JP2841161B2 - Photosensitive resin composition for pattern formation and pattern formation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming a pattern having excellent heat resistance, film formability, adhesion, plasma etching resistance and the like, and a pattern forming method using the same.

[0002]

2. Description of the Related Art In the process of manufacturing a semiconductor device such as an LSI,
2. Description of the Related Art A semiconductor circuit is formed using a microfabrication technique by photolithography. That is, a photoresist film is formed on a substrate such as a silicon single crystal wafer, and after pattern exposure of this film, a photosensitive resin composition pattern formed by performing development processing is used as an etching mask, and the exposed substrate is exposed. It is manufactured by forming fine lines and windows by etching. This microfabrication, L
Finer processing technology has been required with higher integration of SI, and a photosensitive resin material that can cope with the finer processing technology has been required. Characteristics required for such a material include high heat resistance, film forming property, adhesion to a substrate, and high sensitivity to exposure. Conventionally, for such required characteristics,
A photosensitive resin composition material comprising a combination of a polyhydroxystyrene derivative or a phenolic resin derivative and a compound that generates an acid upon irradiation with light has been proposed, but is still insufficient in heat resistance, film formability, and adhesion. There is a problem that is not something.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks, and an object of the present invention is to provide a photosensitive material which is excellent in heat resistance, film formability, photosensitivity and the like and which can be obtained at low cost. An object of the present invention is to provide a photosensitive resin composition for forming a pattern, which is suitable for an ultrafine processing step in the production of semiconductor devices and the like. Another object of the present invention is to provide a pattern forming method which can be applied to an ultra-fine processing step or the like in manufacturing a semiconductor device or the like.

[0004]

The inventor of the present invention has made intensive studies to solve the above problems, and as a result, the following general formula (1)
It has been found that the above problems can be solved by preparing a photosensitive resin composition using an aromatic polyamide containing a repeating unit represented by and a compound that generates an acid upon irradiation with ultraviolet light, X-rays or electron beams. The invention has been completed.

[0005] sensitive photosensitive resin composition of the present invention, the aromatic polyamide containing repeating units represented by the following general formula (1), ultraviolet rays, X-rays or electron beam compound capable of generating an acid upon irradiation (hereinafter, “A compound that generates an acid upon irradiation with light”).

Embedded image (Wherein, Ar ¹ and Ar ² each represent an aromatic group, and R ¹ and R ² each represent a hydrogen atom, —OH, —
OR ³ , —OC (O) R ³ , —OC (O) OR ^3, or —OCH ₂ C (O) OR ³ (where R ³ has a substituent
Linear or branched alkyl groups,
Represents a kill group or an alkyl group-containing siloxy group. ) Represent, with the proviso that at least one is -OR in which R ¹ and R ^{2
3, -OC (O) R 3} , -OC (O) OR 3 or -O
Represents CH ₂ C (O) OR ³ and R ¹ is a hydrogen atom or less
When referring to outside group, Ar ¹ represents a single ring aromatic group, R ²
When represents a group other than a hydrogen atom, Ar ² is a monocyclic aromatic group
Represents )

[0006] sensitive photosensitive resin composition of the present invention, polybutadiene having an aromatic polyamide containing repeating units of formula (1), an amino group at both ends, a carboxyl group, an epoxy group or a hydroxyl group, It may contain a block copolymer of a liquid rubber selected from a polybutadiene-acrylonitrile copolymer, a hydrogenated polybutadiene or a polysiloxane, and a compound that generates an acid by light irradiation . The pattern forming method of the present invention, by coating the photosensitive resin composition of the upper SL on the substrate to form a photosensitive resin layer, performs a desired pattern exposure on the photosensitive resin layer, developed with an alkali aqueous solution containing an alcohol It is characterized by doing.

