 to 5, and the most preferred carbon number is 3. Y"'Z" is independently a direct or branched alkyl group in which at least - (iv) an atom is replaced by a fluorine atom, and the carbon number of the alkyl group is 丨~..., preferably a carbon number of 1 to 7. 'Better is the carbon number is 1~3. · The solubility in the resistive solvent is also good in the above carbon number range. The carbon number of the X" or the carbon number of the γ", z" Moreover, in the alkyl group of X"alkyl or γ", z", the more hydrogen atoms are replaced by fluorine atoms, the more the acid strength is enhanced, and the higher energy of 2()() can be increased. The transparency of light or electron beam is preferred. The proportion of the fluorine atom in the alkyl or the alkyl group is preferably 7 〇 to 10% by weight, more preferably 90 Å, and most preferably all of the hydrogen atoms are replaced by fluorine atoms. Extruded or perfluoroalkyl. In the first aspect of the invention, a compound represented by the following formulas (3G) to (35) can also be used as the photoacid generator. [化 50]

An aryl group or an alkyloxy group, which is 139475.doc • 38 · 200949439 base, a aryl group, a cryptoalkyl group or a aryl group. The compound represented by the above formula (30) is preferably selected from the group consisting of At least one of the group consisting of N-(trifluorosulfonyloxy) succinimide, N-(trifluoromethanesulfonyloxy)phthalimide, N-( Trifluoromethyl fluorenyloxy)diphenylmaleimide, N-(trifluoromethanesulfonyl);bicyclo[221]hept-5-ene-2,3-dicarboxyarminemine, N-(trifluorosulfonyloxy)naphthylimine, N-(10-camphoracyloxy)glass, imino, N-(l〇- camphor oxy) phthalate Yttrium imine, N-(10-camphorsulfonyloxy) di-p-maleimide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3 - bis-sodium imidate, N-(l〇-camphorsulfonyloxy)naphthyl quinone imine 'N-(n-octane decyloxy)bicyclo[2.2_1]hept-5-rare-2,3 - bis-sodium imidate, N-(n-octyloxy)naphthyl quinone imine, N-(p-toluenesulfonyloxy)bicyclo[2.2.1]gly-5-ene-2,3-dicarboxyanthracene Imine, N-(p-toluenesulfonyloxy)naphthylquinone Imine, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo2.1]hept-5-ene-2,3-dioxalimine, N-(2-trifluoromethylbenzenesulfonate Oxy)naphthyl quinone imine, n_(4_ = fluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3.dicarboxy-hallimine, Ν-(4-three Fluorenyl phenylsulfonyloxy)naphthylimine, fluorene-(perfluorobenzene oximeoxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, hydrazine- (all-gas benzenesulfonyloxy)naphthyl quinone imine, N-(l-naphthalenesulfonyloxy)bicyclo[2·2."heptene-ene-2,3-di-rebasic imine, N -(l-naphthyloxy)naphthylimine, Ν_(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-didecylimine, hydrazine -(nonafluoro-n-butyl decyloxy)naphthyl phenyleneimine, ν-(perfluoro-n-octane decyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine and hydrazine -(All sharp octyl sulfonyloxy) naphthyl quinone imine. 139475.doc -39- 200949439 [Chem. 51] 9 Ο R,._ \\ R 9r-s-r« ου 〇〇 (31) In the same, the same or different, each independently is an optionally substituted straight bond, a bond or a cyclic alkyl group, an optionally substituted aryl group, optionally taken a heteroaryl group or an optionally substituted aralkyl group. The compound represented by the above formula (31) is preferably at least one selected from the group consisting of diphenyl disulfone and di(4). Mercaptophenyl) monosulfone, naphthyl disulfone, bis(4-t-butylphenyl) disulfone, bis(4-hydroxyphenyl) monosulfone, bis(3-hydroxynaphthyl)disulfone, Difluorophenyl)disulfone, bis(2-fluorophenyl)disulfone, and bis(4-trifluoromethylphenyl)disulfone. [化52] 〇R"-C=N-〇-1-R" (32) CN 〇 (32) 'R!7 can be the same or different, each independently is an arbitrary substituted linear, branched Or a cyclic alkyl group - an optionally substituted aryl group, an optionally substituted heteroaryl group, or an optionally substituted aralkyl group. The compound represented by the above formula (32) is preferably at least one selected from the group consisting of α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonate).醯oxyimino)_4_methoxyphenylacetonitrile, α-(trifluoroanthracene oxyimino)-phenylacetonitrile, α-(trifluorosulfonyloxyimino)- 4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-4·methoxybenzene 139475.doc 40· 200949439 acetonitrile, α·(propylglycosylimine) _4•Methylphenyl B., and (Methanesulfonyloxyimino)·4·filled with phenylacetonitrile. [化53]

(33)

In the formula (33), 曰 can be different from each other, and each of them is independently one having an upper gas atom and one or more bromine oximes. The number of carbon atoms of the alkyl group is preferably from 1 to 5. [化54] <l18〇)p

J18- γΐ*

(34)

<R1e)q

(35) In the formulae (34) and (35), Rl9 and r20 are each independently a carbon atom such as a thiol group, a propylene group, a propyl group, a methoxy group, a cyclopentyl group, a cyclohexyl group or the like. The base, or ", H H propoxy group and the like, the number of carbon atoms of 1 to 3 is the aryl group of (b) fluorene. Preferably, the carbon atom R19 and R2G are each independently an organic group having a 1,2-naphthalene roll and having a 1,2-naphthoquinonediazide group. The organic group of the diazide group, specifically, preferably 139475.doc -41 - 200949439, exemplified by: 1,2-extracted oxime-brewed base, Cai II^:4: continued sulfhydryl, state II especially The good is (4) 6: Stuffing: 41,2' diazidosulfonyl. Stone yellow base. —#Nitrogen 4-glycol and & Chua Guandiazide-5- PW, an integer of 〇~4, and J is a single bond, and the number of carbon atoms is 聚...:5. a phenyl group, which is represented by the following formula (34a), a methyl group, a cycloalkyl group, a stretch bond or a group of the group (10), having a bond of 1 bond, a chiral amine Y / knife independently being a hydrogen atom, The alkyl group or the aryl group is a group represented by the formula (35a). Then stand as the next [化55]

In the formula (35a), 'Z22 is independently an alkyl group, a cycloalkyl group or an aryl group, and r22 is independently an alkyl group, a cycloalkyl group or an alkoxy group, · It is an integer of 〇~3. Examples of the other acid generator include bis(p-toluenesulfonyl)diazotrimethane, bis(2,4-dimercaptophenylsulfonyl)diazonium, and bis(t-butyl0 ugly). Base diazonium, bis(n-butylsulfonyl)diazononane, bis(iso-,yl)sulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, double (正@基sulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazo crater, bis(iso-diylsulfonyl)diazomethane, 1,3-bis(cyclohexylsulfonyl) Azide, 1,4-bis(phenylsulfonylazomethanesulfonyl)butane, 1,6-double (stupid & 139475.doc • 42· 200949439 sulfonyl sulfonate) Disulfonyldiazomethane, 2-(4-methoxyphenyl), such as carbarylsulfonyl)hexane, 1,1 〇 bis(cyclohexylsulfonylazoazosulfonyl) decane -4,6-(bitrione)-1,3,5-triazine, 2-(4-decyloxynaphthyl)-4,6-(bistrimethylmethyl)-1,3 Halogen-containing triazine derivatives such as 5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)isocyanate Things and so on. Among these photoacid generators, it is particularly preferred to produce a compound of an organic sulfonic acid by the action of active light or radiation.

The blending amount of PAG accounts for 〇4% by weight of the total composition excluding the solvent, preferably 5% to 30% by weight, and more preferably 5 to 2% by weight. In the first aspect of the present invention, an acid diffusion controlling agent (inhibitor) may be formulated in the photoresist composition, and the acid diffusion controlling agent has an acid controlling the acid generated by the acid generating agent due to irradiation of radiation. The diffusion in the film prevents the effects of poor chemical reactions in the unexposed regions and the like. By using the acid diffusion controlling agent, the storage stability of the photoresist composition can be improved. Further, the degree of resolution can be improved, and the change in the line width of the resist pattern due to the delay time before the electron beam irradiation and the delay time after the electron beam irradiation can be suppressed, and the process stability is excellent. Examples of such an acid diffusion controlling agent include a single-compartment amine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine or n-decylamine; diethylamine and di-n-propyl group. A diamine amine such as an amine or a heptylene amine; a trimethylamine, a tri-n-octylamine ethylamine, a tri-n-propylamine, a tri-n-butylamine, a tri-n-hexylamine, or a tri-n-pentylamine , octylamine n-heptylamine tri-n-n-decylamine di-n-decylamine, tri-n-alkylamine such as tri-n-dodecylamine; diethanolamine, triethanolamine, _ 呉 呉 呉 呉 、 、, triiso Propyl alcohol 139475.doc •43· 200949439 Amide, di-n-octanolamine, tri-n-octanolamine and other hospital-containing amines such as nitrogen-containing test compounds, test (4) compounds, test (tetra) compounds and other electron beam radiolysis Test compound. The acid diffusion controlling agent may be used singly or in combination of two or more. The blending amount of the field inhibitor accounts for 〇4% by weight of the total composition excluding the solvent, and preferably occupies 0·〇1 to 丨5 wt%. In the first aspect of the present invention, the additive may be appropriately added as needed, for example, an additive resin for improving the performance of the photoresist film, and an interface activity for improving coatability. Agents, dissolution inhibiting agents, sensitizers, plasticizers, stabilizers, fixatives, colorants, antihalation agents, dyes, pigments, and the like. The bathing agent is a component which has a function of lowering the solubility of the cyclic compound when the solubility of the test developer is too high, and attaining a moderate speed of dissolution at the time of development. ❹ Examples of the dissolution control side include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and hazardous; anthracene such as phenethylamine, benzophenone, and phenylnaphthyl steel; methyl stupid base and diphenyl Hard, two Caiji hard (four) and so on. Further, for example, a bisphenol to which an acid dissociable functional group has been introduced, a tris(hydroxyphenyl)methane to which a third butylcarbonyl group has been introduced, or the like may be mentioned. These dissolution control agents can be used alone: Two or more types are used. The amount of the dissolution controlling agent to be adjusted may be appropriately adjusted depending on the kind of the cyclic compound to be used, preferably in the total weight of the solid component, and then 5% to 50% by weight, more preferably (four)% by weight, more preferably 〇~(4) Set %. Energy, and the sensitizer is a kind of 139475.doc-44·200949439: ancient, which can absorb the irradiated radiation, and is transferred to the ι generating agent, thereby increasing the effect of the amount of acid generated, and the appearance of θ-gate light two The component of the sensitivity. The sensitizer is, for example, a benzoyl group, a acetophenone, a acetophenone, an anthracene, a phenothiazine or an anthraquinone, and is not particularly limited. These sensitizers may be used singly or in combination of two or more. The amount of the sensitizer is preferably from 〇 to 50% by weight, more preferably from 〇 to 20% by weight, more preferably 〇 to 〇 〇 by weight of the solid component (four).

