JPH0545883A - Photosensitive composition - Google Patents

Abstract

(57) [Abstract] [Purpose] The present invention can be applied with exposure to radiation having a short wavelength such as deepUV, has excellent dry etching resistance, and further has a high tolerance in development with an aqueous alkaline solution after exposure, which is favorable. An object of the present invention is to provide a photosensitive composition capable of forming a fine pattern having various sectional shapes. [Structure] (A) an alkali-soluble polymer, (B) a dissolution inhibitor composed of an organic compound having a substituent decomposable by an acid, and (C) a compound which generates an acid upon irradiation with light.
(D) a compound that suppresses diffusion of an acid generated by light irradiation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive composition,
In particular it relates to photosensitive compositions sensitive to deep UV and ionizing radiation.

[0002]

2. Description of the Related Art Photosensitive resins are widely used in the field of electronic components such as semiconductor integrated circuits which require various fine processing. In particular, in order to achieve high-density integration accompanying the multifunctionalization and high density of electronic devices, miniaturization of patterns is required. As an exposure apparatus used for pattern formation, there is a step-and-repeat reduction projection type mask aligner which is usually called a stepper. As a light source used for such a device, a g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 3) of a mercury lamp are used.
65 nm), XeF (wavelength 35 as an excimer laser)
1 nm), XeCl (wavelength 308 nm), KrF (wavelength 248 nm), KrCl (wavelength 222 nm), ArF
(Wavelength 193 nm), F ₂ (wavelength 157 nm) and the like. In order to form a fine pattern, the shorter the wavelength of the light source is, the better, and a photosensitive resin sensitive to deepUV such as an excimer laser is desired.

As a photosensitive resin for the above-mentioned excimer laser, polymethyl methacrylate (PMM) has been conventionally used.
A), a photosensitive composition comprising an acrylic polymer such as polyglutamic maleimide (PGMI) or a polymer having a phenol and an azide type photosensitizer is known. However, the former photosensitive resin has a problem that the sensitivity to an excimer laser is low and the dry etching resistance is poor. In the latter photosensitive composition, the sensitivity,
Although it has excellent dry etch resistance, the formed pattern becomes an inverted triangle, and there is a problem that it is difficult to control the exposure and development processes.

On the other hand, in various exposure methods, another problem has arisen with the reduction of the minimum size. For example,
In light exposure, the interference of reflected light due to the step on the semiconductor substrate has a great influence on the dimensional accuracy. Further, in the electron beam exposure, there is a problem that the height-to-width ratio of a fine resist pattern cannot be increased due to the proximity effect caused by backscattering of electrons.

As one method for solving the above-mentioned problems,
Multilayer resist processes have been developed. Such a multi-layer resist process is outlined in Solid State Technology, [Solid State Technology] 74 (1981), and many other studies on the system have been published. At present, a method that has been generally tried in many cases is a three-layer resist system, which is used for flattening the steps of a semiconductor substrate and for preventing reflection from the substrate, and for etching the bottom layer. And an uppermost layer as a photosensitive layer.

However, the three-layer resist process has an advantage that fine patterning can be performed as compared with the single-layer resist method, but on the other hand, there is a problem that the number of steps until pattern formation is increased. .. That is, de
Since there is no resist that satisfies both the sensitivity to radiation such as epUV and the resistance to reactive ion etching by oxygen plasma, these functions are provided in separate layers, resulting in an increase in the number of steps. There was a problem.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to de
It is highly sensitive to epUV and ionizing radiation, has excellent dry etching resistance, and can be highly tolerated in development with an alkaline aqueous solution after exposure, enabling the formation of fine patterns with good cross-sectional shape. Another object of the present invention is to provide a photosensitive composition.

Another object of the present invention is that it is well exposed to deepUV and ionizing radiation, can be developed by an alkaline aqueous solution, and has resistance to oxygen reactive ion etching (oxygen RIE resistance) after development. It is intended to provide a photosensitive composition which can form an excellent pattern and is suitable for a two-layer resist system.

[0009]

The photosensitive compositions (1) to (4) according to the present invention will be described in detail below. The photosensitive compositions (1) and (3) are applied to a pattern forming method by a single layer process described later, and the photosensitive composition (2) and
(4) is applied to a pattern forming method by a two-layer lithography process described later.

Photosensitive Composition (1) This photosensitive composition comprises (A) an alkali-soluble polymer,
(B) a dissolution inhibitor consisting of an organic compound having a substituent that decomposes with an acid, (C) a compound that generates an acid upon irradiation with light, and (D) a general formula of the following chemical formulas 11, 12, and 13.
And a compound represented by the formulas (I), (II) and (III).

[0011]

[Chemical 11] However, in the formula (I), X ₁ is O atom or S atom, and X ₂ is N atom.
An atom or a CR ⁴ group is shown. R ^{1 to} R ³ and R ^{4 of the} CR ⁴ group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic group. It represents a hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. Incidentally, R ² and R ³ may form a hydrocarbon ring group or a heterocyclic group.

[0012]

[Chemical formula 12] However, in formula (II), X ₃ is O atom or S atom, and X ₄ is N atom.
An atom or a CR ⁷ group is shown. R ⁵ , R ⁶ and R ^{7 of the} CR ⁷ group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic group. It represents a hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom.

[0013]

[Chemical 13] However, in the formula (III), X ₅ represents an O atom or an S atom, and X ₆ represents an N atom or a CR ¹¹ group. R ^{8 to} R ¹⁰ and the CR ¹¹
R ^{11 s} of the group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic hydrocarbon group,
It represents an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. Incidentally, R ⁹ and R ¹⁰ may form a hydrocarbon ring group or a heterocyclic group.

The alkali-soluble polymer as the component (A) is preferably a functional polymer having a hydroxy group-introduced aryl group or carboxy group. In particular,
Phenol novolac resin, cresol novolac resin, xyresole novolac resin, vinylphenol resin, isopropenylphenol resin, vinylphenol and acrylic acid, methacrylic acid derivative, acrylonitrile, styrene derivative copolymer, isopropenylphenol and acrylic acid , Methacrylic acid derivatives, acrylonitrile, copolymers with styrene derivatives, acrylic resins, methacrylic resins, acrylic acid or methacrylic acid and acrylonitrile, copolymers with styrene derivatives, copolymers of malonic acid and vinyl ether, etc. be able to. More specifically, poly (p-vinylphenol)
Copolymer), a copolymer of p-isopropenylphenol and acrylonitrile (copolymerization ratio 1: 1), a copolymer of p-isopropenylphenol and styrene (copolymerization ratio 1: 1), p-vinylphenol Examples of the copolymer include a copolymer of methyl and methyl methacrylate (copolymerization ratio 1: 1), a copolymer of p-vinylphenol and styrene (copolymerization ratio 1: 1), and the like.

As the dissolution inhibitor composed of an organic compound having a substituent which is decomposed by the acid which is the component (B),
For example, poly-t-butylvinylbenzene, poly-t-butoxycarbonyloxystyrene and the corresponding α-methylstyrene polymers described in US Pat. No. 4,491,628; described in US Pat. No. 4,603,101. Poly-t-butoxystyrene, poly-t-butoxy-α-methylstyrene, a polyacrylate having a t-butyl ester group or a benzyl ester group, and a side having such an acid labile group in or corresponding to the main chain. Polymers having a group; examples thereof include aromatic polymers having a carbonate side group such as t-butoxycarbonyl group and a trimethylsilyl ether side group. Specific examples of such organic compounds are shown in Tables 1 to 12 below.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

[Table 5]

[0021]

[Table 6]

[0022]

[Table 7]

[0023]

[Table 8]

[0024]

[Table 9]

[0025]

[Table 10]

[0026]

[Table 11]

[0027]