Hereinafter, the present invention will be described in detail. In the present invention, in the aromatic polyamide containing a repeating unit represented by the above general formula (1), the aromatic groups represented by Ar ¹ and Ar ² include not only a benzene single ring but also 2
It may be a condensed ring composed of two or more benzene rings and two or more benzene rings linked via a direct bond, a carbon atom and / or a hetero atom. Also, the aromatic group is
It may be an aromatic heterocyclic ring such as a pyridine ring. However
And when R ¹ and R ² are groups other than a hydrogen atom,
Nawachimoto ^{-OH, -OR 3, -OC (O} ) R 3, -OC
(O) OR ³ or —OCH ₂ C (O) OR ³ is substituted
Ar ¹ and Ar ² when the benzene ring or
Is a monocyclic aromatic group such as a pyridine ring . Further, at least one of R ¹ and R ² is —OR ³ , —OC (O)
R ³ , —OC (O) OR ³ or —OCH ₂ C (O) O
R ³ represents a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxymethoxy group, a butoxycarbonylmethoxy group, a p-bromophenylcarbonylmethoxy group, a benzyloxy group, an acetoxy group, an ethylcarbonyl group. Oxy group, propylcarbonyloxy group, butylcarbonyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group, butoxycarbonyloxy group,
Examples include a benzyloxycarbonyloxy group, a trimethylsiloxy group, a butylcarbonylmethoxy group, and a phenoxycarbonyloxy group.

[0008] The aromatic polyamide in the present invention is:
R ¹ and R ² are characterized in that the aromatic ring has a group which can be easily converted to a hydroxyl group or a carboxyl group.
Polyamide having a group easily converted to a hydroxyl group or a carboxyl group present in this aromatic ring, when coexisting with a substance that generates an acid upon irradiation with light, is easily converted to a hydroxyl group or a carboxyl group by the acid generated upon exposure. The group converted to is decomposed, and the hydrophobic polyamide is converted into a hydrophilic substance, thereby causing a difference in solvent solubility between the unexposed portion and the exposed portion. Utilizing this difference in solvent solubility enables patterning. In the present invention, the aromatic polyamide has a molecular weight of 1,000.
Those having a range of 0 to 200,000 are preferred. Further, in the aromatic polyamide, the content of the group which is easily converted to a hydroxyl group or a carboxylic group by reacting with an acid is 20 to 100 with respect to the total aromatic group contained in the aromatic polyamide.
% Is preferred. If the content is too small, the molecular structure change after exposure is small, etching is not easily performed,
This causes problems such as poor resolution.

In the present invention, the aromatic polyamide containing a repeating unit represented by the above general formula (1) is used as a dicarboxylic acid component and a diamino component as the following general formula (2)
Or at least one of a dicarboxylic acid represented by the following formula and a diamine represented by the following general formula (3), and a dicarboxylic acid component and a diamino component containing them are subjected to polycondensation (production method (I)), Alternatively, a hydroxyl group of a phenolic hydroxyl group-containing polyamide produced using at least one of a phenolic hydroxyl group-containing dicarboxylic acid and a phenolic hydroxyl group-containing diamine as the dicarboxylic acid component and the diamino component is added to the following general formula (4):
To (7) (Production method (II)).

Embedded image ( Wherein , Ar ¹ and Ar ² are the same as defined above.
Represents an aromatic group, R ¹ 'and R ^2' are each -OR ^3, represents a ^{-OC (O) R 3, -OC} (O) OR 3 or ^{_{-OCH 2 C (O) OR 3}} , Wherein R ³ is a linear or branched alkyl group which may have a substituent,
Represents an aralkyl group or a siloxy group containing an alkyl group. XR ³ (4) XC (＝ O) R ³ (5) R ⁴ OC (＝ O) OR ³ (6) XCH ₂ C (＝ O) OR ³ (7) (X is a halogen atom, R ³ is substituted Represents a linear or branched alkyl group, an aralkyl group, or an alkyl group-containing siloxy group which may have a group, and R ⁴ represents a linear or branched alkyl group or a substituent. Represents an aromatic group which may be substituted.)

In the production of the aromatic polyamide, a conventionally known method (Polymer functional material series 2, Synthesis and reaction of polymer, edited by The Society of Polymer Science, 1991) can be used. That is, when the method for producing a polyamide according to the production method (I) is used, for example, a nylon salt method, a solution condensation method, an active esterification method, a direct method using a condensing agent, and the like can be applied. In the case where the aromatic polyamide is produced via the synthesis of the phenolic hydroxyl group-containing polyamide by the production method (II), a condensing agent capable of reacting without protecting the phenolic hydroxyl group. Can be used. When producing a polyamide using a condensing agent, as the condensing agent,
Known materials can be used (polymer functional material series 2,
Polymer Synthesis and Reaction, edited by The Society of Polymer Science, 1991). In the present invention, there is no limitation on the condensing agent used,
A condensing agent comprising a combination of a phosphite and a pyridine derivative, which is easily available at low cost, is preferably used. For the condensation reaction, a solution polymerization method using a mixed solvent containing a pyridine derivative is usually employed. At this time, as the organic solvent used, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2
Amide solvents such as -pyrrolidone are preferred. The amount of these solvents used is 5-30
It is preferable that the amount is such that it contains% by weight. When the aromatic polyamide is produced using a condensing agent represented by triphenyl phosphite and pyridine, the condensing agent is preferably used in an amount of twice or more mol of the dicarboxylic acid used. preferable. Further, a small amount of lithium chloride and calcium chloride may be added to an amide solvent represented by N-methyl-2-pyrrolidone. The reaction is performed from room temperature to 1
It may be carried out at a temperature of about 20 ° C. for 30 minutes to several hours, whereby the target polyamide can be synthesized.