The interface is a living agent system having a coating property or a stripe which can improve the photoresist composition of the present invention, and is a component (4) which is difficult to be used as a photoresist. As the surfactant, an anionic, cationic, nonionic or both of them can be used. Among these, preferred are nonionic surfactants. The nonionic surfactant has a good affinity with the solvent used in the photoresist composition, and has a better effect. Examples of the nonionic surfactant include polyoxyethylene high-grade alkyl group, polyoxyethylene high-grade benzene scale, and polyethylene glycol high-grade fatty acid, and the like. The following trade names are listed: Eft〇p (manufactured by JEMC), Megafac (manufactured by Dainippon Ink Chemical Industries, Ltd.), Flu〇rad (manufactured by Sumitomo 3m Co., Ltd.), Asahi Guard, and Surfl〇n (above, manufactured by Asahi Glass Co., Ltd.) There are no particular restrictions on each series of products such as Pepol (manufactured by Toho Chemical Industry Co., Ltd.), κρ (manufactured by Shin-Etsu Chemical Co., Ltd.), and Poly flow (manufactured by Kyoei Oil & Fats Chemical Co., Ltd.). The blending amount of the surfactant is preferably 〇 2 by weight based on the total weight of the solid component. /. More preferably, it is % by weight, more preferably 0 to 0.1% by weight. Further, by blending a dye or a pigment, the latent image of the exposed portion can be made visible, and the effect of blooming at the time of exposure can be alleviated. Further, the adhesion to the substrate can be improved by blending the 139475.doc -45-200949439 agent. In order to prevent the deterioration of the sensitivity when the acid diffusion controlling agent is formulated, the shape of the resist pattern, the stability of the retardation, and the like are further increased, and the optional component may contain an organic (tetra) or oxo acid or a derivative thereof. Further, these compounds = can be used in combination with an acid diffusion controlling agent' or can be used alone. As the organic acid, for example, malonic acid, a bar acid, a sucrose acid, a chopped acid, a benzoic acid, a salicylic acid or the like is preferable. Examples of the slave oxyacid or a derivative thereof include acid filling, di-n-butyl phosphate, Wei diphenyl s, etc., or such vinegar, etc., phthalic acid, phosphonic acid, di-decyl phosphonate, Di-n-butyl phosphonate, phenylphosphonic acid, phosphinium hydrazine, δ θ, phosphonic acid, glycerol, etc., such as phosphinic acid, phosphinic acid, etc. Derivatives such as vinegar, and particularly preferred among these are phosphonic acids. When a photoresist pattern is formed, first, a coating method such as spin coating, tape casting, or roll coating is applied to a substrate such as a germanium wafer, a gallium arsenide wafer, or an aluminum wafer. The photoresist composition of the present invention, thereby forming a photoresist film.亦 It is also possible to apply a surface treatment agent to the substrate in advance. Examples of the surface portion include a dream burning coupling agent such as a hexazone or a hydrolyzable polymerizable decane coupling agent having a polyvalent group, a tackifying coating agent or a:-agent (polyvinyl acetal, An acrylic resin, a vinyl acetate-based oxo (tetra) 1 (tetra) ester, or the like, and a coating agent in which the base agent and the inorganic fine particles are mixed. A protective film may be formed on the resist film in order to prevent intrusion of an amine or the like floating in the atmosphere as needed. By forming a protective film, the following conditions can be prevented: 139475.doc -46 - 200949439 Condition: A compound which can react with an acid such as an acid generated by radiation in a photoresist film and an amine floating as an impurity in the atmosphere The reaction is inactivated, and the photoresist image is deteriorated, and the sensitivity is lowered. As the material for the protective film, a polymer having water solubility and acidity is preferred. For example, polyacrylic acid, polyvinyl sulfonic acid, etc. are mentioned. In order to obtain a fine pattern with high precision, and in order to reduce degassing during exposure, it is preferred to perform heating before irradiation (before exposure). The temperature of the heating Φ may vary depending on the composition of the photoresist composition, etc., preferably from 20 to 250 ° C, more preferably from 40 to 150 ° C. Then, the photoresist film is exposed to a desired pattern by using a radiation such as a KrF excimer laser, an extreme ultraviolet ray, an electron beam or a krypton line. The exposure conditions and the like can be appropriately selected depending on the composition of the photoresist composition and the like. In the first aspect of the present invention, in order to stably form a fine pattern having high precision, it is preferred to perform heating after irradiation (after exposure). The exposure temperature after exposure (4) exposure bake, PEB) may be changed according to the composition of the photoresist composition, etc., preferably 20 to 250 ° C, more preferably 40 to 150. (:. Then, the exposed photoresist film is developed with an alkaline developing solution, whereby a specific light can be formed. As the above-mentioned secret developer, for example, a single-, two- or three-burning solution can be used. Alkylamines, mono-, di- or tri-alcoholamines, heterocyclic amines, tetra-ammonium hydroxide (10), etc. TMAH) more than one of the test compounds, preferably H0% by weight, more preferably 5% by weight of an aqueous test solution. A suitable amount of the enzyme such as methanol, ethanol or isopropyl alcohol or the above surfactant may be added to the test developer. Of these, it is especially preferred to add ^(iv) 139475.doc -47- 200949439% by weight of isopropanol. Further, when using the developing solution of the alkaline aqueous solution of 匕3, it is generally washed with water after development. According to the invention, the photo-dissociation inhibiting group is detached by exposing the photoresist film to a desired pattern by using a radiation such as ultraviolet light, electron beam or X-ray by a (4) excimer thunder. Or structural change: 丄 thereby dissolving it in the developer. On the other hand, the unexposed portion of the pattern is insoluble in the test liquid, and as a result, a fine pattern is formed, which can be used as the purpose of the first resist substrate. That is, it is preferable that the average substitution ratio is the first hindrance substrate which is defined in the first aspect of the present invention and has an acid dissociable dissolution inhibiting group, or the film containing the green substrate is insoluble in the (iv) developing solution. = insoluble in the developer solution, the better non-solubility is developed according to the size of the pattern formed, the type of alkaline developer used, etc., and is different - thus it is impossible to specify 2 鄕 hydrogen When the tetramethyl oxidized aqueous solution is used as an in-situ developer, it is insoluble in the dissolution rate of the developer as a thin film containing the photoresist substrate, preferably not less than m/sec, especially preferably Not full 〇·5 nm/second. Further, depending on the case, an organic or inorganic antireflection film may be provided between the substrate and the photoresist film after the alkaline development. After the photoresist pattern is formed, the pattern wiring substrate can be obtained by _. The etching can be carried out by a dry method using a plasma gas, using a known method such as a wet solution such as an inert solution, a vaporized copper solution or a gasified iron solution. After forming the photoresist pattern, it can also be plated with forged copper, solder ore, money recording, ore gold. β 139475.d, -48- 200949439 Strong alkaline solution using organic solvent or alkaline stronger than alkaline developer , peeling off the residual photoresist pattern after etching. Examples of the organic solvent include PGMEA, PGME, EL, (IV), and tetrahydrofuran. Examples of the strongly alkaline aqueous solution include: 0% by weight of an aqueous solution of sodium oxynitride, and 20% by weight of hydrogen and oxygen (IV). Aqueous solution. As the peeling method, for example, an impregnation method, a spray method, or the like can be listed. Further, the wiring substrate on which the photoresist pattern is formed may be a multilayer wiring substrate or a small aperture through hole. The fistula can be formed by forming a photoresist pattern by using the iridium resist composition of the present invention, and then vapor-steaming the metal, followed by a method of dissolving the photoresist pattern by a solution, that is, a stripping method. A semiconductor device can be fabricated by a microfabrication method using the ith photoresist composition of the present invention. The semiconductor device can be used in various devices such as an electric product (electronic device) such as a television receiver, a mobile phone, a computer, a display, and a computer controlled by a computer. Hereinafter, a second aspect of the present invention will be described. Hereinafter, the cyclic compound and the resist substrate of the second aspect of the present invention will be specifically described. The cyclic compound of the second aspect of the present invention (hereinafter sometimes referred to as a second cyclic composition) and the photoresist substrate (hereinafter sometimes referred to as a second photoresist substrate) are represented by the following formula B- 1) A cyclic compound represented by any one of ~(Β·6). These compounds are characterized in that R' has a specific stereoscopic relative configuration. 139475.doc -49- 200949439 [Chem. 56]

, -1) is different from the stereo configuration of the formula (B-4) R'. Formula (4) and formula (Β·5), _·3) and formula, nasal material The above-mentioned three-dimensional liquid is dissolved in a two-door solution. ^ cloth solvent or display

In the second aspect of the state, the pure form of the stereoscopic relative configuration of any one of the formula (Β·1)~叫), or the formula (Β_4)~(Β·人不之异异In the case of a mixture, the coating: medium or 'cold-solution property becomes higher, so it is better. The property when the substrate is blocked ^. ^ </ br> is used together with the formula (Β:) :^

The ratio of any of the isomers of the butyl is 90% or more. The ratio of the presence of V = 'isomers can be determined by the 1H-dirty assay. In the above formula (Β-1) to (Β_6), R is an acid dissociable dissolution inhibiting hydroxyl group, respectively. 4 139475.doc -50- 200949439 In the second cyclic compound of the present invention, it is preferred that the compound oxime molecule contains at least two or more acid dissociable dissolution inhibiting groups. Since the second cyclic compound of the present invention has an increased solubility in an alkaline developing solution due to the action of an acid, it is preferred to contain an alkali-soluble group. Examples of the alkali-soluble group include a hydroxyl group, a sulfonic acid group, a phenol group, a carboxyl group, and a hexafluoroisopropanol group [-(C(CF3)2〇H). Preferred are a phenyl group, a decyl group and a hexafluoroisopropanol group, more preferably a phenol group or a carboxyl group. The acid dissociable dissolution inhibiting group is substituted for the substituent of the hydrogen atom of the OH in the above-mentioned soluble group, preferably -c(Riia)(Ri2aKRi3a), -C(Rl4a)(Rl5a)(〇Rl6a) , -CO-〇C(Rlla)(R12a)(R13a). Here, R&quot;a to RUa each independently represents a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group or an aryl group. R14a&amp;Ri5a independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group. Ri ^ represents a substituted or unsubstituted alkyl group, a ring-based group, an alkenyl group, an aryl group or an aryl group. Further, two of RUa, R12a, and R13a, or two of R14a, R15a, and Ri6a may be bonded to form a ring.

The alkyl group, the cycloalkyl group, and the aralkyl group in R1 la to Rl 6a may further contain a group as a substituent: a cycloalkyl group, a hydroxyl group, an alkoxy group, a pendant oxy group, an alkylcarbonyl group, an alkoxycarbonyl group. , alkyl carbonyloxy group, alkylaminocarbonyl group, alkylcarbonylamino group, alkyl group, alkyl group, alkyl group, alkyl group, alkyl sulfonyl group, amine sulfonate Sulfhydryl, pixel atom, cyano group, etc.

The aryl group or the alkenyl group in R11a to Rl3a and R16a may further contain a substituent as a substituent: an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a pendant oxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkane group. Alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonyl 139475.doc -51 - 200949439 Amino, alkylsulfonyl, alkyl decyl, alkylsulfonylamino, alkylaminosulfonyl Base, aminosulfonyl group, halogen atom, cyano group, and the like.

