JPH03241354A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To enhance sensitivity to deep ultraviolet rays and dry etching resistance and to form a fine pattern with a good cross section by incorporating an alkali-soluble polymer having a phenol structure and a specified heterocyclic compound. CONSTITUTION:This photosensitive composition contains the alkali-soluble polymer having the phenol structure and the heterocyclic compound represented by formula I or II in which Z<1> is a nonmetallic atomic group necessary to form an N-containing hetero ring, and each of R<1> and R<2> is H, 1 - 20 C alkyl, or the like, thus permitting the obtained photosensitive composition to be high in sensitivity to radiation short in wavelength, such as deep ultraviolet rays, and superior in dry etching resistance, and to form a fine pattern having a good cross section.

Description

Detailed Description of the Invention [Object of the Invention] (Industrial Application Field) This invention relates to a photosensitive composition, and in particular to a photosensitive composition
This invention relates to a photosensitive composition that is sensitive to V.

(Prior Art) In recent years, there has been a demand for high-density integration of electronic components in order to increase the functionality and density of electronic devices. Along with this, there is a demand for miniaturization of patterns formed on electronic components.

On the other hand, in the manufacture of semiconductor integrated circuits and other electronic components that require various types of microfabrication, photosensitive resins are widely used to form micropatterns. A step-and-repeat reduction projection mask aligner called a stepper is conventionally known as an exposure apparatus used for forming patterns using this photosensitive resin.

The light source used in such a device is the g of a mercury lamp.
line (wavelength 438 ni+), h line (wavelength 405 n
Im) and i-line (wavelength 365nI11), excimer laser XeF (wavelength 351r+m),
e C, [, (wavelength 308 nm), KrF (wavelength 24 nm)
8tv), K r C1l (wavelength 222 no+
), ArF (wavelength 193na+), F 2
(wavelength: 157 ni). In order to form a fine pattern, the shorter the wavelength of the light used, the better. Therefore, the deep
Resists that are sensitive to UV light are desired.

Photosensitive resins for excimer lasers have conventionally been made from acrylic polymers such as polymethyl methacrylate (PMMA) and polygel tarmaleimide (PGMI) or polymers containing phenol and azide photosensitizers. Compositions are known. However, photosensitive compositions using the former polymer have problems in that they have low sensitivity to excimer lasers and poor dry etching resistance. Furthermore, although a photosensitive composition using the latter polymer has excellent sensitivity and dry etching resistance, the cross-sectional shape of the formed pattern becomes an inverted triangle. Therefore, there was a problem in that it was difficult to manage the exposure and development steps.

(Problems to be Solved by the Invention) This invention was made to solve the above-mentioned conventional problems, and has high sensitivity to short wavelength radiation such as deep UV, and excellent dry etching resistance. An object of the present invention is to provide a photosensitive composition that has high tolerance in controlling exposure and development steps and is capable of forming a fine pattern with a good cross-sectional shape.

[Structure of the invention]

(Means for Solving the Problems) The above object is achieved by preparing the following photosensitive compositions (A) to (F) containing an alkali-soluble polymer having a phenol skeleton and a photosensitizer.
) is achieved by

Photosensitive composition (A) A photosensitive composition containing an alkali-soluble polymer having a phenol skeleton and a heterocyclic compound represented by the following general formula (1-1) or (I-2).

(Ni 1) 2 (Ni 2) (Here, ZI is a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, R1 and R2 may be the same or different, and each is a hydrogen atom. , unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, alkoxy group, acyl group, alkenyl group, hydroxyl group, amino group, dialkylamino group having 1 to 5 carbon atoms, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, cinnamyl group, mercapto group, cyano group, halogen atom) Photosensitive composition ( B) A photosensitive composition containing an alkali-soluble polymer having a phenol skeleton and a heterocyclic compound represented by the following general formula (n-1) or (II-2).

(Here, Z2 and z3 may be the same or different, and R3 and R4, which are nonmetallic atomic groups necessary to form a heterocycle containing oxygen, may be the same or different.) Often hydrogen atoms, each with 1 to 20 carbon atoms
unsubstituted or substituted alkyl group, alkoxy group, acyl group, alkenyl group, hydroxyl group, amino group, carbon number 1-5
dialkylamino group, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, 4-silyl group, mesityl group, benzyl group, styryl group, cinnamyl group, mercapto group, cyano group, halogen atom)'-C-=〇 (Here, Z4 is a group of nonmetallic atoms necessary to form a heterocycle containing oxygen, R5 is a hydrogen atom, and the number of carbon atoms 1 to 20 unsubstituted or substituted alkyl groups, alkoxy groups, acyl groups, alkenyl groups, hydroxyl groups, amino groups, dialkylamino groups having 1 to 5 carbon atoms, nitro groups, carboxyl groups, methoxycarbonyl groups, ethoxycarbonyl groups, carboxy Methyl group, carboquinethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, cinnamyl group, mercapto group, cyano group, halogen atom) Photosensitive composition (C) A photosensitive composition containing an alkali-soluble polymer having a phenol skeleton and any one of the heterocyclic compounds represented by the following general formulas (m-1) to -8).

group, halogen atom) Photosensitive composition (D) An alkali-soluble polymer having a phenol skeleton and a heterocyclic compound represented by any of the following general formulas (rV-1) to (IV-12). A photosensitive composition containing.

R17RIO (Here, R6 and R9 may be the same or different, and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkenyl group, a hydroxyl group, an amino group) , dialkylamino group having 1 to 5 carbon atoms, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group , stylyl group, cinnamyl group, mercapto group, cyano 16 17 14 R15 16 17 17 IO 17 ○ IO 16 17 16 17 14 15 16 17 17 ○ ○ 10 16 R efthyryl group, cinnamyl group, mercapto group, cyano group, halogen atom, Z represents a divalent organic group) photosensitive composition (
E) A photosensitive composition comprising an alkali-soluble polymer having a phenol skeleton and a pyridinium salt represented by the following general formulas (V-1) to V-4).

(Here, R'' to RI7 may be the same or different, and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group,
Alkenyl group, hydroxyl group, amino group, dialkylamino group having 1 to 5 carbon atoms, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group group, mesityl group, benzyl group,
(Here, R'' to R27 may be the same or different, and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkenyl group, a hydroxyl group, an amino group, dialkylamino group having 1 to 5 carbon atoms, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group photosensitive composition (F) an alkali-soluble polymer having a phenol skeleton; A photosensitive composition comprising a polymer having a nitrogen-containing heterocyclic compound as a polymerized unit.

In the photosensitive compositions (A) to (F), the photosensitive compositions (A) and (C) to (F) can be suitably used as negative resists. In addition, photosensitive composition (B
) can be suitably used as a positive resist.