[Table 12] Light that is the component (C) (deep UV, ionizing radiation)
As the compound that generates an acid upon irradiation, various known compounds and mixtures can be used. For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt CF ₃ SO ₃ ⁻ , p-CH ₃ PhSO ₃ ⁻ , p-NO ₂
Examples thereof include salts such as PhSO ₃ ⁻ (where Ph is a phenyl group), organic halogen compounds, orthoquinone-diazide sulfonyl chloride, sulfonic acid ester, and the like. The organohalogen compound is a compound that forms hydrohalic acid, and such a compound is described in US Pat. No. 351.
5552, US Pat. No. 3,536,489, US Pat. No. 3,779,778 and West German Patent Publication No. 2243.
The thing disclosed by No. 621 is mentioned. Compounds which generate an acid upon irradiation with other light described above are disclosed in JP-A-54-7.
4728, JP-A-55-24113, JP-A-55-
77742, JP-A-60-3626, JP-A-60-
It is disclosed in JP-A-138539, JP-A-56-17345 and JP-A-50-36209. Specific examples of such compounds include di (p-tertiarybutylbenzene) diphenyliodonium trifluoromethanesulfonate, benzointosylate, orthonitrobenzyl paratoluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, tri (tert-butylphenylphenyl). ) Sulfonium trifluoromethanesulfonate, benzenediazonium paratoluenesulfonate, 4- (di-npropylamino) -benzonium tetrafluoroborate, 4-p-tolyl-mercapto-2,5-diethoxy-benzenediazonium hexafluorophosphate, tetra Fluoroborate, diphenylamine-4
-Diazonium sulfate, 4-methyl-6-trichloromethyl-2-pyrone, 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone, 4- (4-methoxy-styryl)- 6- (3,3,3-trichloro-propenyl) -2-pyrone, 2-trichloromethyl-benzimidazole, 2-tribromomethyl-quinoline, 2,4-dimethyl-1-tribromoacetyl-benzene, 4- Dibromoacetyl-benzoic acid, 1,4-bis-dibromomethyl-benzene, tris-dibromomethyl-S-triazine, 2- (6-methoxy-naphthyl-2-yl) -4,6-bis-trichloromethyl-S -Triazine, 2- (naphthyl-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (naphthyl-2-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (4-ethoxyethyl-naphthyl-1-yl) -4,6-bis-trichloromethyl-S
-Triazine, 2- (benzopyran-3-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (4-methoxy-anthrac-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (phenanth-9-yl) -4,6-bis- Trichloromethyl-S-triazine, o-naphthoquinonediazide-4
-There are sulfonic acid chlorides. As the sulfonic acid ester, naphthoquinonediazide-4-sulfonic acid ester, naphthoquinonediazide-5-sulfonic acid ester, p-
Examples thereof include toluenesulfonic acid-o-nitrobenzyl ester and p-toluenesulfonic acid-2,6-dinitrobenzyl ester.

In the above general formulas (I), (II) and (III), R ^{1 to} R
Examples of the heterocyclic group introduced as ¹¹ include an unsubstituted heterocyclic group and a substituted heterocycle. The unsubstituted heterocycle is specifically listed in (1) below, and the substituent substituting the heterocyclic group is specifically listed in (2) below.

(1) Unsubstituted heterocyclic pyrrole ring group, pyrroline ring group, pyrrolidine ring group, indole ring group, isoindole ring group, indoline ring group, isoindoline ring group, indolizine ring group, carbazole ring group, carboline Ring group, furan ring group, oxolane ring group, chroman ring group, coumarane ring group, isobenzofuran ring group, phthalane ring group, dibenzofuran ring group, thiophene ring group, thiolane ring group, benzothiophene ring group, dibenzothiophene ring group, Pyrazole ring group, pyrazoline ring group, indazole ring group, imidazole ring group, imidazoline ring group, benzimidazole ring group, naphthimidazole ring group, oxazole ring group, oxozaline ring group, oxozalidine ring group, benzoxazole ring group, benzoxazolidine ring group Group, naphthoxazole ring group, isoxazole ring , Benzoxazole ring group, a thiazole ring group, a thiazoline ring group,
Thiazolidine ring group, benzothiazoline ring group, naphthothiazole ring group, isothiazole ring group, benzisothiazole ring group, triazole ring group, benzotriazole ring group,
Oxadiazole ring group, thiadiazole ring group, benzooxadiazole ring group, benzothiazizole ring group, tetrazole ring group, purine ring group, pyridine ring group, piperidine ring group, quinoline ring group, isoquinoline ring group, acridine ring Group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinoxaline ring group, quinazoline ring group, cinnoline Ring group, phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteringin ring group, oxazine ring group, benzoxazine ring group, phenoxazine ring group, thiazine ring group, benzothiazine ring group, phenothiazine ring group, oxadiazine Ring group, thiadiazine ring group, dioxolane ring group Benzoioxole ring group, dioxane ring group, benzodioxane ring group, dithiosolane ring group, benzodithiosol ring group, dithiane ring group, benzodithiane ring group, pyran ring group, chromene ring group, xanthene ring group, oxane ring group, Chroman ring group, isochroman ring group,
Xanthene ring group, trioxane ring group, thiolane ring group,
Thian ring group, trithian ring group, morpholine ring group, quinuclidine ring group, selenazole ring group, benzoselenazole ring group, naphthoselenazole ring group, tellurazole ring group, benzotelrazole ring group.

(2) Substituent group Di-substituted amino group (for example, dimethylamino group, diethylamino group, dibutylamino group, methylethylamino group, methylbutylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group) Base,
Ditolylamino group, dixylylamino group, etc.), mono-substituted amino group (for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, tert-butylamino group, aninoline group, anisidino group, phenetidino group, toluidino group, Xylidino group, viridylamino group,
Benzylideneamino group, etc.), acylamino group (eg formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, trifluoroacetylamino group etc.), tertiary amino group (eg trimethylamino group, Ethyldimethylamino group, dimethylphenylamino group, etc.), amino group, hydroxyamino group, ureido group, semicarbazide group, di-substituted hydrazino group (eg dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), mono Substituted hydrazino group (eg, methyl hydrazino group, phenyl hydrazino group, viridyl hydrazino group, benzylidene hydrazino group, etc.), hydrazino group, azo group (eg, phenylazo group, pyridylazo group, thiazolylazo group, etc.),
Azoxy group, amidino group, amoyl group (eg carbamoyl group, oxamoyl group, succinamoyl group etc.), cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (eg methoxy group, ethoxy group, propoxy group, butoxy group) Group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, neacetoxy group etc.), hydroxy group, thio group (eg methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolinethio group etc.), mercapto Group, halogen group (fluoro group, bromo group, iodo group), carboxy group, ester group (eg methyl ester group, ethyl ester group, phenyl ester group, viridyl ester group, etc.), thiocarboxy group, dithiocarboxy group, thioester Basis A methoxycarbonyl group,
Methylthiocarbonyl group etc.), acyl group (eg formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group etc.), thioacyl group (eg thioformyl group, thioacetyl group, thiobenzoyl group) Group, thiopyridinecarbonyl group etc.), sulfonic acid group, sulfinyl group (eg methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group etc.), sulfonyl group (eg mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, Tosyl group, tauryl group, trimethylsulfonyl group, aminosulfonyl group, etc., hydrocarbon group (eg, alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, hydrogen silicide group (eg, silyl group) Jishiraniru group, a trimethylsilyl group, and the like).

In the above general formulas (I), (II) and (III), R ^{1 to} R
^The aromatic hydrocarbon group introduced as ¹¹ is as follows.
Examples thereof include the unsubstituted aromatic hydrocarbon group shown in (3) and the substituted aromatic hydrocarbon group obtained by substituting the aromatic hydrocarbon group listed in (3) below with the above-mentioned (2) substituent.

(3) Unsubstituted aromatic hydrocarbon group Phenyl group, naphthyl group, anthryl group, phenanthryl group, tetralinyl group, azulenyl group, biphenylenyl group, acetonaphthylenyl group, acetonaphthenyl group, fluorenyl group, triphenylenyl group, pyrenyl Group, chrysenyl group, picenyl group, perylenyl group, benzopyrenyl group, rubicenyl group, ovalenyl group, indenyl group, pentalenyl group, heptanenyl group, indacenyl group, phenalenyl group, fluoranthenyl group, acephenanthrylenyl group, aceanthrylenyl group Group, naphthacenyl group, preyadenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, trinaphthenyl group, heptaphenyl group, heptaenyl group, pyrantrenyl group.

In the above general formulas (I), (II) and (III), R ^{1 to} R
^{As the} aliphatic hydrocarbon group introduced as ¹¹ ,
Examples thereof include the unsubstituted aliphatic hydrocarbon group represented by (4) and the substituted aliphatic hydrocarbon group obtained by substituting the aliphatic hydrocarbon group listed in (4) below with the substituent of (2) described above.