The alkyl group, cycloalkyl group, alkenyl group or aralkyl group of Rna~Rlea may also have a sulfo group, a thiol group, a aryl group, an ester group, a decylamino group, an amino carboxylic acid sulfonate group, a urea group, and the like in the chain. Sulfonyl, sulfhydryl. The acid dissociable dissolution inhibiting group is preferably a total carbon number of 4 or more, more preferably a total carbon number of 6 or more, more preferably a total carbon number of 8 or more. Further, it is preferred that the acid dissociable dissolution inhibiting group contains an alicyclic structure or an aromatic oxime structure. Examples of the alicyclic structure include a cyclopentane residue, a cyclohexane residue, a norbornane residue, and an adamantane residue. Examples of the aromatic ring structure include a benzene residue, a naphthalene residue, and an anthracene residue. The alicyclic crucible and aromatic ring structures may have a substituent at any position i. The preferred embodiment of the non-acid dissociable dissolution inhibiting group is not limited to these. [化57] CH3 (B-9)

(B-13) 139475.doc -52- 200949439 [化58] -°ί^7〇 (B-1 5) x&gt;_

HaC-(B~l 4) 丨2 Π a c-c H3C- (B-16) H3C-(B-X 7) e Lu

(B-l 8) [Chem. 59] (B-l 9)

P , 0 (B-2 0) (B-2 1)

(B-2 5) (B-2 4) [60] ~〇-C2-8-〇-C2-〇-^^^ (B-26) (B-27)

P (B-2 8) (B-29)

(B-31) 139475.doc -53- 200949439 [Chem. 61]

(B-3 5) (B-3 6) (Formula (B-35) (B-36) ir represents the above formula (B 9) to (b 34), and the following formula (r-1), (r -2) Any of the substituents indicated.) _ [Chem. 62] ~°^〇~iSs (Μ) (r-2) R| of the formula (B-1) to (B-6) a hydroxy group or an ether group (〇Ra: ... is a linear aliphatic hydrocarbon group having a carbon number of 1 to 10, a branched aliphatic hydrocarbon group having a carbon number of 3 to 8, and a monocyclic ring having a carbon number of 3 to 8; a cyclic aliphatic hydrocarbon group, a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of 4 to 10, a stupid group, a naphthyl group, a linear aliphatic nicotine group having a carbon number of ❹ 1 to 12, and a carbon number of 3 a polycyclic hydrocarbon group having a branch bond of ～12, a monocyclic cyclic fat group having a carbon number of 3 to 12, a polycyclic cyclic aliphatic nicotinyl group having a carbon number of _ (4), a stupid base, a p-phenylbenzene group a group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (4), or a combination of two or more of the substituents And constitute a substituent. 139475.doc -54- 200949439 [Chem. 63]

A ^Y (R&gt;x &lt;B-7) l R2Jy (&amp;8): Γ), R is an acid dissociative dissolution inhibitory group or a meridine, a 5 ^ is the same and then 'acid dissociable dissolution Example of suppression base and the above-mentioned postal code

In the formula =), 'Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, and an aromatic group represented by the formula (B-7). fR2 is a hydrogen atom, a substituted or unsubstituted carbonic acid group having a carbon number of (4), a substituted or unsubstituted carbon number of 3 to a branched aliphatic hydrocarbon group, substituted or not a substituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these substituents base. y is an integer from 1 to 4. Preferably, R 'is a monocyclic cyclic aliphatic nicotine group having a carbon number of 3 to 丨2, a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of 4 to 10, a phenyl group, and a p-phenylene group. a 't-butylphenyl group, a naphthyl group, an aromatic diradical group represented by the above formula (B-7), a substituent represented by the above formula (B-8), or two or more of the substituents Substituents formed by combination. Further, the plurality of Rs in the respective formulae (B-1) to (B-6) may be the same or different from each other. The same is true for R/. In the above formulae (B-1) and (B-4), R is a methyl group, a phenyl group or a 4-isopropylphenyl group, and R is a compound of the above formula (B-9), which is not the first aspect of the present invention. 2 ring 139475.doc • 55- 200949439 Compound. However, it corresponds to the second photoresist substrate of the present invention. Regarding the isomers of the above formulas (B-1) to (B-3) and the isomers of the formulae (B_4) to (B-6), which isomers exhibit superior properties in stereoisomeric configuration due to R'R 'The combination is different and cannot be specified. However, when the ruler is the above formula (B-9) and R' is a phenyl group, the isomer of the stereoscopic relative configuration of (B1) to (B_3) and the isomer of (B_4) to (B-6) In comparison, the sensitivity and resolution of the photoresist substrate are further improved. In the second aspect of the present invention, the formula (B_1} or (B_4) represents a group represented by the formula (B-9), and R is an indenyl group, a phenyl group, or a 4-isopropyl group. The cyclic compound of a phenyl group can be particularly preferably used as a photoresist substrate. The second cyclic compound (second photoresist substrate) of the present invention, for example, the compounds of the above (B-1) and (B-4) R is a hydroxyl group, can refer to the literature (j〇urnai

Organic Chemistry, V〇l. 54, 1305~1312 (1989)) When the compound of the formula (B-1) is synthesized by this method, a reaction time of from 68 hours to 21 days is required. Further, in the case of synthesizing the compound of the formula (B_4), it is necessary to use a different recrystallization solvent such as decyl alcohol or ethanol depending on the type of R. Therefore, it is necessary to find a recrystallization solvent based on R, and it is not a method which can be widely used. Therefore, it is preferred to manufacture by the method of the second bear sample of the present invention described below. The manufacturing method of the second aspect of the present invention is carried out in the following manner: a polyphenol compound selected from the group consisting of resorcin, pyrogallol, i'2,3,5-tetrahydrobenzene and an acid catalyst In the mixture of the solid organic sulfonic acid, an alcohol having a concentration of 9 〇t: or more is added as a solvent, and then an aldehyde represented by the following formula (B_24) is added. I39475.doc -56-200949439

The reaction solution is prepared as a compound, and subjected to a cyclization condensation reaction at a temperature of 9 〇〇 c or more and 15 〇 c &gt; c or less. Thereby, a cyclic compound represented by the following formula (B_^-(Β-3') can be produced. [Chem. 64] Rr - CHO (B-24)

(wherein R' represents the same group as R| shown in the above-mentioned second cyclic compound of the present invention.) By the production method, it is selectively suppressed, and all exist on the same side (formula) a stereoisomer of (in the case of ruthenium or the like, on the upper side of the paper). Therefore, the purely soluble inhibitory group is acid-dissolved by a known method, whereby the formula (B-1) to (B-3) can be produced. ) a cyclic compound represented.

In the second aspect of the present invention, the acid catalyst which is a strong right flavonoid is exemplified by a solid-state acid. Specifically, p-toluene acid can be mentioned. Further, the boiling point of the solvent is 9 (rc or more alcohol, propylene glycol, glycerin, or cyclohexanol. The type of the isomer: the reaction temperature of the ethylene is two or more, and the reaction temperature is 15). ^ The proportion of unsatisfied animals increased. Another ιΓ is heterogeneous. On the other hand, if the reaction time is more than the reaction system, the 139475.doc can be manufactured in a very short time from 1 to 57 to 200949439 hours to 24 hours. When the acid dissociable dissolution inhibiting group is introduced into the cyclic compound represented by the above formula (B-1') to (B-3), for example, a halide having an acid dissociable dissolution inhibiting group can be used. Specific examples of the dentate include brominated compounds, vapors, and fluorides. As the reaction example, a catalyst or a condition similar to the previously known method, such as a condensation reaction in which a base reactant is present, a coupling reaction between a transition metal catalyst and a basic reactant, and the like can be employed. Further, in the manufacturing method of the second aspect of the invention described above, the reaction temperature is less than 90. (:, a mixture of the isomers represented by the formula and the isomers of the formula (B-4) to (B-6) wherein R is a hydroxyl group. The mixture is separated by recrystallization or the like. The intermediate of the formula (B_4) to (B_6) can be obtained. In this case, the 'catalyst and the alcohol are not limited to the above, and an inorganic acid such as hydrochloric acid or an alcohol having a lower boiling point can be used. Next, the second aspect of the present invention The second photoresist composition of the present invention contains the second photoresist substrate of the present invention and a solvent. The second photoresist composition of the present invention is described. 2 The solvent used in the photoresist composition is as described in the first aspect. The components other than the solvent in the composition, that is, the amount of the photoresist solid component are as described in the first aspect. In the second photoresist composition, when it is necessary to enhance the sensitivity, a photoacid generator (PAG) or the like is generally included as a chromophore as needed. The photoacid generator is not particularly limited and can be used as a chemical increase 139475. Doc -58- 200949439 The photoresist is disclosed by an acid generator. The acid generator is as described in the first aspect. In the second aspect of the present invention, an acid diffusion controlling agent (inhibitor) may be formulated in the radiation sensitive composition, and the acid diffusion controlling agent may be produced by an acid generator by controlling radiation. The diffusion of acid in the photoresist film prevents the adverse chemical reaction in the unexposed region, etc. By using the acid diffusion control agent, the storage stability of the photoresist composition can be improved. Further, Φ can improve the resolution. The degree of change in the line width of the photoresist pattern caused by the delay time before the electron beam irradiation and the delay time after the electron beam irradiation can be suppressed, and the process stability is excellent. In the second aspect of the present invention, an additive containing a mixture of additives, for example, an additive resin for improving the properties of the photoresist film, for improving the coating may be appropriately added as needed. a surfactant, a dissolution inhibitor, a sensitizer, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a pigment ruthenium, etc. The dissolution control agent is as described in the first aspect. The sensitizer is as described in the first aspect. The surfactant is as described in the first aspect. In addition, by formulating a dye or pigment, the latent image of the exposed portion can be made visible. It is possible to improve the adhesion to the substrate by blending the subsequent auxiliary agent. In order to prevent the deterioration of the sensitivity when the acid diffusion controlling agent is formulated, the shape of the resist pattern, the retardation stability, and the like are improved. The optional component may further comprise 139475.doc -59-200949439 containing an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof. Further, the person may be used in combination with an acid diffusion controlling agent, or may be used alone. The acid-repellent system is described in the first aspect. When the photoresist pattern is formed by using the second photoresist composition of the present invention, first, a coating method such as spin coating, cast coating, or roll coating is used. The second photoresist composition of the present invention is applied onto a substrate such as a wafer, a wafer, or a coated wafer to form a photoresist film. The surface treatment agent may also be applied to the substrate in advance as needed. The surface treatment agent is as described in the first aspect. A protective film may be formed on the resist film in order to prevent intrusion of an amine or the like floating in the atmosphere as needed. By forming the protective film, it is possible to prevent the reaction between the acid generated by the radiation in the photoresist film and the compound which reacts with the acid such as an amine floating in the atmosphere as an impurity, thereby causing the reaction to be inactivated. The photoresist image is deteriorated and the sensitivity is lowered. As the material for the protective film, a polymer having water solubility and acidity is preferred. For example, polyacrylic acid, polyvinyl sulfonic acid, etc. are mentioned. In order to obtain a fine pattern with high precision, and in order to reduce the deaeration of the exposure, it is preferable to perform heating before irradiation (before exposure). The twisting temperature may vary depending on the composition of the photoresist composition, etc., preferably 20 to 250 ° C, more preferably 40 to 15 ° t. Then, the light-receiving film of the KrF excimer laser, the extreme ultraviolet ray, the electron beam or the X-ray is used to expose the photoresist film to a desired pattern. The light condition or the like can be appropriately selected depending on the composition of the photoresist composition and the like. In the second aspect of the present invention, in order to form a fine pattern with high precision, it is preferable to heat the ray after irradiation (after exposure) 139475.doc • 60 - 200949439. The heating temperature after exposure (ρ varies depending on the composition of the photoresist composition, etc., preferably 20 to 250. (:, more preferably 4 〇 15 15 。 疋 疋 ' 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用The photoresist is developed, whereby a specific photoresist pattern can be formed. The description of the above-mentioned test 9. The liquid-liquid system, as in the first aspect, can also be baked after the above-mentioned experimental development according to the situation. In the case of Φ, an organic or inorganic anti-reflection film may be disposed between the substrate and the photoresist. After the photoresist pattern is formed, the pattern wiring substrate can be obtained by using _. (4) Drying by using plasma gas After the surname is engraved, a known method such as a wet solution such as an inert solution, a gas 1 copper solution or a ferric chloride solution can be used to carry out the recording of the photoresist pattern, and then the steel can be recorded and plated. #锡镀,镀镀For the gold plating, etc., the residual photoresist pattern is removed by using the organic solvent m (four) poplar liquid, and the organic solvent is selected as the above organic solvent, such as ΕΑ, PG, PGME, 扯, acetone, tetrahydrogen, etc.; List: 1 to 20% by weight of aqueous sodium hydroxide solution, and 1 to 20% by weight of an aqueous solution of potassium hydroxide. As a peeling method, a misting method, etc., a wiring board in which a pre-resistance pattern is formed can be multi-layered, and a village has a small through-hole. The wiring substrate is formed by the following method: after forming the photoresist pattern using the composition and the composition, vacuum-salting the metal, and then using the solution to dissolve the photoresist pattern (4), that is, the dissociation method. Doc 200949439 When the second photoresist composition of the present invention is used to perform ultrafine processing using a lithography method such as far ultraviolet light or electron beam, a fine pattern can be formed with high sensitivity, high contrast, and low line edge roughness. According to the microfabrication method of the second aspect of the present invention, a semiconductor device such as a ULSI (Ultra Large Scale Integration), a large-capacity memory device, or a super-high-speed logic device can be manufactured. The photoresist substrate of the third aspect of the present invention (hereinafter sometimes referred to simply as the third photoresist substrate) contains a cyclic compound which is represented by the following formula (C4) to (c_3). Either The plurality of R in the formula are respectively an acid dissociable dissolution inhibiting group or a hydroxyl group containing an alicyclic structure, and the average substitution rate of the acid dissociable dissolution inhibiting group is 20 to 60%.