The alkali-soluble polymer having a phenol skeleton used in the photosensitive compositions (A) to (F) is as follows:
For example, phenol tuborac resins; substituted phenol novolak resins such as cresol novolak resins and xylenol novolak resins; vinyl phenol resins; isopropenyl phenol resins; copolymers of vinyl phenol with acrylic acid, methacrylic acid derivatives, acrylonitrile, styrene derivatives, etc. Copolymers of isopropenylphenol and acrylic acid, methacrylic acid derivatives, acrylonitrile, styrene derivatives, etc.; Acrylic resins; Methacrylic resins; Copolymers of acrylic acid or methacrylic acid and acrylonitrile, styrene derivatives; Malonic acid and vinyl ethers; Examples include copolymers of More specifically, poly(p-vinylphenol); copolymer of p-isopropenylphenol and acrylonitrile (monomer ratio 1:1); copolymer of p-isopropenylphenol and styrene (monomer ratio 1:1); Ratio l:1); p
Mention may be made of copolymers of vinylphenol and methyl methacrylate (monomer ratio 1:l); copolymers of p-vinylphenol and styrene (monomer ratio 1:l).

The photosensitive composition (A) according to the present invention contains the above-mentioned alkali-soluble polymer having a phenol skeleton and the heterocyclic compound represented by the following general formula (I-1) or (I-2), It can be suitably used as a negative resist.

Examples of the heterocyclic compound represented by the general formula (I-1) include pyridine or 2-ethylpyridine,
2.4-dimethylpyridine, 2-acetylpyridine, 2
- Pyridine derivatives such as methoxypyridine, 3-hydroxypyridine, 3-pyridinecarboxylic acid, 2-chloropyridine, nicotinamide, 2-phenylpyridine; quinoline or 4-methylquinoline, 2-chloroquinoline,
Quinoline derivatives such as 8-hydroxyquinoline, 8-hydroxy-2-methylquinoline, 6-medoxyquinoline, 4-quinolinecarboxylic acid; acridine or acridine derivatives such as 3-methylacridine, l-chloroacridine, 3-aminoacridine ; imidazole or 1
- Imidazole derivatives such as methylimidazole and 2.4.5-triphenylimidazole; pyrazole or its derivatives; imidacilline or its derivatives; benzimidazole or its derivatives; diazine or its derivatives such as pyridazine, pyrimidine, pyrazine; phthalazine, quinazoline, Examples include benzodiazine or its derivatives such as quinoxaline; 1,3.5-triazine or its derivatives; oxazole or its derivatives; thiazole or its derivatives.

In addition, examples of the heterocyclic compound represented by the general formula (I-2) include pyridine-1-oxide, 2-methylpyridine-1-oxide, 3-methylpyridine-1-oxide, and 4-methylpyridine-1-oxide. -1-oxide, 4-nitropyridine-1-oxide, 4-nitro-2
-Methylpyridine-1-oxide, 4-nitro-3,5
-dimethylpyridine-1-oxide, 4-nitro-2,
6-dimethylpyridine-l-oxide, 4-nitro-3
-chloropyridine-1-oxide, 4-nitro-3-pyridinecarboxylic acid-1-oxide, 4-acetylpyridine-1-oxide, 2-aminopyridine-1-oxide, 3-hydroxypyridine-1-oxide, 2 .Pyridine-1-oxide derivatives such as 6-dimethylpyridine-1-oxide; quinoline-1-oxide derivatives such as quinoline-1-oxide or 4-nitroquinoline-1-oxide, 4-hydroxyaminoquinoline-1-oxide; can be mentioned.

The blending ratio of the heterocyclic compound represented by the general formula (1-1) or (1-2) to the alkali-soluble polymer having a phenol skeleton is 1 to 500 parts by weight per 100 parts by weight of the polymer. , more preferably 0.1~
It is 200 parts by weight. The amount of the heterocyclic compound is 0.1
If the amount is less than parts by weight, it may not be possible to impart sufficient photosensitivity to the composition. On the other hand, if the blending amount is 20
If the amount exceeds 0 parts by weight, the exposure light beam will not reach the surface of the resist film that is in contact with the substrate, and it will tend to be difficult to form a pattern with a good cross-sectional shape.

The photosensitive composition (B) according to the present invention comprises the above-mentioned alkali-soluble polymer having a phenol skeleton and the above-mentioned general formula (
II-1) or (II-2), and can be suitably used as a positive resist.

Examples of the heterocyclic compound represented by the general formula (II-1) include 4-pyrone, 2,6-dimethyl-4-pyrone, 3-hydroxy-4-pyrone, 3-hydroxy-2-methyl-4 -pyrone, 4-pyrone-2-carboxylic acid, 5-hydroxy-4-pyrone-2-carboxylic acid, 4-pyrone-2,6-dicarboxylic acid, 3-hydroxy-4-pyrone-2,6-dicarboxylic acid , 4-pyrone derivatives such as 2,3-benzo-4-pyrone; 4-oxyzolone and its derivatives.

In addition, examples of the heterocyclic compound represented by the general formula (II-2) include 2-pyrone, 3-hydroxy-2-pyrone, 4-hydroxy-6-methyl-2
2-pyrone, 2-pyrone-6-carboxylic acid, 5,6-benzo-2-pyrone, 3,4-benzo-2-pyrone, etc.
Examples include pyrone derivatives; hydrofuran derivatives such as 3-butene-4-olibi-3-carboxylic acid and 3-oxo-4-butanolide; benzofuran derivatives such as phthalide and 3,3-dimethylphthalide.

The blending ratio of the heterocyclic compound represented by the general formula (II-1) or CU-2) to the alkali-soluble polymer having a phenol skeleton is as follows:
The amount is preferably 1 to 500 parts by weight, more preferably 0.1 to 200 parts by weight.

If the amount of the heterocyclic compound is less than 0.1 part by weight, it may not be possible to impart sufficient photosensitivity to the composition. On the other hand, if the amount exceeds 200 parts by weight, the exposure light will not reach the surface of the resist film that is in contact with the substrate, making it difficult to form a pattern with a good cross-sectional shape.

The photosensitive composition (C) according to the present invention comprises the above-mentioned alkali-soluble polymer having a phenol skeleton and the above-mentioned general formula (
It contains any one of the heterocyclic compounds represented by I[[-1) to [-8), and can be suitably used as a negative resist.

Examples of the heterocyclic compound represented by the general formula (III-1) to I[l-8) include pyridazine,
8-methylpyridazine, 4-methylpyrimidine, pyrazine, 2,5-dimethylpyrazine, 1.2.5-) riazine, 2.4.6-dolichloro1,3.5-) riazine, pyridazine-N-oxide, 4-pyridazine-N-
oxide, 4,5-dimethylpyridazine-N-oxide, 4,8-dimethylpyrimidine-N-oxide, 4-methoxypyrimidine-N-oxide, pyrazine-N-oxide, 2,3-dichloropyrimidine-N-oxide, 2,
6-dichloropyrazine-N-oxide, 1.3.5-triazine-N-oxide, 2,4.8-trimethoxy-
1,3,5-triazine-N-oxide, 2.4.8-
Trio-1.3.5-triazine-N-oxide and the like can be mentioned. In addition, general formula (III-5)
The heterocyclic N-oxide compound represented by m-8) is, for example, G.

B. Payne, The Journal of
Organic Chea + 1st try.

It can be synthesized according to the method described in Vol. 2B, p659 (1961).