(4) Unsubstituted aliphatic hydrocarbon group methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, tert-pentyl group, isopentyl Base,
Neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, vinyl group, allyl group, isopropenyl group, propenyl group, methallyl group, crotyl group, ethynyl group, propynyl group, pentenynyl group, benzyl Group, trityl group, femotyl group, styryl group, cinnamyl group, benzhydryl group.

In the above general formulas (I), (II) and (III), R ^{1 to} R
^{As the} alicyclic hydrocarbon group introduced as ¹¹ ,
An unsubstituted alicyclic hydrocarbon group shown in (5), a substituted alicyclic hydrocarbon group obtained by substituting the alicyclic hydrocarbon group enumerated in (5) below with the above-mentioned substituent (2) may be mentioned. it can.

(5) Unsubstituted alicyclic hydrocarbon group cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclo Pentadienyl group, cyclohexadienyl group.

In the above general formulas (I), (II) and (III), R ^{1 to} R
Examples of the characteristic group introduced as ¹¹ include dimethylamino group, diethylamino group, dibutylamino group, methylethylamino group, methylbutylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group. Group, di-substituted amino group such as dixylylamino group; methylamino group, ethylamino group, propylamino group, isopropylamino group, te
rt-Butylamino group, aninoline group, anisidino group, phenetidino group, toluidino group, xylidino group, viridylamino group, monosubstituted amino group such as benzylideneamino group; formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group Acylamino groups such as pyridinecarbonylamino group and trifluoroacetylamino group; tertiary amino groups such as trimethylamino group, ethyldimethylamino group and dimethylphenylamino group; amino group; hydroxyamino group; ureido group; semicarbazide group; dimethyl Disubstituted hydrazino groups such as hydrazino group, diphenylhydrazino group and methylphenylhydrazino group; monosubstituted hydrazino groups such as methylhydrazino group, phenylhydrazino group, viridylhydrazino group, benzylidenehydrazino group Hydrazino group; phenylazo group,
Azo groups such as pyridylazo groups and thiazolylazo groups; azoxy groups; amidino groups; amoyl groups such as carbamoyl groups, oxamoyl groups, succinamoyl groups; cyano groups;
Cyanato group; thiocyanato group; nitro group; nitroso group;
Methoxy group, ethoxy group, propoxy group, butoxy group,
Hydroxyethoxy group, phenoxy group, naphthoxy group,
Oxy group such as pyridyloxy group, thiazolyloxy group, neacetoxy group; hydroxy group; thio group such as methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolinethio group; mercapto group; fluoro group, bromo group, iodo group, etc. Halogen group; carboxy group; ester group such as methyl ester group, ethyl ester group, phenyl ester group, and viridyl ester group; thiocarboxy group; dithiocarboxy group; methoxycarbonyl group,
Thioester groups such as methylthiocarbonyl group and methylthiothiocarbonyl group; acyl groups such as formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group; thioformyl group, thioacetyl group, thio Thioacyl groups such as benzoyl group and thiopyridinecarbonyl group; sulfonic acid groups such as sulfinyl group, methylsulfinyl group, ethylsulfinyl group and phenylsulfinyl group; mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, Examples thereof include a sulfonyl group such as a tauryl group, a trimethylsulfonyl group and an aminosulfonyl group; and a hydrogen silicide group such as a silyl group, a disilanyl group and a trimethylsilyl group.

The compounds represented by the general formula (I) are shown in Tables 13 to 21 below, and the compounds represented by the general formula (II) are shown in Tables 22 to 29 below in the general formula (III). Examples of the compounds are shown in Tables 30 to 38 below.

[0039]

[Table 13]

[0040]

[Table 14]

[0041]

[Table 15]

[0042]

[Table 16]

[0043]

[Table 17]

[0044]

[Table 18]

[0045]

[Table 19]

[0046]

[Table 20]

[0047]

[Table 21]

[0048]

[Table 22]

[0049]

[Table 23]

[0050]

[Table 24]

[0051]

[Table 25]

[0052]

[Table 26]

[0053]

[Table 27]

[0054]

[Table 28]

[0055]

[Table 29]

[0056]

[Table 30]

[0057]

[Table 31]

[0058]

[Table 32]

[0059]

[Table 33]

[0060]

[Table 34]

[0061]

[Table 35]

[0062]

[Table 36]

[0063]

[Table 37]

[0064]

[Table 38] The compounding ratio of the dissolution inhibitor (B) consisting of an organic compound having a substituent decomposable by the acid to the alkali-soluble polymer (A) is 1 per 100 parts by weight of the polymer resin.
It is desirable that the amount is ˜300 parts by weight, more preferably 5 to 100 parts by weight. The reason for this is that if the amount of the dissolution inhibitor is less than 1 part by weight, it may be difficult to obtain a sufficient effect of inhibiting the dissolution in a developer, which may hinder pattern formation. If it exceeds the range, the coating property may be deteriorated and it may be difficult to form a resist film having a uniform film thickness.

The amount of the compound (C) which generates an acid upon irradiation with light is 0.01 to 15% by weight, more preferably 0.5 to 15% by weight based on the total weight of the solid content of the photosensitive composition.
It is desirable to set it in the range of 10% by weight. The reason for this is
When the compounding amount of the compound is less than 0.01% by weight, it becomes difficult to exert a sufficient action as an acid catalyst, while when the compounding amount exceeds 15% by weight, the coating property is deteriorated and uniform photosensitivity is obtained. Formation of the composition film may be difficult.

The compounding ratio of the compound (D) represented by the general formula (I), (II) or (III) to the alkali-soluble polymer is
The amount is preferably 0.01 to 100 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the polymer. The reason for this is that if the compounding amount of the compound is less than 0.01 parts by weight, it becomes difficult to exert a sufficient effect due to the compounding of the compound, while if the compounding amount exceeds 100 parts by weight, the coatability deteriorates. It may be difficult to form a photosensitive composition film having a uniform thickness.

The photosensitive composition (1) comprises, in addition to the four components (A) to (D) described above, an ultraviolet absorber, a sensitizer, and a stabilizer for storage stability, if necessary. , An antihalation agent for preventing halation from the substrate, an adhesion improver for improving the adhesion to the substrate, a surfactant for smoothing the surface of the coating film, or a modification of the coating film. It is also possible to blend other polymers for this purpose, such as epoxy resin, polymethylmethacrylate, polymethylacrylate, propylene oxide-ethylene oxide copolymer, polystyrene or the like.

The photosensitive composition (1) comprises the alkali-soluble polymer (A), a dissolution inhibitor (B), a compound (C) which generates an acid upon irradiation with light, and the general formula (I). , (I
It is prepared by dissolving the compound (D) of I) and (III) in an organic solvent and filtering. Examples of the organic solvent include ketone solvents such as cyclohexanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cellosolve solvents such as butyl cellosolve acetate, ethyl acetate, and the like. Examples thereof include butyl acetate, isoamyl acetate, γ-butyl lactone and other ester solvents, dimethyl sulfoxide, dimethylformamide N-methylpyrrolidone and the like. These solvents may be used alone or in the form of a mixture. However, these may contain an appropriate amount of an aliphatic alcohol such as xylene, toluene or isopropyl alcohol.

Next, a pattern forming method by the single layer process using the above-mentioned photosensitive composition (1) will be described.

First, the above-mentioned photosensitive composition (1) dissolved in an organic solvent is applied on a substrate by a spin coating method or a dipping method and then dried to form a photosensitive composition film (resist film). .. As the substrate used here, for example, a silicon wafer, various insulating films and electrodes on the surface, a silicon wafer having a step formed with wiring, a blank mask,
Examples thereof include III-V compound semiconductor wafers such as GaAs and AlGaAs.

Then, the resist film is selectively irradiated with deep UV through a mask having a desired pattern to perform pattern exposure. As the light source for this pattern exposure, for example, XeF (wavelength 351 nm), Xe
Cl (wavelength 308 nm), KrF (wavelength 248 nm),
KrCl (wavelength 222nm), ArF (wavelength 193n)
m), deep UV of excimer laser such as F ₂ (wavelength 157 nm) can be used. Subsequently, the resist film after the pattern exposure is developed using an alkaline aqueous solution by a dipping method, a spray method or the like. As a result, the unexposed portion of the resist film is dissolved and removed to form a desired resist pattern. The alkali aqueous solution used here may be any one as long as it has a property of rapidly dissolving and removing the unexposed portion of the resist film and having an extremely low dissolution rate in other exposed portions, for example, an aqueous solution of tetramethylammonium hydroxide. Examples thereof include organic alkaline aqueous solutions such as, and inorganic alkaline aqueous solutions such as potassium hydroxide and sodium hydroxide. These alkaline aqueous solutions are usually used at a concentration of 15% by weight or less. Moreover, you may perform a rinse process with water etc. after image development.