[wherein R' represents a hydrogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and carbon, respectively. a monocyclic cyclic aliphatic hydrocarbon group of 3 to 12, a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of 4 to 1 fluorene, a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, and a naphthalene a substituent represented by the formula (C-4), a substituent represented by the formula (c-5), or a combination of two or more of the substituents. 139475.doc • 62· 200949439 Substituent [ (R)x (C-4) (wherein R is a dissociative dissolution inhibiting group or a meridine group containing an alicyclic structure, and x represents an integer of ～5. When 4 2 or more, 1 is the same. Can be different [Chem. 67] ❹ c- -Af (C-5) (wherein Ar represents phenyl, p-phenylphenyl, p-tert-butylphenyl, naphthyl, or formula (C-4) The aromatic group represented by R1 and R2, respectively, a hydrogen atom, a substituted or unsubstituted carbon atom having a carbon number of (4), and a substituted or unsubstituted carbon number of 3 cores. Aliphatic hydrocarbon group, substituted or not taken Instead, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having a carbon number of (4), or a combination of two or more of these groups may be used. An integer of W. When 丫 is 2 or more, r1 and r2 may be the same or different.)] - the average substitution rate in the month of the month, as described in the description of the second aspect. The cyclic compound of (c_33), when it is an acid dissociable dissolution inhibiting group or a meridine represented by the formula (c_1) kg, the average substitution rate of the acid dissociated solvent-based base represented by the formula (C_34) is 35. ～45%, when a small amount of acid dissociative dissolution inhibiting group is detached during exposure, the /glutinability in the liquid can be greatly improved. Therefore, the sensitivity as a photoresist can be improved. 139475.doc •63- 200949439 - Aspect ' ^ The average substitution rate is 45, the fine pattern formed is insoluble in the developer solution, so that the smoothness of the side wall surface of the desired fine pattern is less likely to occur, and the height of the wall surface is lowered. In terms of aspect, it is better. As the proposed photoresist, the most money-based The difference between the resolution and the I is different. However, if the average substitution rate is 20 to 60%, both the sensitivity and the resolution show practically no problem, and it is preferable that 35 ～50%. The cyclic compound of the third aspect of the present invention (hereinafter sometimes referred to simply as the third cyclic compound) increases the solubility in an alkaline developing solution due to the action of an acid. The alkali-soluble group is contained. Examples of the alkali-soluble group include a hydroxyl group, a sulfonic acid group, a phenol group, a carboxyl group, a hexafluoroisopropanol group [-(C(CF3)2〇H), etc., preferably a phenol group. A carboxyl group or a hexafluoroisopropanol group is more preferably a phenol group or a carboxyl group. The acid dissociable dissolution inhibiting group is a substituent replacing the hydrogen atom of OH in the above-mentioned alkali-soluble group, and preferably _c(Rua)(Ri2a)(Rm), -C(R14a)(R15a)( 〇R16a), _CO_〇c(Rna)(Ri2a)(Ri3a). Further, the acid dissociable dissolution inhibiting group of R of the above formulae (C-1) to (C-4) contains an alicyclic structure. Here, R11a to R1Sa each independently represent a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group "Rlu~Ri3a", and each of them contains a cycloalkyl group. Rua and R1Sa each independently represent a hydrogen atom, or a substituted or unsubstituted sulphonyl group or a cycloalkyl group. 0a represents a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, and any one of them contains a cycloalkyl group. Further, two of Rlla, R丨, R]3a, or 139475.doc • 64·200949439 RMa, R1Sa, and Riea may be bonded to form a single ring structure or a polycyclic structure.

The alkyl group, the cycloalkyl group and the aryl group in Rlla to Rl6a may further contain a group as a substituent, a cycloalkyl group, a hydroxyl group, an alkoxy group, a side fluorenyl group, a alkyl group, an alkoxycarbonyl group, an alkane group. Carbocarbonyloxy, alkylaminocarbonyl, alkylcarbonylamino, alkylsulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino group, amino group , ginseng atoms, cyano groups, etc. Ο

The aryl group and the dilute group in R1 la to Rl 3a and Rl 6a may further contain a group as a substituent: an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a pendant oxy group, an alkylcarbonyl group, an alkoxy group. Carbonyl group, alkylcarbonyloxy group, alkylaminocarbonyl group, alkylcarbonylamino group, alkyl group, succinyloxy group, 9-alkyl amide group, alkylaminosulfonyl group, amine sulfonate Sulfhydryl, pixel atom, cyano group, etc.

The alkyl, cycloalkyl, alkenyl or aralkyl group of Rudh may also have an ether group, a thioether group, a carbonyl group, an ester group, a decylamino group, a urethane group 'ureido group, respectively, in the chain. Base 'hard base. The acid dissociable dissolution inhibiting group is preferably a total carbon number of 4 or more, more preferably a total carbon number of 6 or more, more preferably a total carbon number of 8 or more. Examples of the alicyclic structure contained in the acid dissociable dissolution inhibiting group of R of the above formulae (C-1) to (C-4) include a ring residue, a cyclohexane residue, and a norborne burn residue. , adamantane residue, and the like. Further, the acid dissociable dissolution inhibiting group may also contain an aromatic ring structure. As a ring structure, a benzene residue, a naphthalene residue, an anthracene residue, and the like can be used. The alicyclic structure or the quinone 0 aromatic ring structure may have a specific substitution at any position. 139475.doc -65 - 200949439 The following is a preferred example of the acid dissociable dissolution inhibiting group, but the third aspect of the present invention is not Limited to these. [68]

(C-1 0) (C-1 1) [Chem. 69] -C - C-C H3C- 0-C h3c (C-1 2) (C-1 3)

(C-1 4) (c-1 5) H2 • c-o

(C-1 6) p o-c2-o

.0 (c-1 7) [化70]

(C-2 0) (C-21) 139475.doc -66 200949439 (C-22) (C-2 3) [Chem. 71]

❹ (C-2 4) I. (C-2 5) · 〇.

0-C. (C-26) (C-2 7) [化72] -O-C2- h3c

(C-28) ?1

(C-2 9)

(C-30) (C-3i) (wherein r represents each of the substituents represented by the above formulas (C6) to (c_29).) In the above formula (C-1) to (C_3) Rl is preferably a linear aliphatic ketone group having a carbon number of 丨~12, a branched aliphatic hydrocarbon group having a carbon number of 3 to 12, a stupid base, and a Tsai: (C 4) The aromatic group or the substituent represented by the formula (c-5) is more preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, or a phenyl group. . In the above formula (C-4), the preferred acid dissociable dissolution inhibiting group of the ruler is the same as R of the formula 139475.doc-67-200949439 (C-1) to (C-3). Preferably, χ is an integer of 1 to 2. In the above formula (C-5), Ar is preferably a phenyl group or a naphthyl group. R1 and R2 are preferably a hydrogen atom, a methyl group or an ethyl group. y is preferably an integer of 1 to 2. The preferred cyclic compound to be used in the third photoresist substrate of the present invention is represented by the following formula (C-33), wherein R is a substituent represented by the formula (C-34) or a hydroxyl group. The average substitution rate of the substituent represented by (C-34) is 35 to 50% by weight of the cyclic compound. [化73]

Further, a preferred cyclic compound to be used in the third photoresist substrate of the present invention is represented by the following formula (C-33): wherein R is a substituent represented by the formula (c-34,) or a hydroxyl group, respectively. The average substitution rate of the substituent represented by (C_34·) is a cyclic compound of 20 to 60%. [化74]