The blending ratio of the heterocyclic compound represented by the general formula (III-1) to (III-8) to the alkali-soluble polymer having a phenol skeleton is from 1 to 300 parts by weight per 100 parts by weight of the polymer. The amount is preferably 2 to 100 parts by weight, and more preferably 2 to 100 parts by weight. If the proportion of the heterocyclic compound is less than 1 part by weight, it will be difficult to impart sufficient photosensitivity to the composition. Furthermore, if the blending ratio of the heterocyclic compound exceeds 300 parts by weight, the light transmittance of the resist film decreases, making it difficult for the exposure light to reach the substrate side of the resist film, resulting in poor performance. It becomes difficult to form a pattern with a cross-sectional shape.

The photosensitive composition (D) according to the present invention comprises the above-mentioned alkali-soluble polymer having a phenol skeleton and the above-mentioned general formula (
It contains any of the heterocyclic compounds represented by IV-1) to (IV-12) and can be suitably used as a negative resist.

Examples of the divalent organic group Z introduced into the general formula (IV-7) to IV-12) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a vinylene group, a 2-butenylene group, malonyl group, succinyl group, glu, taryl group, fumaroyl group, carbonyl group, oxalyl group, carbonyldioxy group, sulfinyl group,
Sulfonyl group, dithio group, thiocarbonyl group, imino group, hydrazide group, ureylene group, carbonimidoyl group,
Examples include formylimino group.

Examples of the heterocyclic compound represented by any of the general formulas (IV-1) to IV-12) include:
22°-dipyridyl, di-2-pyridylketone, 22°
-dipyridylamine, 33°-dipyridyl, 66'-dimethyl-33°-dipyridyl, di-3-pyridylketone, 44'-dipyridyl, 1,2-bis(4-pyridyl)ethane, 1,2-bis(4- pyridyl) ethylene, 2
2°-dipyridyl-N-oxide, 22′-dithiobis(pyridine-N-oxide), 1,2-bis(2-pyridyl)ethylene-N-oxide, 44″-dimethyl-
22°-dipyridyl-N-oxide, di-1,2-pyridylketone-N-oxide, 33°-dipyridyl-N-
Oxide, 66°-dimethyl-33°-dipyridyl-N
-oxide, 44°-dipyridyl-N-oxide, 1.
Examples include 2-bis(4-pyridyl)ethane-N-oxide, di-4-pyridylketone-N-oxide, and 33°-dimethyl-44′-dipyridyl-N-oxide.

The general formulas (IV-4) to (IV-6) and (I
In the heterocyclic compounds represented by V-10) to (IV-12), N
Although O (oxygen) is bonded to each (nitrogen), the present invention is not limited to this, and O may be bonded only to N of either one of the heterocycles.

The blending ratio of the heterocyclic compound represented by any of the general formulas (rV-1) to (IV-12) to the alkali-soluble polymer having a phenol skeleton is 1 to 300 parts by weight per 100 parts by weight of the polymer. It is preferably 2 to 100 parts by weight, more preferably 2 to 100 parts by weight. When the blending ratio of the heterocyclic compound is less than 1 part by weight, it becomes difficult to impart sufficient photosensitivity to the composition.

Furthermore, when the blending ratio of the heterocyclic compound exceeds 300 parts by weight, the light transmittance of the resist film decreases, making it difficult for the exposure light to reach the substrate side of the resist film.
As a result, it becomes difficult to form a pattern with a good cross-sectional shape.

The photosensitive composition (E) according to the present invention comprises the alkali-soluble polymer having the phenol skeleton and the general formula (V
-1) to V-4), and can be suitably used as a negative resist.

2 introduced into the general formula (V-1) or V-4)
Examples of the valent organic group Z include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a vinylene group,
2-butenylene group, malonyl group, succinyl group, glutaryl group, fumaroyl group, carbonyl group, oxalyl group,
Examples include carbonyldioxy group, sulfinyl group, sulfonyl group, dithio group, thiocarbonyl group, imino group, hydrazide group, ureylene group, carbonimidoyl group, and formylimino group.

In addition, the anion X- in the general formula (V-1) to V-4) is, for example, a halogen ion, a sulfate ion, a perchlorate ion, a sulfonate ion, or boron, aluminum, iron, zinc. Examples include anions of halogen compounds such as , arsenic, antimony, and ricin.

Examples of the pyridinium salt represented by the general formula (V-1) to V-4) include pyridinium-p-toluenesulfonate, 2-methylpyridinium-p-toluenesulfonate, and 2-chloro-1-methylpyridinium- p-toluenesulfonate, 2.4.6-collidine-p-toluenesulfonate, l-ethylpyridinium chloride, l-pentylpyridinium chloride, 1
-dodecylpyridinium chloride, l-hexadecylpyridinium chloride, 1-benzyl-3-hydroxypyridinium chloride, l-carboxymethylpyridinium chloride, 2,6-dimethyl-t-methylpyridinium chloride, 11'-dimethyl-44'-
Bipyridinium dichloride, 11°-dimethyl-4
4′-dimethyl-22°-bipyridinium dichloride, 24°-dipyridinium dichloride, 23′-dipyridinium dichloride, 1,2-bis(4-pyridinium)ethane dichloride, 1,2-bis(2-pyridinium)ethylene Examples include dichloride, 22°-dithiobispyridinium dichloride, di-2-pyridinium ketone dichloride, quinoxalinium-p-ethylsulfonate, and 8-hydroxy-t-methylquinoxalinium-p-1-luenesulfonate.

The pyridinium salts represented by the general formulas (V-1) to V-4) can also be used in a state bound to water molecules.

The pyridinium salt represented by the general formula (V-1) or V-4) can be prepared, for example, according to the method described in Nippon Kagaku Kinpaku "Jikken Chemistry Course 21 Synthesis of Organic Compounds", page 290 (195g). It can be synthesized by

The blending ratio of the pyridinium salt represented by the general formula (V-1) to V-4) to the alkali-soluble polymer having a phenol skeleton is 1 to 300 parts by weight per 100 parts by weight of the polymer. is preferable, and 5
More preferably, the amount is from 100 parts by weight. If the proportion of the heterocyclic compound is less than 1 part by weight, it will be difficult to impart sufficient photosensitivity to the composition. Furthermore, if the blending ratio of the heterocyclic compound exceeds 300 parts by weight, the light transmittance of the resist film decreases, making it difficult for the exposure light to reach the substrate side of the resist film, resulting in poor performance. It becomes difficult to form a pattern having a cross-sectional shape.

The photosensitive composition (F) according to the present invention contains the above-mentioned alkali-soluble polymer having a phenol skeleton and a polymer having a nitrogen-containing heterocyclic compound as a polymerized unit.

This composition can be suitably used as a negative resist.

In the polymer having the nitrogen-containing heterocyclic compound as a polymerized unit, some or all of the nitrogen atoms of the heterocyclic compound may be N-oxidized. Further, the heterocyclic compound may have a pyridine ring, and this heterocyclic compound may form a pyridinium salt. in particular,
For example, poly(2-vinylpyridine), poly(4-vinylpyridine), poly(2-vinyl-3-methylpyridine), poly(2-isopropenylpyridine), poly(4-vinylpyridine),
vinylpyrimidine), poly(2-vinylpyrazine), poly(2-vinylpyridine-1-oxide), poly(2-vinylpyridine-1-oxide),
vinyl-3-methylpyridine-1-oxide), poly(
l-vinylpyridinium fluoroborate), poly(2
-vinyl-1-methylpyridinium methyl sulfate), poly(4-vinyl-1-methylpyridinium-p-
toluenesulfonate), and copolymers of these polymers with polystyrene, polymethyl acrylate, polymethyl methacrylate, polypropylene, polyisobutylene, polyvinylphenol, polyisopropenylphenol, and the like.