The resist film is allowed to be heated at a temperature of 80 to 160 ° C. after the exposure process and before the development process.

Photosensitive Composition (2) This photosensitive composition comprises (A) a silicon-containing alkali-soluble polymer and (B) a dissolution inhibitor similar to that used in the above-mentioned photosensitive composition (1). And (C) a compound capable of generating an acid upon irradiation with light, and (D) a compound of the general formula (I), (II) or (III).

As the silicon-containing alkali-soluble polymer as the component (A), (a) polysiloxane having phenol as a side chain, (b) polysilane having phenol as a side chain, and (c) silicon as a side chain. The novolak resin etc. which were synthesize | combined from the phenol which it has can be mentioned. (A)
Examples of the polysiloxane of Table 1 are shown in Tables 39 to 43 below, and examples of the polysilane of (b) are shown in Tables 44 to 45 below. The novolac resin of (c) above is shown in Table 46 below.
-The thing obtained by condensing the silicon-containing phenolic monomer of Table 57 and phenol with formalin or aldehyde is mentioned. Examples of phenols used here include phenol, o-chlorophenol,
m-chlorophenol, p-chlorophenol, m-cresol, p-cresol, xyresole, bisphenol A,
4-chloro-3-cresol, dihydroxybenzene, trihydroxybenzene and the like can be mentioned. Further, as the silicon-containing alkali-soluble polymer, an acrylic resin,
A methacrylic resin, a copolymer of methacrylic acid, acrylonitrile, and a styrene derivative, or a copolymer of malonic acid and vinyl ether into which silicon is introduced can be used. Specific examples of such silicon-containing alkali-soluble polymers are shown in Table 58 below.

[0075]

[Table 39]

[0076]

[Table 40]

[0077]

[Table 41]

[0078]

[Table 42]

[0079]

[Table 43]

[0080]

[Table 44]

[0081]

[Table 45]

[0082]

[Table 46]

[0083]

[Table 47]

[0084]

[Table 48]

[0085]

[Table 49]

[0086]

[Table 50]

[0087]

[Table 51]

[0088]

[Table 52]

[0089]

[Table 53]

[0090]

[Table 54]

[0091]

[Table 55]

[0092]

[Table 56]

[0093]

[Table 57]

[0094]

[Table 58] A silicon-containing alkali-soluble polymer which is each component constituting the photosensitive composition (2), a dissolution inhibitor, a compound which generates an acid upon irradiation with light, and a compound of the general formula (I), (II) or (III) It is desirable that the compounding ratio be the same as the above-mentioned photosensitive composition (1). In addition, the photosensitive composition (2) contains, in addition to the above-mentioned components, the same additives as the photosensitive composition (1) described above, if necessary, and is dissolved in an organic solvent and filtered. Is prepared.

Next, a pattern forming method by the two-layer lithography process using the above-mentioned photosensitive composition (2) will be described.

First, a polymer material was applied onto a substrate similar to that used in the above-mentioned single layer process, and then 100 to 25
Baking is performed at 0 ° C. for 30 to 150 minutes to form a polymer material layer (planarization layer) having a desired thickness. The polymer material used here may be any material as long as it has a purity that does not hinder the production of semiconductor elements and the like.
Examples of such a polymer material include a positive resist consisting of a substituted o-quinonediazide and a novolac resin, polystyrene, polymethylmethacrylate, polyvinylphenol.
Resin, novolac resin, polyester, polyvinyl alcohol, polyethylene, polypropylene, polyimide, polybutadiene, polyvinyl acetate and polyvinyl butyra
And the like. These resins are used alone or in the form of a mixture.

Then, the above-mentioned photosensitive composition (2) is applied onto the polymer material layer by, for example, a spin coating method or a dipping method, and then dried to form a photosensitive composition film (resist film).

Then, through the mask having the desired pattern on the resist film, the deep UV is emitted from the light source described above.
Is selectively irradiated to perform pattern exposure. For the exposure, either contact exposure or projection exposure may be adopted. Continuously, dipping method using an alkaline aqueous solution,
Develop by a spray method or the like. As a result, the unexposed portion of the resist film is dissolved and removed to form a desired resist pattern. The alkali aqueous solution used here may be any one as long as it has a property of rapidly dissolving and removing the unexposed portion of the resist film and having an extremely low dissolution rate in other exposed portions, for example, an aqueous solution of tetramethylammonium hydroxide. Examples thereof include organic alkaline aqueous solutions such as, and inorganic alkaline aqueous solutions such as potassium hydroxide and sodium hydroxide. These alkaline aqueous solutions are usually used at a concentration of 15% by weight or less.
After the development, a rinse treatment may be performed with water or the like.

Next, the exposed polymer material layer is etched by the oxygen reactive ion etching method (oxygen RIE method) using the resist pattern as a mask. At this time, since the photosensitive composition (2) constituting the resist pattern contains the silicon-containing alkali re-soluble polymer as described above, the resist pattern is exposed to oxygen RIE, Silicon dioxide (SiO ₂ ) or a film similar thereto is formed on the layer, and has a resistance to oxygen RIE that is 10 to 100 times that of the exposed polymer material layer. Therefore, the polymer material layer portion exposed from the resist pattern is selectively removed by the oxygen RIE method, and an optimum pattern profile is obtained.

Etching of the substrate or the like is performed using the pattern formed by the above steps as a mask. As the etching means, a wet etching method or a dry etching method is adopted, and a dry etching method is preferable when a fine pattern of 3 μm or less is formed. As the wet etching agent, a hydrofluoric acid aqueous solution, an ammonium fluoride aqueous solution or the like is used when the silicon oxide film is an etching target, and a phosphoric acid aqueous solution, an acetic acid aqueous solution, a nitric acid aqueous solution, or the like when the aluminum is an etching target, When the chromium-based film is the etching target, an aqueous solution of cerium ammonium nitrate or the like is used. The gas for dry etching is CF ₄ , C ₂ F ₆ , CCl ₄ , B
Cl ₃ , Cl ₂ , HCl, H _{2 and the} like can be mentioned,
These gases are used in combination as required. The etching conditions are the concentration of the wet etching agent in the reaction tank, the concentration of the dry etching gas, and
The reaction temperature, reaction time and the like are determined, but the method and the like are not particularly limited.

After the above-mentioned etching, the pattern made of the polymer material and the resist remaining on the substrate is removed.
For example, a release agent such as J-100 manufactured by Nagase Kasei,
It is removed by oxygen gas plasma or the like.

In addition to the steps described above, it does not matter at all that additional steps may be added depending on the purpose. For example, a rinsing step (usually using water) performed for the purpose of washing and removing the developer after development, and improving adhesion between the resist film made of the photosensitive composition and the planarizing layer or the planarizing layer and the substrate. From the purpose, a pretreatment step performed before coating each liquid, a baking step performed before or after development, an ultraviolet ray re-irradiation step performed before dry etching and the like can be mentioned.

Photosensitive Composition (3) This photosensitive composition comprises (C) the following chemical formulas 14, 15 and 1
Compounds that generate an acid upon irradiation with light, represented by the general formulas (IV), (V), (VI), and (VII) of Chemical Formula 6, and the photosensitive composition (1) described above. (A) an alkali-soluble polymer similar to the above, (B) a dissolution inhibitor, (D) a general formula (I),
It has a composition containing the compounds (II) and (III).

[0104]

[Chemical 14] However, R ¹² , R ¹³ and R ¹⁴ in the formula (IV) may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a silyl group or a monovalent organic group. R ¹⁵ represents a monovalent or higher valent organic group, and n represents an integer of 1 to 7. Note that R ¹³ and R ¹⁴
May form a hydrocarbon ring group or a heterocyclic group.