139475.doc • 68 - 200949439 (C-34) The above cyclic compound can be used as a resist substrate which is used for ultrafine processing by lithography such as extreme ultraviolet light or electron beam. A photoresist composition according to a third aspect of the present invention (hereinafter sometimes referred to simply as a third photoresist composition) contains the above-mentioned photoresist substrate and a solvent. The amount of the cyclic compound is preferably from 50 to 99.9% by weight, more preferably from 75 to 95% by weight, based on the total amount of the composition other than the solvent. When the ring-shaped 9 &amp; compound (4) is used as the photoresist (4), it may be used alone or in combination of two or more kinds within the range which does not impair the effects of the present invention. The solvent used in the photoresist composition of the third aspect of the invention is as described in the i-th aspect. The amount of the component other than the solvent in the composition, i.e., the solid content of the photoresist, is as described in the first aspect. When the molecule of the substrate contains chromophore ® which is active against EUV and/or electron beam and exhibits the ability to act as a silk alone, the third photoresist composition of the present invention does not require special additives, but needs to be reinforced as light. When the meniscus (sensitivity) is blocked, a photoacid generator (pAG) or the like is generally included as a 'chromophore group' as needed. The photoacid generator is as described in the first aspect. In the third aspect of the present invention, an acid diffusion controlling agent (inhibitor) may be formulated in the photoresist composition. The acid diffusion controlling agent has an acid controlling the acid generated by the acid generating agent due to irradiation of radiation. The diffusion in the film prevents the adverse chemical reaction in the unexposed areas and the like. By using the acid diffusion 139475.doc -69 - 200949439 control agent, the stability of the photoresist composition can be improved. Further, the degree of resolution can be improved, and the change in the line width of the resist pattern due to the delay time before the electron beam irradiation and the delay time after the electron beam irradiation can be suppressed, and the process stability is extremely excellent. The acid diffusion controlling agent is as described in the first aspect. In the third aspect of the invention, in addition, it is possible to add an additive which is miscible according to the necessity, for example, for improving the performance of the photoresist film: an additive resin for improving coating properties. Surfactant, dissolution inhibitor 'enhanced 1, plasticizer, stabilizer, colorant, j material, pigment, etc. Soaps The dissolution control agent is as described in the first aspect. The sensitizer is as described in the first aspect. The surfactant is as described in the description of the first aspect. Further, by blending a dye or a pigment, the latent image of the exposed portion can be made visible, and the effect of blooming at the time of exposure can be alleviated. Further, the adhesion to the substrate can be improved by blending the adhesive agent'. In order to prevent the deterioration of the sensitivity when the acid diffusion controlling agent is formulated, the shape of the resist pattern, the retardation stability, and the like are further increased, and further, an organic (tetra) or oxo acid or a derivative thereof may be contained as an optional component. Further, the I = acid diffusion controlling agent may be used in combination, or may be used alone, as described in the description of the first aspect. When the photoresist pattern is formed, 'the first photoresist composition of the present invention is coated on a substrate such as a round or a gallium material with a circle by a coating method such as spin coating or flow coating. Thereby a photoresist 139475.doc 200949439 film is formed. The surface treatment agent may also be applied to the substrate in advance as needed. The surface treatment agent is as described in the first aspect. A protective film may be formed on the resist film in order to prevent intrusion of an amine or the like floating in the atmosphere as needed. By forming a protective film, it is possible to prevent the following conditions: Inactivation by an acid which is generated by radiation in a photoresist film and a compound which reacts with an acid such as an amine floating in the atmosphere as an impurity, The photoresist image is deteriorated and the sensitivity is lowered. As the material for the protective film, a polymer having water solubility and acidity is preferred. For example, polyacrylic acid, polyvinyl sulfonic acid, etc. are mentioned. In order to obtain a fine pattern with high precision, and in order to reduce degassing during exposure, it is preferred to perform heating before irradiation (before exposure). The heating temperature may vary depending on the composition of the photoresist composition, etc., preferably 20 to 25 (TC, more preferably 40 to 150. (:. Further, using KrF excimer laser, extreme ultraviolet light, electrons) The beam or the radiation such as the line is irradiated, and the photoresist film is exposed to a desired pattern. The exposure conditions and the like can be appropriately selected according to the composition of the photoresist composition, etc. In the third aspect of the present invention, in order to stably It is preferable to form a fine pattern with high precision, and it is preferable to perform heating after irradiation (after exposure). The heating temperature (PEb) after exposure can be changed according to the composition of the photoresist composition, etc., preferably 20 to 250 ° C. More preferably, it is 40 to 150 ° C. Then, the exposed photoresist film is developed with an alkaline developing solution, whereby a specific photoresist pattern can be formed. The above-mentioned experimental developer is as described in the explanation. &quot; 139475.doc -71- 200949439 When the third photoresist substrate of the present invention is used, the photoresist film is exposed to a desired state by using radiation such as KrF excimer Leihu purple wire, electron beam or x-ray. ® case, and the acid dissociation dissolution inhibitor is detached, The structure is changed, thereby dissolving it in the alkaline developing solution. On the other hand, the unexposed portion of the pattern is insoluble in the in-situ developer, and as a result, fine (four) is formed, and the purpose as a photoresist substrate can be achieved. It is desirable that the photoresist substrate having an average substitution ratio as defined in the third aspect of the present invention and having an acid dissociable dissolution inhibiting group or a thin shirt containing a filament is dissolved in the developer. The non-rotation property in the liquid, the good non-solubility is the same according to the size of the formed (4), the conditions of the tested developer solution, and the purpose is not possible - generally, 2.38% hydrogen ^ = 曱 钱 money soluble (4) As a hybrid developing material, as a film containing a photoresist substrate, the insolubility expressed by the developing solution dissolution rate, preferably not less than nanometer/second, particularly preferably less than 5 nm/sec. In addition, 'according to the situation' may also include post-baking treatment after the above-mentioned qualitative development. 'A (four) or inorganic anti-reflection film may be disposed between the substrate and the photoresist film. After forming the photoresist pattern, Etching can obtain a pattern wiring substrate. Money can be obtained by using plasma The dry etching of the body is carried out by using a wet solution such as an alkaline solution, a vaporized copper solution or a vaporized iron. After the photoresist pattern is formed, it can also be subjected to the etching treatment of the solder and the solder. The solvent or the alkali is stronger than the strong alkaline aqueous solution of the alkaline developing solution, and the residual photoresist pattern after peeling off (4). As the above organic solvent, 139475.doc • 71· 200949439 PGMEA, PGME, EL, acetone, tetrahydrofuran, etc.; Examples of the strong alkaline aqueous solution include a 1 to 20% by weight aqueous sodium hydroxide solution and a 1 to 20% by weight aqueous potassium hydroxide solution. Examples of the release method include a dipping method, a spraying method, and the like. The wiring substrate on which the photoresist pattern is formed may be a multilayer wiring substrate or may have a small aperture through hole. The wiring pattern can be formed by forming a photoresist pattern using the third photoresist composition of the present invention, vacuum-depositing the metal, and then depositing the photoresist pattern by a solution, that is, a stripping method. A semiconductor device can be fabricated by a microfabrication method using the third photoresist composition of the present invention. The semiconductor device can be used in various devices such as a television receiver, a mobile phone, a computer product (electronic device), a storm computer, a computer controlled car, and the like. [Examples] [Experimental Example 1] Resorcin was filled in a three-necked flask (capacity: 500 ml) provided with a drip drain hopper, a Dairy cooling tube, and a thermometer under nitrogen flow under a nitrogen gas flow. After (33 g, 300 mmol) and acetaldehyde (17 ml, 3 Torr), distilled methanol (300 ml) was placed under a slight pressure of nitrogen to prepare a solution of the alcohol. - In the oil Luo (4) the methanol solution, the surface was heated to 75 C, and then 75 ml of concentrated hydrochloric acid was gradually added from the dropping funnel, and then heating and stirring was continued for 2 hours at 75 t. After completion of the reaction, the mixture was allowed to cool to room temperature, and then cooled in an ice bath. After standing, the white target was coarsely crystallized and separated. The crude crystals were washed twice with pure water (100 ml), and then recrystallized by mixing 139475.doc • 73-200949439 with ethanol and water, and dried under reduced pressure to synthesize the following formula (A). -20) a cyclic compound (16 g, yield 40.2%). This cyclic compound was confirmed by 1 H-NMR. [化75]

[Experimental Example 2] The cyclic compound (A-20) (135) produced in Experimental Example 1 was filled in a four-necked flask (capacity: 3000 ml) equipped with a nitrogen gas introduction tube, a thermometer, a mechanical stirrer, and a Dairy cooling tube. g, 249.7 mmol, N,N-didecylguanamine (1557 ml), sodium carbonate (294.29 g, 2776.48 mmol), gas-gas displacement. Then, a third butyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd., 444.96 g '2280.68 mmol) was added, and in a nitrogen atmosphere, in an oil bath of 65 (&gt;c, heating and reflux were started while stirring. 10 ml of the reaction solution was extracted from each reaction time shown in Table ,, and each reaction solution was filtered, and diethyl ether was added to the obtained filtrate to prepare a homogeneous solution, and the mixture was separated into a clear funnel in a/jw Wash the (4) solution with 0.5 ΜB 1 ^ exchange water until the water layer is neutral, and use the (4) solution cleaned with anhydrous sulphuric acid to remove the water. Use the rotating hair dryer to remove the moisture after decompression. The mystery solution was concentrated, and the concentrated liquid was transferred to a fresh liquid to obtain a solid 'transition separation m wonderful Taikoo carving solid under vacuum for 5 〇. (^ 139475.doc -74 - 200949439 which was dried for 8 hours, and obtained the following a cyclic compound represented by the formula (A-21). For each cyclic compound (A-21-1) to (A-21-h), the structure was confirmed by 1 h nmr, and the substitution included by LC/MS was confirmed. Calculation of acid dissociation dissolution inhibition by LC using several isomers The average substitution rate. The results are shown in Table 1. [Formula 76]

[Experimental Example 3] and experiment In the experimental example 1, the cyclic compound (A-22) was produced in the same manner as in Example 1 except that benzaldehyde was used instead of acetaldehyde. This cyclic compound is confirmed by W-NMR or the like. [化77]

[Experimental Example 4] Using the cyclic compound (A-22) obtained in Experimental Example 3, a cyclicated human represented by the following formula (A-23) was obtained by the same method as in Experimental Example 2. For each of the cyclic compounds (Α-23-1) to (Α-23-12), the structure was confirmed by 1h 139475.doc •75·200949439 NMR, and the average of the acid dissociable dissolution inhibiting groups was calculated in the same manner as in Experimental Example 2. Replacement rate. The results are shown in Table 1. [化78]