An aromatic polyamide containing a repeating unit represented by the general formula (1) used in the second photosensitive resin composition of the present invention, and an amino group at both terminals,
Polybutadiene having a carboxyl group, an epoxy group or a hydroxyl group, a polybutadiene-acrylonitrile copolymer, a block copolymer with a liquid rubber selected from hydrogenated polybutadiene or polysiloxane has an amino group at both ends, a carboxyl group, an epoxy group or It can be produced by subjecting a corresponding aromatic polyamide having an amino group or a carboxyl group at both terminals to block polymerization of a liquid rubber having a hydroxyl group. Such an aromatic polyamide having an amino group or a carboxyl group at both terminals can be obtained by reacting an excess of either the dicarboxylic acid component or the diamine component.

The dicarboxylic acids represented by the general formula (2) and the diamines represented by the general formula (3) used in the production of the polyamide containing the repeating unit represented by the general formula (1) in the present invention. Is 5-methoxyisophthalic acid, 5-ethoxyisophthalic acid, 5-isopropyloxyisophthalic acid, 5-tert-butylester isophthalic acid, 4-tert-butoxyisophthalic acid, 4-ethoxyphthalic acid, 5-benzyloxyisophthalic acid , 5
-Trimethylsiloxyisophthalic acid, 3-trimethylsiloxyphthalic acid, 4-trimethylsiloxyphthalic acid, 5
-T-butoxycarbonylmethoxyisophthalic acid, 5-
t-butoxycarbonylmethoxyphthalic acid, 2-t-butoxycarbonyloxyterephthalic acid, 5-methoxy-
1,3-diaminobenzene, 5-t-butoxy-1,3
- diaminobenzene, 5-benzyloxy-2,6-diaminobenzene, 5-t-butoxy-2,6-diaminopyridine, although 5-trimethyl ether 1,3-diamino <br/> pyridine emissions, and the like However, the present invention is not limited to these. Further, these two or more kinds may be used as a mixture.

In the present invention, as the dicarboxylic acid component in the aromatic polyamide, in addition to the dicarboxylic acid represented by the general formula (2), other dicarboxylic acids ( R ¹ ′)
May be used. Examples of the aromatic dicarboxylic acids other than the dicarboxylic acid represented by the general formula (2) include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid,
3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyl dibenzoic acid, 4, 4 '
-Sulfonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybenzophenone, 2,2-bis (4-carboxyphenyl) Propane, bis (4-carboxyphenyl) methane, 2,2
-Bis (4-carboxyphenyl) hexafluoropropane, 2,6-dicarboxypyridine, N, N'-methylenephthalimide-3,3'-dicarboxylic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid,
-Hydroxyisophthalic acid, 3-hydroxyphthalic acid,
Examples thereof include, but are not limited to, dicarboxylic acids such as 4-hydroxyphthalic acid and 4-hydroxy-2,5-dicarboxypyridine and derivatives thereof. Further, one or more of these may be used in combination. Moreover, you may use together with the dicarboxylic acid shown by the said general formula (2).