The polymer having the nitrogen-containing heterocyclic compound as a polymerized unit is described, for example, in the Journal of America
an Chemical 5ociety, vol.
7B, p1879 (1954) Journal o
f Polymer 5science, vol.

B-9, p13 (1971) and the like.

The blending ratio of the polymer having the nitrogen-containing heterocyclic compound as a polymerization unit to the alkali-soluble polymer having a phenol skeleton is 100 parts of the alkali-soluble polymer.
It is preferably 5 to 400 parts by weight, more preferably 10 to 200 parts by weight. If the amount of the polymer having a nitrogen-containing heterocyclic compound as a polymerized unit is less than 5 parts by weight, it will be difficult to impart sufficient photosensitivity to the composition. Furthermore, if the proportion of the heterocyclic compound exceeds 400 parts by weight, the dry etching resistance tends to decrease.

In addition, in this photosensitive composition (F), in addition to the alkali-soluble polymer having the phenol skeleton and the polymer having the nitrogen-containing heterocyclic compound as a polymerization unit, the following general formula (Vl-1) is used. or VI-15).
Sensitivity to UV can be further increased.

(Here, R28 to R'' may be the same or different, and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group,
Alkenyl group, hydroxyl group, amino group, dialkylamino group having 1 to 5 carbon atoms, nitro group, carboxy group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group group, mesityl group, benzyl group, styryl group, cinnamyl group, mercapto group, cyano group, or halogen atom, X- represents an anion, and Z represents a divalent organic group) the general formula (VI-6) (Vl-12) and (■1
Examples of the divalent organic group 2 introduced in 5) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a vinylene group, a 2-butenylene group, a malonyl group, a succinyl group, a glutaryl group, a fumaroyl group, Examples include carbonyl group, oxalyl group, carbonyldioxy group, sulfinyl group, sulfonyl group, dithio group, thiocarbonyl group, imino group, hydrazide group, ureylene group, carbonimidoyl group, and formylimino group.

Moreover, the general formula (VI-13) or VI-1
Examples of the anion X- in 5) include halogen ions, sulfate ions, perchlorate ions, sulfonate ions, or anions of halogen compounds such as boron, aluminum, iron, zinc, arsenic, antimony, and phosphorus. be able to.

Examples of the heterocyclic compound represented by the general formula (VI-1) to VI-6) include pyridine, 2-ethylpyridine, 2,4-dimethylruviridine, 2-acetylpyridine, and 2-methoxypyridine. , 3-hydroxypyridine, 3-pyridinecarboxylic acid, 2-chloropyridine, nicotinamide, 2-phenylpyridine, pyridazine, 3-methylpyridazine, 4-methylpyrimidine, pyrazine, 2,5-dimethylpyrazine, 22'-dipyridyl , di-2-pyridylketone, 22"-dipyridylamine, 33°-dipyridyl, 66°-dimethyl-3,
3°-dipyridyl, di-3-pyridylketone, 44′-dipyridyl, 1,2-bis(4-pyridyl)ethane,
Mention may be made of 1,2-bis(4-pyridyl)ethylene.

Moreover, the general formula (Vl-7) or Vl-12)
Examples of the heterocyclic compounds include pyridine-1-oxide, 2-methylpyridine-1-oxide, 3-methylpyridine-1-oxide, 4-methylpyridine-t-oxide, 4-nitro pyridine-1-oxide, 4-nitro-2-methylpyridine-1-oxide,
4-nitro-3,5-dimethylpyridine-1-oxide, 4-nitro-2,6-dimethylpyridine-1-oxide, 4-nitro-3-chloropyridine-1-oxide,
4-nitro-3-pyridinecarboxylic acid-i-oxide,
4-acetylpyridine-1-oxide, 2-aminopyridine-1-oxide, 3-hydroxypyridine-1-oxide, 2,6-dimethylpyridine-1-oxide, pyridazine-N-oxide, 4-methylpyridazine- n-
oxide, 4,5-dimethylpyridazine-N-oxide, 4,6-dimethylpyrimidine-N-oxide, 4-methoxypyrimidine-N-oxide, pyrazine-N-oxide, 2,3-dichloropyridazine-N-oxide, 2.
6-dichloropyrazine-N-oxide, 22'-dipyridyl-N-oxide, 22'-dithiobis(pyridine-
N-oxide) 1,2-bis(2-pyridyl)ethylene-N-oxide, 4,4°-dimethyl-22°-dipyridyl-N-oxide, di(,2-pyridylketone-N
-oxide, 33゛-dipyridyl-N-oxide,
66°-dimethyl-33°-dipyridyl-N-oxide, 24'-dipyridyl-N-oxide, 1,2-bis(
4-pyridyl)ethane-N-oxide, di-4-pyridylketone-N-oxide, 33'-dimethyl-4,4
Mention may be made of '-dipyridyl-N-oxide.

In addition, the general formula (Vl-8) or VI-12)
In , O is bonded to each of the two N, but
It is also possible to use a heterocyclic compound in which O is bonded to only one of the N atoms.

The N-oxide compound represented by the general formula (Vl-7) to Vl-12) is, for example, TheJou
rnal of Organic Cherin1s
tryS vol, 2B, p659<1961).

The general formula (Vl -13) or Vl -15)
Examples of the pyridinium salt represented by
-Methylpyridinium-p-toluenesulfonate, 2
, 4.6-collidine-p-toluenesulfonate, l-
Ethylpyridinium chloride, 1-dodecylpyridinium chloride, 1-benzyl-3-hydroxypyridinium chloride, 1-carboxymethylpyridinium chloride, 2,6-dimethyl-1-methylpyridinium chloride, 11°-dimethyl-44′-bipyridinium dichloride, 11 °-dimethyl-44゛-dimethyl-22°-bipyridinium dichloride, 24゛-dipyridinium dichloride, 23゛-dipyridinium dichloride, l,2-bis(4-pyridinium)ethane dichloride, l,2-bis(2) -pyridinium) ethylene dichloride, 22°-dithiobispyridinium dichloride, di-2-pyridinium ketone dichloride, quinoxalinium-p-ethylsulfonate, 8-
Mention may be made of hydroxy-1-methylquinoxalinium-p-toluenesulfonate.

The general formula (Vl -13) or Vl -15)
For example, the pyridinium salt represented by
(195g).

In addition, these general formula (VI-13) or Vl −
The pyridinium salt represented by 15) can also be used in the form of a hydrate bound to water molecules.