139475.doc • 76· 200949439

(A-23- 12) — (A-21- Π) ΓΟ 99.8 (A-23- 11) tn (A-21- l〇) (A-23- 10) 105 (A-21- 9) 00 % (A-23- 9) QO (A-21- 8) fS in (A-23- 8) (S in 64.7 (A-21- 7) o 67.3 (A-23- 7) to yd (A-21 - 6) Os (A-23- 6) ON rs (A-21- 5) 53.8 (A-23- 5) r5 47.2 (A-21- 4) r- 5 (A-23- 4) (A- 21- 3) rj (A-23- 3)_ (A-21- 2) 00 (A-23- 2) 00 38.4 (A-21- 1) in % (A-23- 1) 37.9 Name Reaction Time (hour) Average substitution rate of acid dissociative dissolution inhibitory group (%) Name Reaction time (hour) 镏趄 硌 W硌w Experimental Example 2 Experimental Example 4 139475.doc -77- 200949439 [Evaluation Example 1] For Experimental Example 2 The cyclic compound (11) produced in the above, and the cyclic compound (A_23 i) to (A 23_ 12) manufactured in Experimental Example 4, a representative coating solvent used in the use of light a, namely, propylene glycol hydrazine _Acetic acid 'GMEA) 'Performed solubility test. The solubility is as follows. ◎. ◎: After the powder was put into the solvent at room temperature, it became a homogeneous solution immediately without the transfer operation. . : At room temperature, the powder is put into the solvent, and after intense mixing for 1 minute, it becomes a homogeneous solution. △: The powder was placed in a solvent at room temperature, and after vigorous mixing for 3 minutes, it became a homogeneous solution. X: The powder was placed in a solvent at room temperature, and insoluble matter remained even after vigorous stirring for 3 minutes. Further, 'the solution obtained by the solubility test was spin-coated on a silicon wafer treated with HMDSOiexamethyldisilazane 'bis-trimethylguanamine) and heated at HKTC for 180 seconds to form a film. The bismuth developer (2.380/. tetramethylammonium hydroxide aqueous solution) was immersed for (9) seconds. After the investigation, the state of the film was visually observed and the film thickness was measured, and the dissolution rate in the test developer was calculated from the difference from the thickness before the immersion. The above results are shown in Table 2. As a result, the developing solution dissolution rate of (A 2i i) to (A 2i_ 5) and (A-23-1HA-23-4) is 〇5 nm/sec = upper, which is a higher value 'X, (A-23.5) and (A_23_6) film can be peeled off on one of the knives, (A-21-11) and (A_23_12) produce 139475.doc -78· 200949439 insoluble matter in the coating solvent, so it is impossible to , Bu media solubility is good, resistance. (A·23-11), although it cannot be said that the coating solution is good, it does not generate insoluble matter in the coating solvent, and therefore can be used as a photoresist. According to the above, it can be confirmed that (A_2i_6)~(AH〇) and (into the good 7)~(Α-23-11) (that is, when the average substitution ratio is 5S to 9〇%) can be favorably used as a photoresist substrate. And it can be confirmed that: (Α-21-6)~(Α_21-1〇) (that is, when the average substitution rate is 60% to 90%), and (A-23-7) to (A-23-10) ( That is, when the average substitution ratio is 55% to 80%, it can be particularly preferably used as a resist substrate.

139 139475.doc -79- 200949439 (Α-23- 12) X 1 1 (A-21- 11) X 1 1 (Α-23- 11) &lt; 〇 No change (A-21- 10) 〇〇 No Change (Α-23-10) No change (A-21- 9) ◎ No change (Α-23-?) _ No change (A-21- 8) ◎ No change (Α-23 -8) — 〇〇 No change (A-21- 7) ◎ c5 No change (Α-23- 7) 〇〇 No change (A-21- 6) ◎ No change (Α-23- 6) 〇〇 Partial peeling (A-21-5) 〇1 (Α-23-5) 〇is Partial peeling (A-21-4) 〇2 or more 1 (Α-23-4) 〇tn ο (A-21- 3 )_ ο 2 or more 1 (Α-23- 3) 〇rs 1 (A-21- 2) 〇2 or more 1 (Α-23- 2) 〇'Ο 1 (A-21- 1) 〇2 or more 1 ( Α-23- 1) 〇(4) 1 Name 轶趄w 金埃:鸵S ^ P-4 Alkaline developer dissolution rate (nm/sec) 迤&quot;6-蜍Name lack w $ Alkaline developer dissolution rate ( Nm/sec) Invited·θ~miss m m. Experimental Example 2 Experimental Example 4 139475.doc -80 - 200949439 [Manufacture of a cyclic compound] Example 1 Production of a structure having the following formula (B-1-1) Cyclic compound. [化79]

❹

(B-1-1) In a flask having a capacity of 1 liter, resorcinol 1 〇〇g (〇9 l mol) and p-toluenesulfonic acid monohydrate 86.2 g (0.45 mol) were placed, and nitrogen substitution was performed. Then, 490 ml of ethylene glycol was charged and stirred with a mechanical stirrer to obtain a homogeneous solution. Next, after adding benzaldehyde 96 4 g (〇 91 mmol) with a syringe at room temperature, it was heated to 120. (: The oil tank was heated and stirred for 2 hours. After the reaction, 'cooled to room temperature, and 95 ml of ion-exchanged water was added to the reaction liquid. After stirring for 30 minutes, the crude solid was separated by filtration. Under 8 〇β (: vacuum drying) After 8 hours, the crude solid was poured into tetrahydrofuran (15 liters), stirred at 65 C for 1 hour and heated to reflux, and washed. The washed solid was separated by filtration and dried under vacuum at 8 (TC) for 8 hours. The product was obtained. It was confirmed by W-NMR (Fig. 1) that the product contained only the isomer of the stereoscopic relative configuration (175.3 g, yield 97%) shown by (β]"). a cyclic compound of the structure of the formula (B-4-1). 139475.doc -81- 200949439 [Chem. 80]

Stupid phenol 1〇〇

To the flask in which the capacity of the dropping funnel was soared, g (0.91 mol), benzofural 96.4 g &lt;lt; and then 490 ml of 2-propanol were added to obtain a homogeneous solution. Next, the flask was cooled to 5 in an ice bath. (: After stirring, a solution of concentrated hydrochloric acid in 2-propanol (concentrated hydrochloric acid / 2 - propanol = 4 〇 ml / 4 〇 ml) was slowly added dropwise via a dropping funnel while stirring at an internal temperature of not more than 15 t. After completion, the reactor was taken out from the ice bath, stirred at room temperature for 4 minutes, and then heated and stirred for 2 hours in an oil bath heated to 65 ° C. After the reaction, it was cooled to room temperature. Ion exchange water was added to the reaction liquid. 95 ml of water, after stirring for 3 minutes, the crude solid was separated by filtration. The solid was washed with ion-exchanged water until the filtrate became neutral, and dried under vacuum at 80 ° C for 8 hours to obtain a crude solid (144.9 g yield) 81%). The crude product solid was confirmed to be a mixture of the above formula (b_4-1) and the formula (B-1-1) by H-NMR (Fig. 2) ((Β-4-1)/(Β-1-1) ) = 73. / / 27%). A mixture of the crude solid (144.9 g) and N,N-dimethylformamide (2.0 L) was heated to 65 ° C to prepare a homogeneous solution. After cooling for 12 hours, the precipitated solid was separated by filtration, and the N,N-dimethyl 139475.doc-82-200949439 base-branched amine (30 ml) was cooled by ice bath. After the solid was washed, it was washed with water, and the precipitated solid which was washed was separated and separated, and the recrystallized product was recovered by vacuum drying at 8 (TC for 8 hours). The obtained compound was confirmed to be a formula (B- by W-NMR (Fig. 3). 4-1) a cyclic compound (76 3 g, a recrystallization recovery of 53%, and a standard yield of 42%). Example 3 Production of a cyclic compound having the structure of the following formula (B_丨) 81]

R: ~〇H 0 two

Hj (B-1-2) was filled into a flask of each volume ι ml, and the cyclic compound of the formula (B-1-1) (2G g, 2 5 mmol) prepared in Example 1 was filled. NMp (23 ml), sodium carbonate (3.0 g, 28.2 mmol) were replaced with nitrogen. Then add the third butyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd., 4.5 g, 23.2 mmol), and in a nitrogen atmosphere, in a 65 χ: oil tank, the surface was heated for 24 hours. Ethyl acetate was added to the filtrate obtained by the transition to prepare a homogeneous solution, which was washed with a 0.5 Μ acetic acid aqueous solution in a separatory funnel. Further, (4) Ion-exchanged water The ethyl acetate solution was washed until the water layer became neutral, and the acetic acid (tetra) solution was treated with anhydrous sulfuric acid to remove water. After filtration, (iv) the rotary evaporator is concentrated under reduced enthalpy (four) liquid, and the concentrated liquid is poured into a self-burning to obtain a body. The solid was separated by filtration and dried under vacuum for a period of 8 hours to obtain a cyclic compound represented by the formula (B-1-2) 139475.doc - 83 - 200949439. The average conductivity of the acid dissociation dissolution inhibitory group was calculated by LC using 1h_nmr (Fig. Example 4 A cyclic compound having a structure of the following formula (B-4-2) was produced.

In the third embodiment, 'the cyclic compound of the formula (B-4) produced in Example 2 was used instead of the cyclic compound (B·^) produced by the example wipes, except for the examples and the examples. 3 is implemented in the same way. A ring-like compound represented by the formula (B_42) is obtained. The structure was confirmed by NMR (Fig. 5), and the average introduction rate of the acid dissociable dissolution inhibiting group was calculated by LC using "?"; g). Reference Example 1 In Example 3, a crude product solid produced in Example 2, that is, a mixture of a cyclic compound (Μ-1) and a cyclic compound (BH) ((b_4_ 1 )/(B-1 · 1) = 73% / 27%) was carried out in the same manner as in Example 3 except that the cyclic compound (B-1-1) produced in Example} was used. The structure was confirmed by 丨&amp; NMR (Fig. 6) and the substituted 139475.doc •84-200949439 number isomers were identified by lc/ms, and the average introduction rate of the acid dissociation inhibition group was calculated by LC (average protection) The import rate was 69%, 1.8 g). As a result, as shown below, a mixture of the cyclic compounds represented by the formula (B-1-2) and the formula (B-4-2) was obtained. [化83]

[Photoresist composition] Example 5 The cyclic compound produced in Example 3 or 4 was used as a resist substrate. To the 87 parts by weight of each of the above-mentioned photoresist substrates, 1 part by weight of diphenyl sulfonium trifluoromethanesulfonate as PAG was added as an inhibitor, and 4-diazabicyclo[2.2.2]octane 3 was added. Parts by weight. The resist component was produced by dissolving it in propylene glycol oxime ether acetate so that the concentration of the solid components was 5% by weight φ. Reference Example 2 A photoresist composition was produced in the same manner as in Example 5 except that the cyclic compound produced in Reference Example 1 was used as the resist substrate. Evaluation Example Using the obtained photoresist composition, a pattern was formed on a germanium wafer. The photoresist composition was spin-coated on a HMDS-treated ruthenium wafer and heated at 100 C for 180 seconds, thereby forming a film. Then, the substrate having the film was drawn using an electron beam 139475.doc -85-200949439 (acceleration voltage 50 kV), and after baking at 100 ° C for 60 seconds, the concentration was 3.88% by weight. The tetrabutylammonium aqueous solution was developed for 60 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream to form a pattern. Observation by a scanning electron microscope confirmed that the cyclic compound (Β_1_2) had the highest resolution and the most excellent sensitivity. Then, the cyclic compound (Β-4-2) has high resolution and good sensitivity. The photoresist composition using the mixture of the cyclic compound (B_i_2) and (β_4 2) produced in Reference Example 1 had the lowest resolution and the lowest sensitivity. Further, an EUV exposure apparatus was used instead of the electron beam patterning apparatus, and the substrate having the photoresist film was irradiated with EUV light (wavelength·· 13.5 nm). Thereafter, it was baked at 100 C for 90 seconds to a weight of 2.38. /. The aqueous solution of tetramethylammonium hydroxide was rinsed for 30 seconds and rinsed with ion-exchanged water for 3 seconds to form a pattern. Observation by a scanning electron microscope confirmed that the cyclic compound (B-i-2) had the highest resolution and the best sensitivity as in the case of the electron beam charter. Then, the cyclic compound (b_4_2) has high resolution and has good sensitivity. The photoresist composition using the mixture of the cyclic compound (Bdd) and (B_4_2) produced in Reference Example 1 had the lowest resolution and had the lowest sensitivity. Production Example 1 Under a nitrogen stream, a fully-filled, nitrogen-substituted three-necked flask (capacity 5 〇〇 ml) provided with a dropping funnel, a Dairy cooling tube, and a thermometer was filled with 139475.doc -86 - 200949439 (33 g '3 〇〇 millimolar) and benzoquinone (3i8 g 3 〇 () millimolar), under the slight pressure of nitrogen, steamed methanol (9) ^ ..., and (iv) methanol solution. The methanol solution was stirred in an oil bath while heating to m; Then, while adding dropwise from the dropping funnel, gradually adding 75-ml of hydrochloric acid, and then continuing heating at 7 rc for 2 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and then cooled in an ice bath. After standing for 1 hour, a white target crude crystal was formed, which was separated by filtration. The crude crystals were washed twice with pure water (10 ml), and then recrystallized from a mixed solution of ethanol and water, purified, and dried under reduced pressure to synthesize a ring represented by the following formula 35). Compound (yield 82%). The cyclic compound _ was confirmed by H-NMR. [化84]