Similarly, as the diamine component in the aromatic polyamide of the present invention, other aromatic diamines (diamines having no R ² ′ ) other than the diamine represented by the above general formula (3) may be used. Good. Examples of aromatic diamines other than the diamine represented by the general formula (3) include m-phenylenediamine, p-phenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 1,3-diaminoxylene 4,4'-diamino-
3,3 ', 5,5'-tetramethylbiphenyl, bis (3-methyl-4-aminophenyl) methane, 2,2'
-Bis (4-aminophenyl) hexafluoropropane, 2,2'-fluoromethane-4,4'-diaminobiphenyl, 1,3-bis (3-aminophenoxy) benzene, 2,2'-bis-[(4 -(4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, metatolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- dimethyl-4,4'-diaminodiphenyl thio ether, 3, 3'-diaminodiphenyl thioether, 4,4'-diamino benzophenone,
Bis (3,5-dimethyl-4-aminophenyl) methane, bis (3,5-diethyl-4-aminophenyl) methane, bis (3-ethyl-5-methyl-4-aminophenyl) methane, 3,3 '-Dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-
Dimethoxy-4,4'-diaminodiphenylmethane,
2,2-bis (3-aminophenyl) propane, 2,2
- bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, benzidine, 3,3'-dimethyl bench di emissions,
3, 3'-amino-biphenyl, p- xylylenediamine, m- xylylenediamine, trimethylene - bis (4
- aminobenzoate), 1,1-bis (4-aminophenyl) cyclohexane, bis [4- (3-aminophenoxy) phenyl] sulfonyl emissions, 2, 5-diaminopyridine, 2,6 Jiaminopiriji emissions, 2, 6 - There is Jiaminofe <br/> no Le etc., it can be used as a mixture thereof or agents. These are represented by the above general formula (3)
May be used in combination with the diamine represented by

Further, the phenolic hydroxyl group-containing dicarboxylic acid and phenolic hydroxyl group-containing diamine used for producing the phenolic hydroxyl group-containing polyamide in the production method (II) include, for example, 5-hydroxyisophthalic acid and 4-hydroxy isophthalic acid, 2-hydroxy-isophthalic acid, 3-hydroxy phthalic acid, 4-hydroxy phthalic acid, 2, 3-diamino-4-hydroxy <br/> pyridine down, 4 - hydroxy-2,5-dicarboxylate pyridine and However, the present invention is not limited to these. When the phenolic hydroxyl group-containing polyamide is produced, the phenolic hydroxyl group-containing carboxylic acid may be used in combination with a dicarboxylic acid having no hydroxyl group or R ¹ ′ . The phenolic hydroxyl group-containing diamine may be used in combination with the above-mentioned diamines having no hydroxyl group or R ² ′ .

Examples of the compounds represented by the general formulas (4) to (7) to be reacted with the phenolic hydroxyl group-containing polyamide include methyl chloride, methyl bromide, and the like.
Ethyl bromide, n-propyl chloride, i-propyl bromide, n-butylcarbonyl chloride, t
-Butylcarbonyl chloride, i-butyl bromide, benzyl chloride, benzyl bromide, acetyl chloride, propanoyl chloride, n-propylcarbonyl bromide, i-propylcarbonyl bromide, n-butylcarbonyl chloride, t-butylcarbonyl chloride, i-butyl Carbonyl chloride, methoxymethyl bromide, p-bromophenacyl chloride, trimethylsilyl chloride, benzyloxycarbonyl chloride, t-butyl bromoacetate, 4-t-butylbenzyl chloride, di-t dicarbonate
-Butyl, diethyl carbonate, diphenyl carbonate, isopropyl chloroformate, isobutyl chloroformate, t-butoxycarbonyl chloride, t-butylpentachlorophenyl carbonate, p-carboxyphenyl-n-butyl carbonate, p-carboxyphenyl-n-ethyl carbonate, Examples thereof include p-carboxyphenyl-n-pentyl carbonate, p-carboxyphenyl-n-amyl carbonate, p-carboxyphenylethyl carbonate and the like.

[0017] As used sensitive photosensitive resin composition of the present invention
The block copolymer which can be produced is an aromatic polyamide having a repeating unit represented by the above general formula (1) produced as described above, and having an amino group, a carboxyl group, an epoxy group or a hydroxyl group at both terminals. Polybutadiene,
It can be produced by block copolymerizing a polybutadiene acrylonitrile copolymer, a liquid rubber selected from hydrogenated polybutadiene or polysiloxane. These liquid rubbers have a glass transition temperature of 10
C. or lower and a molecular weight in the range of 500 to 10,000 are preferred, and commercially available ones can be used. Specific examples of liquid rubbers that can be used include amino groups, carboxyl groups, hydroxyl groups, polybutadiene having an epoxy group at both ends, polybutadiene-acrylonitrile copolymer as a Hycar series from Goodrich, and carboxyl groups or hydroxyl groups at both ends. Hydrogenated polybutadiene having G1 and G2 series from Nippon Soda Co., Ltd.
Polycycloxane having a hydroxyl group and an epoxy group having various molecular weights are commercially available from Toshiba Silicon, Shin-Etsu Silicon, Chisso and the like.