The general formula (VI-1) or Vl for the mixture of the alkali-soluble polymer having the phenol skeleton and the polymer having the heterocyclic compound as a polymerized unit.
The compounding ratio of the heterocyclic compound represented by any one of -15) is preferably 2 to 300 parts by weight, and 2 to 100 parts by weight, based on 100 parts by weight of the polymer mixture.
Parts by weight are more preferred. When the proportion of the heterocyclic compound is less than 1 part by weight, the sensitivity of the resulting photosensitive composition tends to decrease. Also, the blending amount is 3
If it exceeds 0.00 parts by weight, the light transmittance of the resist film decreases, making it difficult for the exposure light to reach the substrate side of the resist film, and as a result, it becomes difficult to form a pattern with a good cross-sectional shape. becomes difficult.

In addition, the photosensitive composition (A) or F) according to the present invention
In addition to the above-mentioned components, a surfactant as a coating film modifier, a dye as an antireflection agent, and the like may be blended as necessary.

Next, pattern formation using the photosensitive composition according to the present invention will be explained.

First, a resist solution is prepared by dissolving any one of the photosensitive compositions (A) to F) in an organic solvent. Examples of solvents used at this time include cyclohexanone,
Ketone solvents such as furfural, methyl ethyl ketone, methyl isobutyl ketone, cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, Alcohol solvents such as 1-butanol, 2-butanol, isoamyl alcohol, diethylene glycol, polyhydric alcohol derivative solvents such as ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, ethyl carpitol, morpholine, N
Examples include nitrogen compound solvents such as -methyl-2-pyrrolidone, benzonitrile, and pyridine. These solvents can be used alone or in combination of two or more.

Thereafter, the prepared resist solution is applied onto the substrate by a conventional method such as a spin coating method or a dipping method, and is dried to form a resist film. Examples of substrates on which a resist film is formed include silicon wafers, silicon wafers having steps formed with various insulating films, electrodes, wiring, etc.;
■-V group compound 5uch as GaAs, AlGa
Examples include As semiconductor wafers, crystal, piezoelectric wafers such as lithium tantalate, and blank masks.

Next, pattern exposure is performed by selectively irradiating the resist film with deep UV through a mask having a desired pattern. For example, a mercury lamp can be used as a deep UV light source.

After pattern exposure, the resist film is developed using an alkaline aqueous solution. As a result, in the resist film formed using the photosensitive compositions (A) and (C) or F) of the present invention, the unexposed portions are dissolved and removed to form a desired negative pattern. Furthermore, in the resist film formed using the photosensitive composition (B) of the present invention, the exposed portion is dissolved and removed to form a positive pattern. The alkaline aqueous solution used when developing the resist film is as follows:
For example, tetramethylammonium hydroxide (
Examples include organic alkali aqueous solutions such as TMAH) aqueous solutions, and inorganic alkali aqueous solutions such as potassium hydroxide solutions and sodium hydroxide solutions. As a developing method, a usual dipping method, spraying method, etc. can be used. Further, after the development process, a rinsing process can be performed using water or the like.

(Function) The photosensitive composition (A) according to the present invention comprises an alkali-soluble polymer having a phenol skeleton, a heterocyclic compound represented by the general formula (1-1) or (1-2), and a photosensitive composition. Product (C) comprises an alkali-soluble polymer having a phenol skeleton, a heterocyclic compound represented by any one of the general formulas (m-1) to m-8), and a photosensitive composition (
D) is an alkali-soluble polymer having a phenol skeleton and a heterocyclic compound represented by any one of the above general formulas (IV-1) to (IV-12); and the photosensitive composition (E) is an alkali-soluble polymer having a phenol skeleton. By combining an alkali-soluble polymer having the formula (V-1) or a pyridinium salt represented by any of the above general formulas (V-1) to V-4), a negative resist that is well sensitive to deep UV can be obtained. can be used.

Further, the photosensitive composition (B) according to the present invention comprises an alkali-soluble polymer having a phenol skeleton and the general formula (n
By combining it with a heterocyclic compound represented by -1) or (II-2), it can be used as a positive resist that is well sensitive to deep UV.

Furthermore, the photosensitive composition (F) of the present invention has good resistance to deep UV by combining an alkali-soluble polymer having a phenol skeleton and a polymer having a nitrogen-containing heterocyclic compound as a polymerized unit. It can be used as a negative resist that is sensitive to light.

In addition, by performing exposure and development using these photosensitive compositions, it is possible to increase the tolerance of control in the exposure and development process, and it has excellent dry etching resistance, and it is possible to form fine particles with a rectangular cross-sectional shape. It is possible to form various patterns.

(Example) Examples of the present invention will be described in detail below.

Example 1 Poly(p-vinylphenol) toor and 2-
20 g of ethylpyridine was dissolved in 300 g of ethyl cellosolve acetate. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Next, apply this resist solution onto a silicon wafer,
Dry on a hot plate for 4 minutes at 90°C to obtain a thickness of 1.
A resist film of 0μ was formed. After that, the formed resist film was exposed to KrF excimer laser light (wavelength 248 nm).
Pattern exposure was performed using a reduction projection exposure machine using a (200a+J/cd). After pattern exposure, the resist film was diluted with a TMAH aqueous solution with a concentration of 0.95% by weight.
Development was performed by immersing the film for a minute.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.40 and a rectangular cross-section was obtained.

Example 2 3.5-xylenol novolak resin 100. and 2
-15g of chloropyridine (ethyl cellosolve acetate)
Dissolved in 300g. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 1. However, the pattern exposure is 260 J/cd.
The concentration of the TMAH aqueous solution was 1.43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A resist pattern with a line width of 0.40M and a rectangular cross-section was obtained.

Example 3 100 g of poly(p-vinylphenol) and 4-
20 g of methylpyridine-1-oxide was dissolved in 400 g of cyclohexanone. This solution was then added to 0.2μ
Filtered using a fluororesin membrane filter,
This was used as a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 1. However, pattern exposure is 180mJ/cd
I did it.

As a result, the unexposed parts of the resist film are dissolved and removed.
A resist pattern with a line width of 0.35 n and a rectangular cross-section was obtained.

Example 4 3.5-xylenol novolac resin ioo and 25 g of pyridine-N-oxide were dissolved in 300 g of ethyl cellosolve acetate. This solution was then diluted to 0.
It was filtered using a fluororesin membrane filter (No. 2) to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 1. However, pattern exposure is 250mJ/c-
The concentration of the TMAH aqueous solution was 1.43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.40 and a rectangular cross-section was obtained.

Example 5 Poly(p-vinylphenol) 100. and quinoline-1-oxide 12 tr to cyclohexanone 40
Dissolved in 0g. Next, this solution was filtered using a 0.2-mm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 1. However, pattern exposure is 180J/
It was done at cj.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern having a line width of 0.35 mm and a rectangular cross-sectional shape was obtained.

Example 6 Poly(p-vinylphenol) long and 4-
Nitropyridine-N-oxide 25K was dissolved in 400 g of cyclohexanone. This solution was then diluted to 0.
It was filtered using a fluororesin membrane filter (No. 2) to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 1. However, pattern exposure is 140 times J/c.
It was done in d.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.35 μm and a rectangular cross-section was obtained.

Example 7 Aluminum film (l film) formed on silicon wafer
The resist solution prepared in Example 3 was applied to the surface of the substrate, and a resist pattern having a line width of 0.35 tlM was formed according to the same procedure as in Example 3.