Example 6 In a sufficiently dried, nitrogen-substituted daisy-cooled tube, two: a bottle (capacity_ml), one side was cooled in an ice bath, :: base _ phase 07 ml), in the production example 1 The synthesized cyclic compound (4) is controlled to be 3 millimoles, and the substitution is performed. Add / / in the amount described in Table 3 to dissolve in the N-methyl phase (5 ml: (chloromethoxy) diamond just (hereinafter referred to as (10)), dihydrobicyclo 139475.doc • 87- 200949439 [5.4·0]-7-undecene (hereinafter referred to as DBUUJ-diazabicydotnopi undecene) was stirred at room temperature for 4 hours under a nitrogen atmosphere. The reaction solution was poured into ion-exchanged water (200 ml) to stop the reaction while obtaining a white precipitate. These were subjected to filtration and separation, and dried under reduced pressure to obtain a cyclic compound represented by the following formula (c-36) having an average substitution ratio of the acid dissociable dissolution inhibiting group described in Table 3. (c-36-1) ~ (C-36-7). Furthermore, the cyclic compounds were confirmed to have an average substitution ratio and structure by 1 h nmr^. [化85]

(C-36)

R: -OH Evaluation Example 2 For the cyclic compounds (c_36_1} to (c_36_7) produced in Example 6, a representative coating solvent generally used in the photoresist, propylene glycol methyl ether acetate (PGMEA), was used. The solubility test was carried out. The evaluation criteria of the solubility were as follows.

〇. At room temperature, the powder is put into the solvent, and after vigorous stirring for 1 minute, it becomes a homogeneous solution D, and the powder is put into the solvent, and even if it is stirred for 1 minute, insoluble matter remains, but heating After 1 (10) t, the insoluble matter is dissolved, and even if it is cooled to room temperature, the homogenous solution can be maintained. ^9475.()) 200949439 X: The powder was put into a solvent at room temperature, and insoluble matter remained even when heated to 100 °C. Further, the solution obtained by the solubility test was spin-coated on a ruthenium wafer treated with hexamethyldiazepine, and heated at 100 ° C for 180 seconds to form a film, and the film was measured. The film thickness was immersed in an alkaline developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and the developing solution dissolution rate was calculated from the difference from the film thickness before the immersion.

The above results are shown in Table 3. It can be confirmed that (C-36-1) and (C-36-7) are insoluble in the coating solvent and thus cannot be used as a photoresist substrate, (C-36-2) to (C-36-6) (ie, When the average substitution ratio is 30% to 55%, it can be used as a photoresist substrate. Further, (C-36-2) and (C-36-6) are hardly soluble in the coating solvent, and are insoluble in the alkaline developing solution. Although they are used as a photoresist substrate, they are not good, (C-36 -3)~(C-36-5) (that is, when the average substitution ratio is 35% to 50%), it can be favorably used as light from the viewpoint of coating solvent solubility and solubility of an alkaline developer. Resisting substrate. [Table 3] Name (C-36-1) (C-36-2) (C-36-3) (C-36-4) (C-36-5) (C-36-6) (C- 36-7) CMA addition amount (mole) 3 5 6.7 10.1 11.6 14.1 40.4 DBU addition amount (mole) 5.9 5.9 7.9 11.9 14.1 17.1 47.3 Average substitution rate of acid dissociative dissolution inhibitory group (%) 23 30 35 45 50 55 87 Coating solvent solubility (S wt% in PGMEA) X Δ 〇〇〇Δ X Developer solution dissolution rate (nm/sec) - 0.04 0 0 0 0 - 139475.doc •89- 200949439 Example 7 The ring compound (12.0 g, 15 mmol) and sodium carbonate synthesized in the production example were filled in a two-necked flask (capacity: 200 ml) provided with a Dy's cooling tube and a thermometer, which were sufficiently dried and replaced with nitrogen. (18 〇 g, 168 millimolar), nitrogen replacement. Then, add N_methylpyrrolidone 12 〇 ml to make; after the gluten solution, add brook acetic acid 2·methyl 2_ Donkey Kong vinegar (287 g, 26 mAh) 'under nitrogen atmosphere, at 1 Hey. (The oil tank was stirred for 1 hour while being heated and refluxed for reaction. After standing to cool to room temperature, 8 mL of an aqueous vaporized ammonium solution was poured into the reaction solution, and 15 mL of ethyl acetate was used. After extracting, the ethyl acetate layer was washed with water and dried over magnesium sulfate, and filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was reprecipitated in two rows and purified by ion exchange to obtain The cyclic compound represented by the formula (C-37) (yield 75%) was confirmed by NMR (Fig. 7).

139475.doc •90· 200949439 Example 8 In Example 7, except that DBU was used instead of sodium carbonate, 2-methyl-2-adamantyl carbonate was used instead of 2-methyl-2-amantane bromoacetate. In the same manner as in Example 7, a cyclic compound which is not represented by the following formula (C-38) was obtained in the same manner as in Example 7 (yield 6 % by weight). The cyclic compound was subjected to W-NMR (Fig. 8) Confirm its structure. [Chem. 87]

Evaluation Example 3 Using 87 parts by weight of the compound synthesized in Examples 7 and 8 and 87 parts by weight of a known compound (C-3 9) shown below as a substrate, trifluoromethanesulfonic acid was used as the substrate. Triphenylene plating salt 1 part by weight as PAG, using 1,1_1 gas heterobicyclo[2.2.2] octane 3 parts by weight as an inhibitor. The photo-resist solution was prepared by dissolving the solid components in propylene glycol methyl ether acetate so that the concentration of the solid components was 5% by weight. The photoresist solutions were spin-coated on a ruthenium wafer treated with 1,1,1,3,3,3-hexamethyldioxane (HMDS), and heated at a loot for 180 seconds. A film is formed. Then, the substrate having the film was drawn using an electron beam charter (acceleration voltage 5 〇 kV). After baking for 60 seconds at 10 ° C, 139475.doc -91 · 200949439 was used at a concentration of 2.38 by weight. /. The tetrabutylammonium aqueous solution was subjected to development treatment for 6 seconds, and washed with pure water for 60 seconds. Thereafter, it was dried by a nitrogen stream. As a result, when the compound synthesized in Examples 7 and 8 was used as a photoresist solution for a substrate, a line and a gap pattern of 1 〇〇 nm having good squareness and linearity were obtained. On the other hand, when the comparative compound (c_39) was used as a photoresist solution for a substrate, only a random wave-shaped electron beam irradiation mark was observed, and a line and gap pattern of 100 nm could not be obtained. The EUV light (wavelength: 13.5 nm) was irradiated onto the substrate having the photoresist film by using an EUV exposure apparatus instead of the electron beam patterning apparatus. Thereafter, it was baked at 1 Torr (90 seconds after rc), rinsed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and rinsed with ion-exchanged water for 30 seconds, thereby forming a pattern. Using a scanning electron microscope After observation, it was confirmed that, in the same manner as in the case of the electron beam charter, when the compound synthesized in Examples 7 and 8 was used as a photoresist solution for a substrate, a line of 1 〇〇 nm having a good squareness and linearity was obtained. On the other hand, when the comparative compound (c_39) was used as the photoresist solution of the substrate, only the random wavy EUV light irradiation marks which were the same as those in the case of using the electron beam drafting instrument were observed, and it was not obtained. 1〇〇nm line and gap pattern. [化88]

139475.doc -92- 200949439 [Industrial Applicability] The photoresist substrate of the present invention and the composition using the same can be preferably used in electrical, electronic, or optical fields such as semiconductor devices. . It is especially suitable for photoresists for far ultraviolet light and/or electron beam. With the photoresist composition of the present invention, the performance of a semiconductor device such as ULSI can be greatly improved. Further, the semiconductor device manufactured by using the photoresist composition of the present invention as a component can greatly improve the performance of semiconductor device products such as information home appliances, computer equipment, memory device products, and display devices. The cyclic compound of the present invention is useful as a photoresist substrate. Further, the photoresist substrate of the present invention and the composition thereof can be preferably used in an electrical, electronic or optical field such as a semiconductor device. Thereby, the performance of the semiconductor device such as the port 1^1 can be greatly improved. The contents of the documents described in this specification are hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1H-NMR chart of a cyclic compound produced in Example 1. Figure 2 is a 1H-NMR chart of the crude product solid produced in Example 2. Fig. 3 is a 1H-NMR chart of the cyclic compound produced in Example 2. 4 is a 1H-NMR chart of the cyclic compound produced in Example 3. Fig. 5 is a 1H-NMR chart of the cyclic compound produced in Example 4. Fig. 6 is a 1H-NMR chart of the cyclic compound produced in Comparative Example 1. Figure 7 is a h-NMR chart of the cyclic compound produced in Example 7. Figure 8 is a 1h_nmr diagram of the cyclic compound produced in Example 8. 139475.doc -93·

Claims (1)