[0105]

[Chemical 15] However, R ¹⁶ and R ¹⁷ in the formula (V) may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group silyl group, or a monovalent organic group. R ¹⁸ represents a monovalent or higher valent organic group. X ₇ is, -O -, - S -, - SO 2 -, - CO-,
_{-CR 1 R 2 -,> N} -COR 3 (R 1, R 2, R 3;
A hydrogen atom, a halogen atom, a cyano group, a silyl group or a monovalent organic group, which may be the same or different from each other), and n represents an integer of 1 to 7.

[0106]

[Chemical 16] However, R ¹⁹ and R ²⁰ in the formula (VI) may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group silyl group, or a monovalent organic group. R ²¹ represents a monovalent or higher valent organic group. X ₈ is, -O -, - S -, - SO 2 -, - CO-,
_{-CR 1 R 2 -,> N} -COR 3 (R 1, R 2, R 3;
A hydrogen atom, a halogen atom, a cyano group, a silyl group or a monovalent organic group, which may be the same or different from each other), and n represents an integer of 1 to 7.

[0107]

[Chemical 17] However, R ²² , R ²³ , R ²⁴ , and R ²⁵ in the formula (VII) may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a silyl group, or a monovalent organic group. R ²⁶ represents a monovalent or higher valent organic group, and n represents an integer of 1 to 7.

In the above general formulas (IV) to (VII), R ¹² , R ¹³ and R
¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ , R ²² , R ²³ , R ²⁴ , R ²⁵
Examples of the group introduced as hydrogen, halogen such as chlorine or bromine, cyano group, trimethylsilyl, silyl group such as triphenylenesilyl, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert- Alkyl groups such as butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, substituted or unsubstituted phenyl groups, aryl groups such as naphthyl groups, methoxy, ethoxy, propoxy, butoxy, phenoxy, etc. Examples thereof include alkoxy groups, amino groups such as dimethylamino and diphenylamino, and the following substituted or unsubstituted heterocyclic groups. Examples of the heterocyclic group include a pyrrole ring group, a pyrroline ring group, a pyrrolidine ring group, an indole ring group, an isoindole ring group, an indoline ring group, an isoindoline ring group, an indolizine ring group, a carbazole ring group, and a carboline ring group. , Furan ring group, oxolane ring group, chroman ring group, coumarane ring group,
Isobenzofuran ring group, phthalane ring group, dibenzofuran ring group, thiophene ring group, thiolane ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, pyrazoline ring group, indazole ring group, imidazole ring group, imidazoline ring group Group, benzimidazole ring group, naphthimidazole ring group, oxazole ring group, oxozaline ring group, oxozalidine ring group, benzoxazole ring group,
Benzoxazolidine ring group, naphthoxazole ring group,
Isoxazole ring group, benzoxazole ring group, thiazole ring group, thiazoline ring group, thiazolidine ring group, benzothiazoline ring group, naphthothiazole ring group, isothiazole ring group, benzisothiazole ring group, triazole ring group, benzotriazole ring group Group, oxadiazole ring group,
Thiadiazole ring group, benzooxadiazole ring group, benzothiazizole ring group, tetrazole ring group, purine ring group, pyridine ring group, piperidine ring group, quinoline ring group,
Isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group,
Quinoxaline ring group, quinazoline ring group, cinnoline ring group,
Phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteringin ring group, oxazine ring group, benzoxazine ring group, phenoxazine ring group, thiazine ring group, benzothiazine ring group, phenothiazine ring group, oxadiazine ring group, Thiadiazine ring group, dioxolane ring group,
Benzioxole ring group, dioxane ring group, benzodioxane ring group, dithiosolane ring group, benzodithiosole ring group, dithian ring group, benzodithian ring group, pyran ring group, chromene ring group, xanthene ring group, oxane ring group , Chroman ring group, isochroman ring group, xanthene ring group, trioxane ring group, thiolane ring group, thiane ring group, trithiane ring group, morpholine ring group, quinuclidine ring group, selenazole ring group, benzoselenazole ring group, naphthoselena Examples thereof include a sol ring group, a tellurazole ring group, and a benzotelrazole ring group.

R ¹⁵ , R ¹⁸ and R in the general formulas (IV) to (VII)
^The groups introduced as R ²¹ and R ²⁶ include R ¹² and
R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ , R ²² , R ²³ , R
^In addition to monovalent substituents similar to R ²⁴ and R ²⁵ , divalent or higher valent organic groups can be mentioned. Examples of the divalent or higher valent group include substituted or unsubstituted alkylene such as methylene, methine, ethylene and propylene, substituted or unsubstituted aromatic ring,
Examples thereof include heterocycles, phenylene, diphenylene ether, diphenylene ether, diphenylene methane, diphenylene propane, bisphenylenedimethylsilane, and those having the structure shown in Chemical formula 18 below.

[0110]

[Chemical 18] The compounds that generate the acids represented by the general formulas (IV) to (VII), which are the components (C), are specifically illustrated in Tables 59 to 74 below.

[0111]

[Table 59]

[0112]

[Table 60]

[0113]

[Table 61]

[0114]

[Table 62]

[0115]

[Table 63]

[0116]

[Table 64]

[0117]

[Table 65]

[0118]

[Table 66]

[0119]

[Table 67]

[0120]

[Table 68]

[0121]

[Table 69]

[0122]

[Table 70]

[0123]

[Table 71]

[0124]

[Table 72]

[0125]

[Table 73]

[0126]

[Table 74] An alkali-soluble polymer which is each component constituting the photosensitive composition (3), a dissolution inhibitor, a compound represented by the general formulas (IV) to (VII) which generates an acid upon irradiation with light and a general formula
The compounds (I), (II) and (III) are preferably mixed in the same proportion as in the above-mentioned photosensitive composition (1). In addition, the photosensitive composition (3) contains, in addition to the above-mentioned components, the same additives as the above-described photosensitive composition (1), if necessary, and is dissolved in an organic solvent and filtered. Is prepared. Further, the photosensitive composition (3) is applied to the pattern forming method by the single layer process described above.

Photosensitive Resin Composition (4) This photosensitive resin composition comprises the same (A) silicon-containing alkali-soluble polymer as used in the above-mentioned photosensitive resin composition (2) and the above-mentioned photosensitive resin composition. (B) a dissolution inhibitor similar to that used in the acidic composition (1), and (D) the general formula (I), (I)
An acid is generated by the light irradiation represented by the general formulas (IV) to (VII) of the compounds (I) and (III) and the same (C) as used in the above-mentioned photosensitive resin composition (3). And a compound containing the compound.

A silicon-containing alkali-soluble polymer which is each component constituting the photosensitive composition (4), a dissolution inhibitor,
The compounds represented by the general formulas (IV) to (VII) which generate an acid upon irradiation with light and the compounds of the general formulas (I), (II) and (III) are the same as those of the above-mentioned photosensitive composition (1). It is desirable to use the same mixing ratio. In addition, the photosensitive composition (4) contains, in addition to the above components, the same additives as the photosensitive composition (1) described above, if necessary, and is dissolved in an organic solvent and filtered. Is prepared. Furthermore, the photosensitive composition (4) is applied to the pattern forming method by the above-mentioned two-layer lithography process.

[0129]

According to the photosensitive compositions (1) and (3) of the present invention, by irradiating light such as deepUV or ionizing radiation, an acid which is the component (C) in the composition is generated. From an organic compound having a substituent, which is generated from a compound or a compound generating an acid represented by any one of the general formulas (IV) to (VII) and is decomposed by the acid which is the component (B) in the composition by the acid. The dissolution inhibiting agent is decomposed, the dissolution inhibiting force disappears, and a pattern latent image can be formed. Further, the compounds represented by the general formulas (I) to (III), which are the component (D) in each composition, have an action of suppressing the diffusion of the acid generated by the light irradiation, and thus the latent image The resolution of can be improved. As a result, the latent image can be preferentially dissolved and removed by the development process, so that a pattern (positive pattern) can be formed. Moreover, since each of the photosensitive resin compositions contains an alkali-soluble resin as the component (A), it can be developed with an alkaline aqueous solution after exposure, and swelling and the like can be suppressed. Therefore, it is possible to form a fine positive pattern which is well exposed to light such as deepUV and ionizing radiation, has a rectangular cross-section with high accuracy and a large tolerance in the above process, and has excellent dry etching resistance. ..