Next, using this resist pattern as a mask, the exposed Al film is coated with CBrCj! Dry etching was performed using i-gas. As a result, a pattern with a line width of 0.35 m, similar to the resist pattern, could be faithfully transferred onto the Al film.

Comparative Example 1 A polymethyl methacrylate solution was applied to the surface of an Al film formed on a silicon wafer, and a resist pattern was formed in the same manner as in Example 1.

Next, using this resist pattern as a mask, the exposed Ar1 film was dry etched using CBrCρ gas. As a result, the polymethyl methacrylate pattern disappeared during etching of the Ar1 film.
The pattern could not be transferred completely.

Example 8 Poly(p-vinylphenol) 100g and 3
-Hydroxy-2-methyl-4-pyrone 18 was dissolved in 300 g of ethyl cellosolve acetate. Next, this solution was filtered using a 0.2p fluororesin membrane filter to obtain a resist solution.

Next, apply this resist solution onto a silicon wafer,
Dry on a hot plate for 1 minute at 90°C to obtain a thickness of 1.
An ON resist film was formed. After that, the formed resist film was exposed to KrF excimer laser light (wavelength 248 nm).
Pattern exposure was carried out using a reduction projection exposure machine using a (200 Jlcd). After pattern exposure, the resist film was developed by immersing it in a 0.95% by weight aqueous TMAH solution for 1 minute.

As a result, the exposed portion of the resist film was dissolved and removed, resulting in a highly accurate resist pattern having a line width of 0.40 mm and a rectangular cross-sectional shape.

Example 9 100 g of 3.5-xylenol novolac resin and 3
15 g of -hydroxy-4-pyrone was dissolved in 300 g of ethyl cellosolve acetate. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 8. However, pattern exposure is 240Jlc
The concentration of the TMAH aqueous solution was 1.43% by weight.

As a result, the exposed portion of the resist film was dissolved and removed, resulting in a line width of 0.40. A highly accurate resist pattern with a rectangular cross-sectional shape was obtained. - Example 10 Poly(p-vinylphenol) 100g and 4-
15 g of hydroxy-6-methyl-2-pyrone was dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 8. However, pattern exposure is 220 J/cd.
I did it.

As a result, the exposed portion of the resist film was dissolved and removed, and a highly accurate resist pattern with a line width of 0.40 μm and a rectangular cross-sectional shape was obtained.

Example 11 A, l! formed on a silicon wafer. The resist solution prepared in Example 8 was applied to the surface of the film, and a resist pattern with a line width of 0.40 μm was formed in accordance with the same procedure as in Example 8.

Next, using this resist pattern as a mask, the exposed Ag film was dry etched using CB r CII 3 gas. As a result, a pattern with a line width of 0.40 μm, similar to the resist pattern, could be faithfully transferred onto the Ag film.

Example 12 Poly(p-vinylphenol) 100g and 3-
Methylpyridine 20i to ethyl cellosolve acetate 3
Dissolved in 00g. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Next, apply this resist solution onto a silicon wafer,
Dry on a hot plate for 5 minutes at 90°C to obtain a thickness of 1.
A 0- resist film was formed. After that, KrF excimer laser light (wavelength 248 ns) was applied to the formed resist film.
Pattern exposure was performed using a reduction projection exposure machine using a (500 sJ/cd). After pattern exposure, the resist film was developed by immersing it in a 0.95% by weight aqueous TMAH solution for 1 minute.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.40 μm and a rectangular cross-sectional shape was obtained.

Example 13 Ioo g of 3.5-xylenol novolak resin and 18 g of 4-methylpyridine were dissolved in 300 g of ethyl cellosolve acetate. Then, add this solution to 0.2
It was filtered using a μ fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 12. However, pattern exposure is 580sJ/c
The concentration of the TMAH aqueous solution was 1.43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 μm and a rectangular cross-section was obtained.

Example 14 100 g of poly(p-vinylphenol) and 2.
20 g of 5-dimethylpyrazine and 40 g of cyclohexanone
Dissolved in 0g. Next, this solution was filtered using a 0.2 μm membrane filter made of fluorine resin to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 12. However, nokuturn exposure 1t480
/C-.

As a result, the unexposed parts of the resist film were dissolved and removed, and a highly accurate negative pattern with a line width of 0.40 trs and a rectangular cross-section was obtained. 100 g of resin and 16 g of 1.3.5-) riazine were dissolved in 300 g of ethyl cellosolve acetate. This solution was then reduced to 0
．． It was filtered using a 2μ fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 12. However, the concentration of TMAH aqueous solution is 1.4
The content was 3% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40x and a rectangular cross-sectional shape was obtained.

Example 16 100 g of poly(p-vinylphenol) and 18 g of pyridazine-N-oxide were mixed with 4 g of Schif-lohexanone.
Dissolved in 00g. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 12. However, pattern exposure is 220 J/c.
It was done in d.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.35 tries and a rectangular cross-section was obtained.

Example (7 poly(p-vinylphenol) long and 4,
18 g of 6-dimethylpyrimidine-N-oxide was dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 12. However, pattern exposure is 180a+J/
It was done at cj.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.35 μm and a rectangular cross-sectional shape was obtained.

Example (8 poly(p-vinylphenol) long and 2,
20 g of 3-diethylpyrazine-N-oxide was dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed in the same manner as in Example 12. However, pattern exposure is 160 J/c.
I did it with j.

As a result, the unexposed parts of the resist film are dissolved and removed.
The line width is 0.35. A highly accurate negative pattern with a rectangular cross-section of cm was obtained.

Example 19 Poly(p-vinylphenol) loog and 2,
4゜s-trimethoxy-1,3,5-triazine-N-
Oxide IB g: was dissolved in cyclohexanone 400f. Next, this solution was filtered using a 0.2-mm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 12. However, pattern exposure is 160J/c.
It was done in d.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.35 mm and a rectangular cross-sectional shape was obtained.

Example 20 An Ag film was formed on a silicon wafer, and the resist solution prepared in Example 18 was applied onto this Afi film.

After that, the line width was adjusted to 0.3 according to the same procedure as in Example 18.
A 5μ negative pattern was formed.

Next, using this negative pattern as a mask, the exposed Ag film was dry etched using CBrCj73 gas.

As a result, a pattern with a line width of 0.35# could be faithfully transferred to the Ag film.

Comparative Example 2 A film was formed on a silicon wafer, and a polymethyl methacrylate solution was applied onto the Ap pattern film.

Thereafter, a negative pattern was formed according to the same procedure as in Example 12.

Next, using this negative pattern as a mask, the exposed Al film was dry etched using CBrCg gas.

As a result, the polymethyl methacrylate pattern disappeared during etching of the Ag film, and the pattern could not be completely transferred.

Example 21 Poly(p-vinylphenol) 100g and 22
20 g of '-dipyridylamine was dissolved in 300 g of ethyl cellosolve acetate. This solution was then reduced to 0
．． It was filtered using a fluororesin membrane filter (No. 2) to obtain a resist solution.