200949439 VII. Patent application scope: 1. A photoresist substrate comprising any one of the following (Α-1)~(Α_3) indicating a dissociative dissolution inhibitory group or a hydroxyl group, and the substitution rate is 55 to 90%, [ a cyclic compound of the formula: wherein the plurality of Rs in the formulae below are the average of the acid-acid dissociative dissolution inhibitory groups [wherein R' represents a hydrogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and carbon, respectively. a monocyclic cyclic aliphatic hydrocarbon group of 12, a polycyclic cyclic aliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, (Α-4) the aromatic group represented by the formula, the substituent represented by the formula (Α-5), or a substituent formed by combining two or more of the substituents; (Α-4) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group, respectively, and X represents an integer of 1 to 5; when X is 2 or more, R may be the same or different) 139475.doc 200949439 [Chem. 91] .RM y (AS) (wherein Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (A-4); R, R2 a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or An unsubstituted substituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups y represents an integer from 1 to 4; when y is 2 or more, R1 and r2 may be the same or different)]. 2. The photoresist substrate according to claim 1, wherein the acid dissociable dissolution inhibiting group is selected from the group consisting of the following formulas (A-6) to (A-10), and -occo-Ah » CHj &lt;A-6) Q CH3 一〇-〇-〇—|—CH3 CH3 (A-7) (A-8) (A-9) 139475.doc 200949439 (In the formula (Ad), (Α·1〇), r represents any of the following substituents; *&quot; of the formula _ may be the same or different); [Chem. 93] © 3. &amp; The photoresist substrate of the present invention, wherein the above cyclic compound is represented by the following formula (Α·11), wherein the ruler is a substituent represented by the formula (A12) or a hydroxyl group, The average substitution ratio of the substituent represented by the formula (AU) is 6〇~9〇%, [Chem. 94] 4. The photoresist substrate according to claim 2, wherein the cyclic compound is represented by the following formula (A-13): wherein R is a substituent represented by the formula (A-14) or a hydroxyl group, respectively ( The average substitution rate of the substituents represented by A-14) is 55 to 80%, 139475.doc 200949439 [Chem. 95] 5. A photoresist composition, such as ash, substrate and solvent. The photoresist of any one of items 1 to 4 6. 7. A microfabrication method A semiconductor device is fabricated. A photoresist composition as claimed in claim 5, which is characterized by the microfabrication method of claim 6, wherein the device is provided with the semiconductor device of claim 7. Any one of the following formulae (bi) to (B6), wherein the ratio of the cyclic compound to the total oxime stereoisomer is 9 〇 mol% or more, [化96] 139475.doc 200949439 [wherein R is an acid dissociable dissolution inhibitor or a hydroxyl group, respectively. ❹ R' is a hydroxyl group or an ether group respectively (_〇R\ Ra is a linear chain of a long-lived aliphatic group L group having a carbon number of 〇1〇, a branched aliphatic hydrocarbon group of 3 to 8 and a carbon number a linear monocyclic aliphatic fat having a monocyclic cyclic aliphatic hydrocarbon group of 3 to 8 , a polycyclic ring having a carbon number of 4 to 10 = a cyclic aliphatic hydrocarbon group, a phenyl group, a naphthyl group, and a carbon number of 〜12. a sulfhydryl group, a branched aliphatic hydrocarbon group having a carbon number of 3 to 丨2, a monocyclic cyclic aliphatic hydrocarbon group having a carbon number of 3 to 12, and a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of '(7) a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (B-8), or a substituent formed by combining two or more of the substituents; [Chem. 97] (R)x (B-7) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group, and χ represents the number of 55) &amp; [Chem. 98] (wherein 'Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the above formula (B-7); and R1 and R2 are each independently a hydrogen atom; a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted Carbon 139475.doc 200949439 A cyclic aliphatic hydrocarbon group of 3 to 20, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these substituents a substituent; y is an integer of 1 to 4) R may be the same or different, and R may be the same or different from each other; wherein, in the above formulae (B-1) and (B-4), R is a fluorenyl group. , phenyl or 4-isopropylphenyl, and excluding R in the case of the following formula (B-9)] [Chem. 99;) The cyclic compound group according to claim 9 is selected from the above formula (B-9), a group, wherein the acid dissociation dissolution is inhibited or in the following formula (Β-1〇)~(Β-36) base 139475.doc 200949439 [Chem. 101] Ο —O-C-H,C- -o-c h3c °jC) (B-l 5) (B-l 7) -o-c (B—1 6) —o-c -c (B-l 8) (B-l 9) [化102] p p (B-2 0)0』 H2 _C—I (B-23) (B-22) -0-8 (B-24) (B-2 5) ❿ [Chem. 103] 一0私〇』: (B-27) -o-c -o (B-26) (B-28) (B-29) Hi. H2 ?\ O-cv —o-c -&lt;&gt;vT7 (B-30) 139475.doc 200949439 [Chem. 104] (B-3 5) (B-3 6) (wherein 'r each represents any one of the substituents represented by the above formula (B_9) to (b_34), and the following formula (r) 2). 105] (M&gt; (r-2) 〇 π. A photoresist substrate comprising a cyclic compound having a stereoscopic relative configuration represented by a formula of the following formula (Β-1) to (Β_6), and the above ring The ratio of the compound to the total stereoisomer is 90 mol% or more, [Chem. 106] 139475.doc 200949439 R· are each a hydroxyl group or an ether group (_〇Ra: Ra is a linear aliphatic nicotine group having a carbon number of 丨~1〇, a branched aliphatic hydrocarbon group having a carbon number of 3 to 8, and a carbon number of 3 a monocyclic cyclic aliphatic hydrocarbon group of ～8, a polycyclic cyclic aliphatic hydrocarbon group having a carbon number of 4 to 10, a phenyl group, a naphthyl group, a linear aliphatic hydrocarbon group having a carbon number of 丨12, and carbon a branched aliphatic hydrocarbon group of 3 to 12, a monocyclic cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms, a polycyclic cyclic aliphatic hydrocarbon group having 4 to 10 carbon atoms, a stupid base, and a pair a stupid base, a tributyl phenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (B_ ❹ 8), or the substitution thereof a substituent composed of a combination of two or more kinds of groups; (B-7) (wherein R is an acid dissociable dissolution inhibiting group or a hydroxyl group, an integer of X 5 ) ', [Chem. 108] R2 Jy (B-8) (wherein Ar represents a stupid base' to a certain lean + phenyl group, a p-tert-butylphenyl group, a naphthyl group, and an aromatic group represented by the above formula (B-7); 139475. Doc 200949439 R1 and R2 are hydrogen respectively Atom, substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted a substituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these substituents ; y is an integer from 1 to 4) R may be the same or different 'R, may be the same or different from each other'. 12. The photoresist substrate according to claim 11, wherein the acid dissociable dissolution inhibiting group is selected from the group consisting of the following formulas (B-9) to (B-36); [Chem. 109] (B-9) ) (B-1 〇) (B-l 1) (B — 12) (B-l 3) [Chem. 110] (B-14) (B-15) (B-16) (B-17) (B-18) (B-19) 139475.doc -10· 200949439 [Chem. 111] ρ -? (Β-20) (Β-2 1) φ [化112] (Β-26) Ο 0-^ ,0 -ο (Β-2 7) ,^4-O-^-C (Β-29) Ρ (Β-28) _ [Chem. 113] (Β-34) (wherein r represents the above formula (Β-9)~(Β-34), the following formula (r-1), (r- 139475.doc -11 - 200949439 2) Any of the substituents - [114] ?HipHs—O-Si-^-CH, 0Hj CHS &lt;Μ) (Γ-2) 〇13. 14. 15. 16. 17. 18. 19. If the item Η or m is blocked, the towel is R , _ is a monocyclic cyclic aliphatic hydrocarbon group of carbon 3 to 12, a polycyclic aliphatic hydrocarbon group having a carbon number of 4 to 〇, a phenyl group, a p-phenylphenyl group, a third butyl group, a naphthalene The substituent, the aromatic group represented by the above formula (Β7), the substituent represented by the above (10)-[), or a combination of two or more of these groups. The photoresist substrate of the claim ", which is represented by the above formula (Β)) or (Β4), wherein R is a group represented by the following formula (Β·9), and R is a methyl group, respectively. , phenyl, or 4-isopropylphenyl, [Chem. 115] -o^4-〇4^H3 CHj (B*9&gt;. A photoresist composition containing the contents of the request A photoresist substrate and a solvent. A microfabrication method using the photoresist composition of claim 15. A semiconductor device produced by the microfabrication method of claim 6. A semiconductor device according to claim 17, which is a method for producing a cyclic compound which is represented by the formula (Β-l) to (B_3) of claim 139475.doc -12- 200949439 9 The method is characterized in that a boiling point of 9 添加 is added to a mixture of a polyphenol compound selected from the group consisting of bisphenol, pyrogallol, 1,2,3,5-tetrahydrobenzene and a solid organic sulfonic acid of an acid catalyst. &lt;T or more alcohols as a solvent, and then an aldehyde compound represented by the following formula (B-24) is added to prepare a reaction solution, and 90 t: or more and 15 (The temperature below TC is subjected to a cyclization condensation reaction to produce a cyclic compound represented by the following formula (Β-Γ)~(BJ,), σ followed by a formula (Β-η~(Β-3') At least i merid groups of the cyclic compound represented are introduced into an acid dissociable dissolution inhibitory group, [Chem. 116] κ, -CHO (B-2 4) In the formula, R represents the same group as R represented by the claim 9, and a photoresist substrate comprising the following cyclic compound: the following f-υ~(C- 3) The term "represented" is that the plural R in the formula is the acid-dissociable dissolution inhibiting group or the meridine of the ring structure, and the average substitution rate of the lytic dissolution inhibitory group is 20 to 60%, 139475 .doc •13· 200949439 [化117] [wherein R| represents a hydrogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having a carbon number of 1 to 12, a branched aliphatic hydrocarbon group having a carbon number of 3 to 12, and carbon, respectively. a monocyclic cyclic aliphatic hydrocarbon group of 3 to 12, a polycyclic cyclic aliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group a substituent represented by the formula (C-4), a substituent represented by the formula (C-5), or a substituent formed by combining two or more of the substituents; In the above, R is an acid dissociable dissolution inhibiting group containing an alicyclic structure, or a hydroxyl group 'X represents an integer of 1 to 5; when X is 2 or more, R may be the same or different) [Chem. Wherein 'Ar represents a phenyl group, a p-phenylene group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (C-4); 139475.doc -14· 200949439 R1, R2 a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or An unsubstituted substituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these substituents y represents an integer of 1 to 4; when y is 2 or more, Ri and R2 are the same or different)]. 21. The photoresist substrate of claim 20, wherein the acid dissociable dissolution inhibiting group is selected from the group consisting of the following formulas (C-6) to (C-3 1), [Chem. 120] (C-6) ) (C-7) (C-8) (C-9) + History! 27〇-.尨^7〇 (C-10) (C-11) [Chem. 121] (C-l 4) (C-1 5) (C-l 6) (C-1 7) 139475.doc -15- 200949439 [化122] -o-c Hz H2 (C-l 8) (C-l 9) (C-2 1) (C-2 3) (C-2 0) H2 9 h2 -c -C-〇~C, (C-2 2) [化123] (C-2 4) (C-2 5) (C-26) (C-2 7) [Chem. 124] (C-2 9) (C-3 1) (wherein r represents any one of the substituents represented by the above formulae (C-6) to (C-29)). [16] 139475.doc 200949439 22. The photoresist substrate of claim 21, wherein the cyclic compound is represented by the following formula (C-33), wherein R is represented by the formula (C-34), respectively. The average substitution rate of the substituent or the substituent represented by the formula 'C-34' is 35 to 5 %, m [Chem. 125] 23. The photoresist substrate according to claim 21, wherein the cyclic compound is represented by the following formula (C-3 3): wherein R is a substituent represented by the formula (c_34i) or a trans-formula ( The average substitution rate of the substituent represented by C-34') is 20 to 60%, ❿ A photoresist composition comprising the photoresist substrate and the solvent according to any one of claims 20 to 23. 139475.doc -17. 200949439 25. A microfabrication method using the photoresist composition of claim 24. 26. A semiconductor device produced by the microfabrication method of claim 25. 27. A device comprising the semiconductor device of claim 26. 139475.doc 18-