According to the photosensitive compositions (2) and (4) of the present invention, the above-mentioned photosensitive compositions (1) and
A positive pattern can be formed by the same operation as described in (3). In addition, since each of the above-mentioned compositions contains the silicon-containing alkali-soluble resin as the component (A), it can be developed with an aqueous alkali solution after exposure, can suppress swelling and the like and has oxygen RIE resistance. A fine pattern can be formed. Therefore, the pattern is provided with an oxygen resistant RI for the lower polymeric material layer (flat lower layer).
By performing dry etching using oxygen plasma as an E-type mask, a fine two-layer pattern having a high aspect ratio and a favorable rectangular cross section can be formed.

[0131]

【Example】

Examples 1 to 3 First, an alkali-soluble resin shown in Table 75 below, a compound that generates an acid upon irradiation with light, a dissolution inhibitor shown in Table 76 below, and compounds represented by the general formulas (I) to (III) Table 7
5, blended in a ratio shown in Table 76, dissolved in 250 g of ethyl cellosolve acetate, and filtered using a 0.2 μm fluororesin membrane filter to prepare three types of photosensitive resin compositions.

[0132]

[Table 75]

[0133]

[Table 76] Then, each photosensitive composition was applied onto a silicon wafer and dried on a hot plate at 90 ° C. for 5 minutes to form a photosensitive resin composition film (resist film) having a thickness of 1.0 μm. Next, KrF is added to these resist films.
Pattern exposure (100 mJ / cm ² ) was performed with a reduction projection exposure machine using excimer laser light. After that, it was immersed in a tetramethylammonium hydroxide aqueous solution (hereinafter, abbreviated as TMAH aqueous solution) having a concentration of 1.8% by weight for 1 minute and developed to form three types of positive type patterns.

Examples 4 to 7 Alkali-soluble resins shown in Table 77 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 78 below, represented by the general formulas (I) to (III) Table 7
7, the proportions shown in Table 78 were mixed, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare four types of photosensitive resin compositions.

[0135]

[Table 77]

[0136]

[Table 78] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Pattern exposure and development with a TMAH aqueous solution to form four types of positive patterns.

Examples 8 to 10 First, alkali-soluble resins shown in Table 79 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 80 below, and compounds represented by the general formulas (I) to (III) Table 7
9, blended in the ratios shown in Table 80, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare three types of photosensitive resin compositions.

[0138]

[Table 79]

[0139]

[Table 80] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 11 to 13 First, alkali-soluble resins shown in Table 81 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 82 below, and compounds represented by the general formulas (I) to (III) Table 8
1, and were mixed in the proportions shown in Table 82, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare three types of photosensitive resin compositions.

[0141]

[Table 81]

[0142]

[Table 82] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 14 to 16 First, alkali-soluble resins shown in Table 83 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 84 below, and compounds represented by the general formulas (I) to (III) Table 8
3, blended in a ratio shown in Table 84, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare three types of photosensitive resin compositions.

[0144]

[Table 83]

[0145]

[Table 84] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 17 to 19 First, alkali-soluble resins shown in Table 85 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 86 below, and compounds represented by the general formulas (I) to (III) Table 8
5, the proportions shown in Table 86 were mixed, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare three types of photosensitive resin compositions.

[0147]

[Table 85]

[0148]

[Table 86] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 20 to 22 First, alkali-soluble resins shown in Table 87 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 88 below, and compounds represented by the general formulas (I) to (III) Table 8
7, the proportions shown in Table 88 were mixed, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare three types of photosensitive resin compositions.

[0150]

[Table 87]

[0151]

[Table 88] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 23 to 25 First, alkali-soluble resins shown in Table 89 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 90 below, and compounds represented by the general formulas (I) to (III) Table 8
9, blended in a ratio shown in Table 90, dissolved in ethyl cellosolve acetate in the same manner as in Example 1, and further filtered to prepare three types of photosensitive resin compositions.

[0153]

[Table 89]

[0154]

[Table 90] Then, each of the above-mentioned photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 1 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

The shapes of the positive type patterns of Examples 1 to 25 were examined. As a result, it was confirmed that each of them had a steep pattern profile of 0.35 μm and could form a fine and highly precise positive pattern having a rectangular shape.

Examples 26 and 27 First, alkali-soluble resins shown in Table 91 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 92 below, and compounds represented by the general formulas (I) to (III) Table 9
1 and 2 were mixed in a ratio shown in Table 92, dissolved in 250 g of ethyl cellosolve acetate, and filtered using a 0.2 μm fluororesin membrane filter to prepare two types of photosensitive resin compositions.

[0157]

[Table 91]

[0158]

[Table 92] Then, a polymer material solution made of a commercially available novolac resin was applied on the silicon substrate to a thickness of 2.0 μm, and then 2
The polymer material layer (planarization layer) was formed by heat treatment at 20 ° C. for 30 minutes. Subsequently, each of the above-mentioned photosensitive compositions was applied onto this flattening layer and dried at 90 ° C. for 5 minutes on a hot plate to form a photosensitive composition film (resist film) having a thickness of 0.6 μm. .. Continuing, Kr is added to these resist films.
Pattern exposure (100 mJ / cm ² ) was performed with a reduction projection exposure machine using F excimer laser light. After this 1.8
Develop by immersing in a TMAH aqueous solution having a concentration of 1% by weight for 1 minute,
A hosi type pattern (upper layer pattern) was formed.

Next, the silicon substrate on which the upper layer pattern was formed was placed in a dry etching device (trade name: HIRRIE manufactured by Tokuda Manufacturing Co., Ltd.), and an output of 0.8 W / cm ² ,
Reactive ion etching (RIE) with oxygen plasma was performed for 2 minutes under the conditions of an oxygen gas pressure of 4 pa and a flow rate of 50 sccm, and the lower flattening layer was etched using the upper layer pattern as a mask.

Examples 28 and 29 Alkali-soluble resins shown in Table 93 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 94 below, compounds represented by the general formulas (I) to (III) Table 93, Table 94
In the same proportion as in Example 26, they were dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0161]

[Table 93]

[0162]

[Table 94] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 30 and 31 Alkali-soluble resins shown in Table 95 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 96 below, compounds represented by the general formulas (I) to (III) Table 95 and Table 96
In the same proportion as in Example 26, they were dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0164]

[Table 95]

[0165]

[Table 96] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 32 and 33 Alkali-soluble resins shown in Table 97 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 98 below, compounds represented by the general formulas (I) to (III) The same table 97, table 98
In the same proportion as in Example 26, they were dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0167]

[Table 97]

[0168]

[Table 98] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 34 and 35 Alkali-soluble resins shown in Table 99 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 100 below, compounds represented by the general formulas (I) to (III) The same table 99, table 1
Compounded in a ratio shown in 00, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0170]

[Table 99]

[0171]

[Table 100] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 36 and 37 Alkali-soluble resins shown in Table 101 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 102 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 101,
Compounded in the proportions shown in Table 102, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0173]

[Table 101]

[0174]

[Table 102] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 38 and 39 Alkali-soluble resins shown in Table 103 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 104 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 103,
Compounded in the proportions shown in Table 104, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0176]

[Table 103]

[0177]

[Table 104] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 40 and 41 Alkali-soluble resins shown in Table 105 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 106 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 105,
Compounded in the proportions shown in Table 106, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0179]

[Table 105]

[0180]

[Table 106] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 42 and 43 Alkali-soluble resins shown in Table 107 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 108 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 107,
Compounded in the proportions shown in Table 108, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0182]

[Table 107]

[0183]

[Table 108] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 44 and 45 Alkali-soluble resins shown in Table 109 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 110 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 109,
Compounded in the proportions shown in Table 110, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0185]

[Table 109]

[0186]

[Table 110] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 46 and 47 Alkali-soluble resins shown in Table 111 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 112 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 111,
Compounded in the proportions shown in Table 112, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0188]

[Table 111]

[0189]

[Table 112] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 48 and 49 Alkali-soluble resins shown in Table 113 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 114 below,
Compounds represented by the general formulas (I) to (III) are shown in Table 113,
Compounded in the proportions shown in Table 114, dissolved in ethyl cellosolve acetate in the same manner as in Example 26, and further filtered to prepare two types of photosensitive resin compositions.