Next, apply this resist solution onto a silicon wafer,
Dry on a hot plate for 5 minutes at 90°C to obtain a thickness of 1.
A resist film of 0μ was formed. After that, KrF excimer laser light (wavelength 248 ns) was applied to the formed resist film.
Pattern exposure was carried out using a reduction projection exposure machine using a (400 J/cj). After pattern exposure,
The resist film was developed by immersing it in a TMAH aqueous solution having a concentration of 0.95% by weight for 1 minute.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.40 μm and a rectangular cross-sectional shape was obtained.

Example 22 100 g of 3.5-xylenol novolak resin and 18 g of 33'-dipyridyl were dissolved in 300 g of ethyl cellosolve acetate. Then, add this solution to 0.2
It was filtered using a μ fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 21. However, pattern exposure is 460sJ/c
The concentration of the TMAH aqueous solution was 43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 μm and a rectangular cross-section was obtained.

Example 23 Poly(p-vinylphenol) 100g and 44
20 g of ゛-dipyridyl was dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 m membrane filter made of fluorine resin to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 21. However, pattern exposure is 380 J/c.
It was done in d.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 nm and a rectangular cross-section was obtained.

Example 24 Poly(p-vinylphenol) 100g and 22
'-dithiobis(pyridine-N-oxide) 10g
was dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 21. However, pattern exposure is 280mJ/c
I did it with -.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.35 μm and a rectangular cross-sectional shape was obtained.

Example 25 100 g of 3.5-xylenol novolac resin and 8 g of 33°-dipyridyl-N-oxide were dissolved in 300 g of cyclohexanone. Then, add this solution to 0.2
It was filtered using a μ fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 21. However, pattern exposure is 320J/c.
The concentration of the TMAR aqueous solution was 1.43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.35 n and a rectangular cross-section was obtained.

Example 26 100 g and 1 of poly(p-vinylphenol),
2-bis(4-pyridyl)ethane-N-oxide 10
g was dissolved in 400 g of cyclohexanone. Next, this solution was passed through a 0.2-mm fluororesin membrane filter.
The solution was filtered to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 21. However, pattern exposure is 240J/c.
I did it with j.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.35 tag and a rectangular cross-section was obtained.

Example 27 An AI film was formed on a silicon wafer, and the resist solution prepared in Example 26 was applied onto this Al film. After that, the line width was adjusted to 0.35 according to the same procedure as in Example 26.
．． A negative pattern was formed.

Next, using this negative pattern as a mask, dry etching was performed on the exposed AI film using CBrCj13 gas.

As a result, it was possible to faithfully transfer a pattern with a line width of 0.35 to the /l film.

Example 28 100 g of poly(p-vinylphenol) and 25 g of pyridinium-p-toluenesulfonate were dissolved in a mixed solvent of 400 g of cyclohexanone and 50 g of ethyl lactate. Next, add 0.2t! of this solution! It was filtered using a fluororesin membrane filter (M) to obtain a resist solution.

Next, apply this resist solution onto a silicon wafer,
Dry on a hot plate for 5 minutes at 90°C to obtain a thickness of 1.
A 0- resist film was formed. After that, KrF excimer laser light (wavelength 248n) is applied to the formed resist film.
Pattern exposure was performed using a reduction projection exposure machine using a (36 hJ/cd). After pattern exposure, the resist film was developed by immersing it in a TMAH aqueous solution having a concentration of 0.95% by weight for 1 minute.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.35 μm and a rectangular cross-section was obtained.

Example 29 100 g of 3.5-xylenol novolac resin and 2.4.6-collidine-p-toluenesulfonate
0 g was dissolved in 300 g of ethyl cellosolve acetate.

Next, this solution was filtered using a 0.2N fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 28. However, pattern exposure is 380mJ/c
-, and the concentration of the TMAH aqueous solution was 1.43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 μm and a rectangular cross-section was obtained.

Example 30 Poly(p-vinylphenol) loog and L
L'-dimethyl-44'-bipyridinium chloride 1
8 [was dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 28. However, pattern exposure is 280iJ/c
d, and the concentration of TMAH water/solution was 0.85% by weight.
And so.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 M and a rectangular cross-section was obtained.

Example 31 3.5-xylenol novolak resin 100g and 1
．． 2-bis(4-pyridinium)ethane dichloride 2
0 g was dissolved in 300 g of ethyl cellosolve acetate. Next, this solution was filtered using a 0.21 gm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 28. However, pattern exposure is 340mJ/c
-, and the concentration of the TMAH aqueous solution was 1.43% by weight.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 and a rectangular cross-sectional shape of IIM was obtained.

Example 32 100 g of poly(p-vinylphenol) and 20 g of quinoxalinium-p-ethylsulfonate were dissolved in 400 g of cyclohexanone. Next, this solution was filtered using a 0.2 μm fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 28. However, pattern exposure is 300IIJ/
cj, and the concentration of the TMAH aqueous solution was 0.85% by weight.
And so.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 ts and a rectangular cross-section was obtained.

Example 33 An Al1 film was formed on a silicon wafer, and the resist solution prepared in Example 28 was applied onto this Al film.

After that, following the same procedure as in Example 28, the line width was 0.35.
A negative pattern of M was formed. However, pattern exposure was performed at 320a+J/cj.

Next, using this negative pattern as a mask, the exposed Al film was dry etched using CBrC#t gas.

As a result, a pattern with a line width of 0.35 μm could be faithfully transferred to the Al film.

Comparative Example 3 An Al film was formed on a silicon wafer, and a polymethyl methacrylate solution was applied onto the Al film.

Thereafter, a negative pattern was formed according to the same procedure as in Example 28.

Next, using this negative pattern as a mask, the exposed Al film was dry etched using CBrC1 gas.

As a result, the polymethyl methacrylate pattern disappeared during etching of the Aρ film, and the pattern could not be completely transferred.

Example 34 Poly(p-vinylphenol) (0 mouth g and poly(p-vinylphenol)
80 g of 2-vinylpyridine-CO-styrene was dissolved in 500 g of ethyl cellosolve acetate. Then,
This solution was filtered using a 0.2-mm fluororesin membrane filter to obtain a resist solution.

Next, apply this resist solution onto a silicon wafer,
Dry on a hot plate for 5 minutes at 90°C to obtain a thickness of 1.
An Otrm resist film was formed. After that, the formed resist film is exposed to KrF excimer laser light (wavelength 248 nm).
) Pattern exposure was performed using a reduction projection exposure machine (580 mJ/c4). After pattern exposure, the resist film was diluted with a TMAH aqueous solution with a concentration of 0.95% by weight.
Development was performed by immersing the film for a minute.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate resist pattern with a line width of 0.40 and a rectangular cross-section was obtained.

Example 35 100 g of poly(p-vinylphenol) and 50 g of poly(2-vinylpyridine-1-oxide) were dissolved in 600 g of cyclohexanone. This solution was then reduced to 0
．． It was filtered using a 2μ fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 34. However, pattern exposure is 400mJ/c
It was done in d.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 μm and a rectangular cross-section was obtained.

Example 36 Poly(p-vinylphenol) loog and poly(4
-vinyl-1-methylpyridinium-p-)luenesulfonate) was dissolved in a mixed solvent of 500 g of cyclohexanone and too much ethyl lactate. Then,
This solution was filtered using a 0,2-fluororesin membrane filter to obtain a resist solution.

Thereafter, a resist pattern was formed according to the same procedure as in Example 34. However, pattern exposure is 320mJ/c
I did it with j.

As a result, the unexposed parts of the resist film are dissolved and removed.
A highly accurate negative pattern with a line width of 0.40 m and a rectangular cross-section was obtained.

Examples 37 to 41 100 g of poly(p-vinylphenol) 20 g of poly(4-vinylpyridine-CO-styrene) and the following first
Cyclohexanone 8
Dissolved in 00g. The amount of each heterocyclic compound added is also listed in Table 1. Next, this solution was filtered using a 0.2N fluororesin membrane filter to obtain resist solutions of Examples 37 to 41, respectively.

Thereafter, a resist pattern was formed using each resist solution according to the same procedure as in Example 34.

However, pattern exposure for each resist film was performed at the exposure doses listed in Table 1.

As a result, the unexposed portions of each resist film were dissolved and removed, and highly accurate negative patterns having line widths listed in Table 1 and having a rectangular cross-sectional shape were obtained.

Examples 42-46 Poly(p-vinylphenol) 100g, poly(p-vinylphenol)
2-vinyl-3-methylpyridine-1-oxide) 15
g and the heterocyclic compounds shown in Table 2 below were dissolved in 600 g of cyclohexanone. The amount of each heterocyclic compound added is also listed in Table 2. This solution was then diluted to 0.
It was filtered using a 2μ fluororesin membrane filter to obtain resist solutions of Examples 42 to 46, respectively.

Thereafter, a resist pattern was formed using each resist solution according to the same procedure as in Example 34.

However, pattern exposure for each resist film was performed at the exposure doses listed in Table 2.

As a result, the unexposed portions of each resist film were dissolved and removed, and highly accurate negative patterns having line widths shown in Table 2 and having a rectangular cross-sectional shape were obtained.

Examples 47-51 Poly (p-vinylphenol) 100g, poly
(2-vinyl-1-methylpyridinium methyl sulfate) and the heterocyclic compounds shown in Table 3 below were mixed with 500 g of cyclohexanone and 1 gram of ethyl lactate.
00 g dissolved in a mixed solvent. The amount of each heterocyclic compound added is also listed in Table 3. Then, add this solution to 0.2
The resist solutions of Examples 47 to 51 were obtained by filtration using a μ fluororesin membrane filter.

Thereafter, a resist pattern was formed using each resist solution according to the same procedure as in Example 34.

However, pattern exposure for each resist film was performed at the exposure doses listed in Table 3.

As a result, the unexposed portions of each resist film were dissolved and removed, and highly accurate negative patterns with a rectangular cross-sectional shape and line widths shown in Table J3 were obtained.

The methacrylate pattern disappeared and the pattern could not be completely transferred.

〔Effect of the invention〕

As described above, the photosensitive composition according to the present invention has a deep
It is well sensitive to UV light, and by using this photosensitive composition, it has excellent dry etching resistance and can form a fine pattern with a rectangular cross section. Therefore, it has remarkable effects such as being able to be effectively used as a mask in the dry etching process in the manufacture of semiconductor devices. Further, in pattern formation using the photosensitive composition according to the present invention, it is possible to increase the tolerance in controlling the exposure and development steps.

Claims (1)

[Scope of Claims] (1) A photosensitive composition containing an alkali-soluble polymer having a phenol skeleton and a heterocyclic compound represented by the following general formula (I-1) or (I-2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I -1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I -2) (Here, Z^1 is the number necessary to form a nitrogen-containing heterocycle. The nonmetallic atomic groups R^1 and R^2 may be the same or different, and each has a hydrogen atom and a carbon number of 1 to
20 unsubstituted or substituted alkyl groups, alkoxy groups,
Acyl group, alkenyl group, hydroxyl group, amino group, carbon number 1
-5 dialkylamino group, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, Cinnamyl group, mercapto group,
(2) A photosensitive composition containing an alkali-soluble polymer having a phenol skeleton and a heterocyclic compound represented by the following general formula (II-1) or (II-2). . ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II-1) (Here, Z^2 and Z^3 may be the same or different, and each is necessary to form a heterocycle containing oxygen. The nonmetallic atomic groups R^3 and R^4 may be the same or different, and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkenyl group. , hydroxyl group, amino group, dialkylamino group having 1 to 5 carbon atoms, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group,
Carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, cinnamyl group, mercapto group, cyano group, halogen atom) ▲ Numerical formula, chemical formula,
There are tables, etc. ▼ (II-2) (Here, Z^4 is a group of nonmetallic atoms necessary to form a heterocycle containing oxygen, R^5 is a hydrogen atom, and has a carbon number of 1 to 20.
unsubstituted or substituted alkyl group, alkoxy group, acyl group, alkenyl group, hydroxyl group, amino group, carbon number 1-5
dialkylamino group, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, cinnamyl group , a mercapto group, a cyano group, or a halogen atom) (3) An alkali-soluble polymer having a phenol skeleton and any of the heterocyclic compounds represented by the following general formulas (III-1) to (III-8). A photosensitive composition containing. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III-2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III-3) ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ (III-4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III-5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III-6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III-7) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III-8) (Here, R^6 and R^9 may be the same or different, and each represents a hydrogen atom and a carbon number of 1. ~20 unsubstituted or substituted alkyl groups, alkoxy groups, acyl groups, alkenyl groups, hydroxyl groups, amino groups, dialkylamino groups having 1 to 5 carbon atoms, nitro groups, carboxyl groups, methoxycarbonyl groups, ethoxycarbonyl groups, carboxymethyl (4) Alkali-soluble having a phenol skeleton A photosensitive composition containing a polymer and a heterocyclic compound represented by any one of the following general formulas (IV-1) to (IV-12). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-3) ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ (IV-4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-7) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-8) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-9) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV-10) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV-11) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV-12) (Here, R^1^0 to R^1^7 are the same and may also be different, each having a hydrogen atom and a carbon number of 1 to
20 unsubstituted or substituted alkyl groups, alkoxy groups,
Acyl group, alkenyl group, hydroxyl group, amino group, carbon number 1
-5 dialkylamino group, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, Cinnamyl group, mercapto group,
Cyano group, halogen atom, Z represents a divalent organic group) (
5) an alkali-soluble polymer having a phenol skeleton;
A photosensitive composition containing any one of pyridinium salts represented by the following general formulas (V-1) to (V-4). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V-2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V-3) ▲ Mathematical formulas, chemical formulas, There are tables, etc.▼(V-4) (Here, R^1^8 and R^2^7 may be the same or different, and each represents a hydrogen atom and a carbon number of 1 to 1.
20 unsubstituted or substituted alkyl groups, alkoxy groups,
Acyl group, alkenyl group, hydroxyl group, amino group, carbon number 1
-5 dialkylamino group, nitro group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, carboxymethyl group, carboxyethyl group, carbamoyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, styryl group, Cinnamyl group, mercapto group,
(6) An alkali-soluble polymer having a phenol skeleton and a polymer having a nitrogen-containing heterocyclic compound as a polymer unit. A photosensitive composition containing.