[0191]

[Table 113]

[0192]

[Table 114] Then, a flat underlayer was formed on a silicon substrate in the same manner as in Example 26, and each of the photosensitive resin compositions was applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

The pattern shapes of the flattening layer after oxygen RIE in Examples 26 to 49 were observed with a scanning electron microscope. As a result, it was confirmed that it is possible to form a highly precise two-layer pattern having a fine and rectangular shape, each having a steep pattern profile of 0.35 μm.

Examples 50 to 52 First, the alkali-soluble resins and the general formulas shown in Table 115 below are used.
Compounds represented by (IV) to (VII) that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 116 below, and general formulas (I) to (I
The compounds represented by II) are blended in the ratios shown in Tables 115 and 116, dissolved in 250 g of ethyl cellosolve acetate, and filtered using a 0.2 μm fluororesin membrane filter to obtain three types of photosensitivity. A resin composition was prepared.

[0195]

[Table 115]

[0196]

[Table 116] Then, each photosensitive composition was applied onto a silicon wafer and dried on a hot plate at 90 ° C. for 5 minutes to form a photosensitive resin composition film (resist film) having a thickness of 1.0 μm. Next, KrF is added to these resist films.
Pattern exposure (100 mJ / cm ² ) was performed with a reduction projection exposure machine using excimer laser light. After that, it was immersed in a tetramethylammonium hydroxide aqueous solution (hereinafter, abbreviated as TMAH aqueous solution) having a concentration of 1.8% by weight for 1 minute and developed to form three types of positive type patterns.

Examples 53 to 56 First, the alkali-soluble resins shown by the following Table 117, the general formula
Compounds represented by (IV) to (VII) which generate an acid upon irradiation with light, dissolution inhibitors shown in Table 118 below, and general formulas (I) to (I
Compounds represented by II) were blended in the ratios shown in Tables 117 and 118, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and further filtered to prepare four photosensitive resin compositions. did.

[0198]

[Table 117]

[0199]

[Table 118] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 50 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Pattern exposure and development with a TMAH aqueous solution to form four types of positive patterns.

Examples 57 to 59 First, the alkali-soluble resins and the general formulas shown in Table 119 below are used.
Compounds represented by (IV) to (VII) that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 120 below, and general formulas (I) to (I
The compounds represented by II) are blended in the ratios shown in Tables 119 and 120, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and further filtered to prepare three types of photosensitive resin compositions. did.

[0201]

[Table 119]

[0202]

[Table 120] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 50 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 60 to 62 First, the alkali-soluble resins and the general formulas shown in Table 121 below were used.
(IV) to (VII) compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 122 below, and general formulas (I) to (I
The compounds represented by II) were blended in the ratios shown in Tables 121 and 122, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and further filtered to prepare three types of photosensitive resin compositions. did.

[0204]

[Table 121]

[0205]

[Table 122] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 50 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 63 to 65 First, the alkali-soluble resins shown in Table 123 below and the general formula
(IV) to (VII) compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 124 below, and general formulas (I) to (I
The compounds represented by II) were blended in the ratios shown in Tables 123 and 124, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and further filtered to prepare three types of photosensitive resin compositions. did.

[0207]

[Table 123]

[0208]

[Table 124] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 50 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 66 to 68 First, the alkali-soluble resins shown by the following Table 125, the general formula
(IV) to (VII) compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 126 below, and general formulas (I) to (I
The compounds represented by II) were blended in the ratios shown in Tables 125 and 126, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and filtered to prepare three types of photosensitive resin compositions. did.

[0210]

[Table 125]

[0211]

[Table 126] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 20 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 69 to 71 First, the alkali-soluble resins and the general formulas shown in Table 127 below are used.
(IV) to (VII) compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 128 below, and general formulas (I) to (I
The compounds represented by II) are blended in the ratios shown in Tables 87 and 88, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and further filtered to prepare three types of photosensitive resin compositions. did.

[0213]

[Table 127]

[0214]

[Table 128] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 50 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

Examples 72 to 74 First, the alkali-soluble resins shown in Table 129 below and the general formula
Compounds (IV) to (VII) that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 130 below, and general formulas (I) to (I
Compounds represented by II) were blended in the ratios shown in Tables 129 and 130, dissolved in ethyl cellosolve acetate in the same manner as in Example 50, and further filtered to prepare three types of photosensitive resin compositions. did.

[0216]

[Table 129]

[0217]

[Table 130] Then, each of the photosensitive compositions was applied onto a silicon wafer and dried in the same manner as in Example 50 to form a resist film having a thickness of 1.0 μm, and subsequently a reduction projection exposure machine using KrF excimer laser light. Then, three types of positive patterns were formed by performing pattern exposure and developing with a TMAH aqueous solution.

The shapes of the positive type patterns of Examples 50 to 74 were examined. As a result, it was confirmed that each of them had a steep pattern profile of 0.35 μm and could form a fine and highly precise positive pattern having a rectangular shape.

Examples 75 and 76 First, the alkali-soluble resins and the general formulas shown in Table 131 below are used.
(IV) to (VII) compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 132 below, and general formulas (I) to (I
The compounds represented by II) are blended in the ratios shown in Tables 131 and 132, dissolved in 250 g of ethyl cellosolve acetate, and filtered using a 0.2 μm fluororesin membrane filter to obtain two types of photosensitivity. A resin composition was prepared.

[0220]

[Table 131]

[0221]

[Table 132] Then, a polymer material solution made of a commercially available novolac resin was applied on the silicon substrate to a thickness of 2.0 μm, and then 2
The polymer material layer (planarization layer) was formed by heat treatment at 20 ° C. for 30 minutes. Subsequently, each of the above-mentioned photosensitive compositions was applied onto this flattening layer and dried at 90 ° C. for 5 minutes on a hot plate to form a photosensitive composition film (resist film) having a thickness of 0.6 μm. .. Continuing, Kr is added to these resist films.
Pattern exposure (100 mJ / cm ² ) was performed with a reduction projection exposure machine using F excimer laser light. After this 1.8
Develop by immersing in a TMAH aqueous solution having a concentration of 1% by weight for 1 minute,
A hosi type pattern (upper layer pattern) was formed.

Then, the silicon substrate on which the upper pattern was formed was placed in a dry etching apparatus (trade name: HIRRIE manufactured by Tokuda Manufacturing Co., Ltd.), and an output of 0.8 W / cm ² ,
Reactive ion etching (RIE) with oxygen plasma was performed for 2 minutes under the conditions of an oxygen gas pressure of 4 pa and a flow rate of 50 sccm, and the lower flattening layer was etched using the upper layer pattern as a mask.

Examples 77 and 78 Alkali-soluble resins shown in Table 133 below, represented by general formula (IV) to
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 134 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 133 and 134, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0224]

[Table 133]

[0225]

[Table 134] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 79 and 80 Alkali-soluble resins shown in Table 135 below, represented by general formula (IV)
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 136 below and the compounds represented by the general formulas (I) to (III) were blended in the proportions shown in Tables 135 and 136, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0227]

[Table 135]

[0228]

[Table 136] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 81, 82 Alkali-soluble resins shown in Table 137 below, represented by the general formula (IV):
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 138 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 137 and 138, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0230]

[Table 137]

[0231]

[Table 138] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 81, 82 Alkali-soluble resins shown in Table 139 below, represented by the general formula (IV):
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 140 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 139 and 140, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0233]

[Table 139]

[0234]

[Table 140] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 83 and 84 Alkali-soluble resins shown in Table 141 below, represented by general formula (IV)
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 142 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 141 and 142, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0236]

[Table 141]

[0237]

[Table 142] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 85, 86 Alkali-soluble resins shown in Table 104 below, represented by the general formula (IV)
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 144 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 143 and 144, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0239]

[Table 143]

[0240]

[Table 144] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 87, 88 Alkali-soluble resins shown in Table 145 below, represented by general formula (IV)
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 146 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 145 and 146, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0242]

[Table 145]

[0243]

[Table 146] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 89 and 90 Alkali-soluble resins shown in Table 147 below, represented by general formula (IV)
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 148 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 147 and 148, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0245]

[Table 147]

[0246]

[Table 148] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 91 and 92 Alkali-soluble resins shown in Table 149 below, represented by general formula (IV) to
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 150 below and the compounds represented by the general formulas (I) to (III) were blended in the proportions shown in Tables 149 and 150, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0248]

[Table 149]

[0249]

[Table 150] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 93, 94 Alkali-soluble resins shown in Table 151 below, represented by the general formula (IV):
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 152 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 151 and 152, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0251]

[Table 151]

[0252]

[Table 152] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

Examples 95 and 96 Alkali-soluble resins shown in Table 153 below, represented by general formula (IV) to
A compound that generates an acid by light irradiation represented by (VII),
The dissolution inhibitors shown in Table 154 below and the compounds represented by the general formulas (I) to (III) were mixed in the proportions shown in Tables 153 and 154, and dissolved in ethyl cellosolve acetate in the same manner as in Example 75. Then, the mixture was further filtered to prepare two kinds of photosensitive resin compositions.

[0254]

[Table 153]

[0255]

[Table 154] Then, a flat underlayer is formed on the silicon substrate in the same manner as in Example 75, each of the photosensitive resin compositions is applied onto the flat underlayer, dried and exposed, and then developed with an aqueous TMAH solution to produce a positive pattern. An upper layer pattern was formed, and oxygen RIE was performed on the lower flat lower layer using the upper layer pattern as a mask.

The pattern shapes of the planarizing layer after oxygen RIE in Examples 75 to 96 were observed with a scanning electron microscope. As a result, it was confirmed that it is possible to form a highly precise two-layer pattern having a fine and rectangular shape, each having a steep pattern profile of 0.35 μm.

Examples 99 to 101 First, alkali-soluble resins shown in Table 155 below, compounds that generate an acid upon irradiation with light, dissolution inhibitors shown in Table 156 below, and compounds represented by the general formulas (I) to (III) Table 1
55, blended in a ratio shown in Table 156, dissolved in 250 g of ethyl cellosolve acetate, and filtered by using a 0.2 μm fluororesin membrane filter to obtain 3
A variety of photosensitive resin compositions were prepared.

[0258]

[Table 155]

[0259]

[Table 156] Then, each photosensitive composition was applied onto a silicon wafer and dried on a hot plate at 90 ° C. for 5 minutes to form a photosensitive resin composition film (resist film) having a thickness of 1.0 μm. Next, KrF is added to these resist films.
Pattern exposure (100 mJ / cm ² ) was performed with a reduction projection exposure machine using excimer laser light. Subsequently, heat treatment was performed on a hot plate at 110 ° C. for 1 minute.
After that, it was immersed in a TMAH aqueous solution for 1 minute and developed to form three types of positive pattern. In Example 99, an aqueous TMAH solution having a concentration of 2.0% by weight was used.
For 0 and 101, a 2.38 wt% TMAH aqueous solution was used.

The shapes of the positive type patterns of Examples 99 to 101 were examined. As a result, it was confirmed that each of them had a steep pattern profile of 0.35 μm and could form a fine and highly precise positive pattern having a rectangular shape.

[0261]

As described above in detail, according to the photosensitive composition of the present invention, the composition is excellently exposed to deepUV and ionizing radiation, has excellent dry etching resistance, and can be developed with an aqueous alkaline solution after exposure. In addition, it is possible to form a fine positive type pattern having a highly accurate and highly tolerant rectangular cross section in which swelling is suppressed, and to effectively use it as a mask in the dry etching process of semiconductor devices. Play. Further, according to the photosensitive composition of the present invention, it is satisfactorily exposed to deepUV and ionizing radiation, and after exposure, it can be developed with an alkaline aqueous solution to form a fine positive pattern having oxygen RIE resistance after development. It can be applied to a two-layer resist system, and has a remarkable effect that it is extremely convenient for fine processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08K 5/54 KCD 7167-4J C08L 101/00 G03F 7/004 7124-2H 503 7124-2H 7 / 029 9019-2H 7/038 7124-2H 7/075 511 7124-2H H01L 21/00 8518-4M 21/027

Claims (4)

[Claims] 1. A (A) alkali-soluble polymer, (B) a dissolution inhibitor comprising an organic compound having a substituent decomposable by an acid, (C) a compound which generates an acid upon irradiation with light, and (D) The following general formulas (I), (II) and (II
A photosensitive composition comprising: a compound represented by I); [Chemical 1] However, in the formula (I), X ₁ is O atom or S atom, and X ₂ is N atom.
An atom or a CR ⁴ group is shown. R ^{1 to} R ³ and R ^{4 of the} CR ⁴ group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic group. It represents a hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. Incidentally, R ² and R ³ may form a hydrocarbon ring group or a heterocyclic group. [Chemical 2] However, in formula (II), X ₃ is O atom or S atom, and X ₄ is N atom.
An atom or a CR ⁷ group is shown. R ⁵ , R ⁶ and R ^{7 of the} CR ⁷ group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic group. It represents a hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. [Chemical 3] However, in the formula (III), X ₅ represents an O atom or an S atom, and X ₆ represents an N atom or a CR ¹¹ group. R ^{8 to} R ¹⁰ and the CR ¹¹
R ^{11 s} of the group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic hydrocarbon group,
It represents an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. Incidentally, R ⁹ and R ¹⁰ may form a hydrocarbon ring group or a heterocyclic group. 2. The photosensitive composition according to claim 1, wherein the alkali-soluble polymer contains silicon. 3. A (A) alkali-soluble polymer, (B) a dissolution inhibitor comprising an organic compound having a substituent capable of decomposing by an acid, and (C) a compound represented by the following chemical formulas 4, 5, 6 and 7. General formula (IV), (V)
, (VI) and (VII) which generate an acid upon irradiation with light, and (D) the following general formulas (I), (II) and (I)
A photosensitive composition comprising a compound represented by II): [Chemical 4] However, R ¹² , R ¹³ and R ¹⁴ in the formula (IV) may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a silyl group or a monovalent organic group. R ¹⁵ represents a monovalent or higher valent organic group, and n represents an integer of 1 to 7. Note that R ¹³ and R ¹⁴
May form a hydrocarbon ring group or a heterocyclic group. [Chemical 5] However, R ¹⁶ and R ¹⁷ in the formula (V) may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group silyl group, or a monovalent organic group. R ¹⁸ represents a monovalent or higher valent organic group. X ₇ is, -O -, - S -, - SO 2 -, - CO-,
_{-CR 1 R 2 -,> N} -COR 3 (R 1, R 2, R 3;
A hydrogen atom, a halogen atom, a cyano group, a silyl group or a monovalent organic group, which may be the same or different from each other), and n represents an integer of 1 to 7. [Chemical 6] However, R ¹⁹ and R ²⁰ in the formula (VI) may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group silyl group, or a monovalent organic group. R ²¹ represents a monovalent or higher valent organic group. X ₈ is, -O -, - S -, - SO 2 -, - CO-,
_{-CR 1 R 2 -,> N} -COR 3 (R 1, R 2, R 3;
A hydrogen atom, a halogen atom, a cyano group, a silyl group or a monovalent organic group, which may be the same or different from each other), and n represents an integer of 1 to 7. [Chemical 7] However, R ²² , R ²³ , R ²⁴ , and R ²⁵ in the formula (VII) may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a silyl group, or a monovalent organic group. R ²⁶ represents a monovalent or higher valent organic group, and n represents an integer of 1 to 7. [Chemical 8] However, in the formula (I), X ₁ is O atom or S atom, and X ₂ is N atom.
An atom or a CR ⁴ group is shown. R ^{1 to} R ³ and R ^{4 of the} CR ⁴ group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic group. It represents a hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. Incidentally, R ² and R ³ may form a hydrocarbon ring group or a heterocyclic group. [Chemical 9] However, in formula (II), X ₃ is O atom or S atom, and X ₄ is N atom.
An atom or a CR ⁷ group is shown. R ⁵ , R ⁶ and R ^{7 of the} CR ⁷ group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic group. It represents a hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. [Chemical 10] However, in the formula (III), X ₅ represents an O atom or an S atom, and X ₆ represents an N atom or a CR ¹¹ group. R ^{8 to} R ¹⁰ and the CR ¹¹
R ^{11 s} of the group may be the same or different and each is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted aliphatic hydrocarbon group,
It represents an unsubstituted or substituted alicyclic hydrocarbon group, various other characteristic groups, or a hydrogen atom. Incidentally, R ⁹ and R ¹⁰ may form a hydrocarbon ring group or a heterocyclic group. 4. The photosensitive composition according to claim 3, wherein the alkali-soluble polymer contains silicon.