On the other hand, as the compound that generates an acid upon irradiation with light, various known compounds and mixtures can be used. For example, CF ₃ SO ₃ such as diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, etc.
^{_{-, p-CH 3 C 6}} H 4 SO 3 -, p-NO 2 C 6 H 4
SO ₃ ^- salts such as organic halogen compounds, o-quinone diazide sulfonyl chloride, sulfonic acid esters, and the like. The organic halogen compound is a compound that forms hydrohalic acid. These specific compounds are
U.S. Pat. No. 3,515,552;
No. 489, No. 3777978, and Japanese Patent Application Laid-Open No. 54-74728, and 55-24.
No. 113, 55-77742 and the like. Specific examples of such compounds include di (pt-butylphenyl) iodonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, benzoin tosylate, o-nitrobenzyl paratoluenesulfonate, bis (4-t- Butylphenyl) iodonium trifluoromethanesulfonate, t-butyl-α- (p-toluenesulfonyloxy) acetate, triphenylsulfonium trifluoromethanesulfonate, tri (t-butylphenyl) sulfonium trifluoromethanesulfonate, benzenediazoniumtoluenesulfonate,
4- (di-n-propylamino) -benzonium tetrafluoroborate, 4-p-trimercapto-2,5-
Diethoxybenzenediazonium hexafluorophosphate, tetrafluoroborate, diphenylamine-
4-diazonium sulfate, 4-methyl-6-trichloromethyl-2-pyrone, 4- (3,4,5-trimethoxystyryl) -6-trichloromethyl-2-pyrone, 2-trichloromethylbenzimidazole, 2- Tribromomethylquinoline, 4-dibromoacetylbenzoic acid, 1,4-bis (dibromomethyl) benzene, tris (dibromomethyl) -S-triazine, 2- (6-methoxy-naphth-2-yl) -4,6 -Bis (trichloromethyl) -S-triazine, 2- (naphth-1-yl)
-4,6-bis (trichloromethyl) -S-triazine, 2- (naphth-2-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-ethoxymethylnaphth-1-) Yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-anthran-1-yl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (phenan-9-yl) -4,
6-bis-trichloromethyl-S-triazine, 0-naphthoxydiazide-4-sulfonic acid chloride, naphthoxydiazide-4-sulfonic acid ester, naphthoxydiazide-5-sulfonic acid ester, p-toluenesulfone Acid-0-nitrobenzyl ester, p-toluenesulfonic acid-2,6-dinitrobenzyl ester, bis (phenylsulfonyl) diazomethane, bis (phenylsulfonyl) methane, 2,3,4,4'-tetrahydroxybenzophenone and 1 And ester compounds of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid. However, the present invention is not limited to these.

The compound capable of generating an acid upon irradiation with light is:
It is desirable that the content is contained in the range of 0.1 to 30% by weight, particularly 0.5 to 20% by weight of all solid forming components of the photosensitive resin composition for pattern formation. If the content is lower than 0.1% by weight, it becomes difficult to obtain sufficient photosensitive characteristics. On the other hand, if the compounding ratio of the compound exceeds 30% by weight, it may be difficult to form a uniform resist film, or residues may be generated during removal after development or etching.

Further, the photosensitive resin composition of the present invention can be colored by adding a dye or a pigment. Examples of such dyes and pigments, azo, anthraquinone, phthalocyanine, indigo, thioindigo,
Dyes such as diphenylmethane type, polymethine type, azomethine type, acridine type, quinone imine type, cyanine type, quinoline type, nitro type, naphthoquinone type, perylene type,
Oxides, hydroxides, sulfides, phthalocyanines,
Inorganic pigments such as chromate, sulfate, carbonate, phosphate and metal powders, and organic pigments such as nitro, nitroso, azo, phthalocyanine and condensed polycyclic can be used. . In the present invention, these pigments are 1 μm or less,
A fine color pattern can be obtained by using particles having a size of preferably 0.1 μm or less.

The photosensitive resin composition for forming a pattern according to the present invention may be used in combination with the aromatic polyamide or its block copolymer and a compound capable of generating an acid upon irradiation with light, if desired.
Pigments or dyes, and other components are added and used after being dissolved or dispersed in an organic solvent. Examples of such a solvent include ketone solvents such as cyclohexanone, acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, ethyl acetate, and acetic acid. Ethyl solvents such as butyl, isoamyl acetate, and methyl lactate, solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, dioxane, and tetrahydrofuran, or a mixed solvent thereof are used depending on the purpose of use. be able to. The photosensitive resin composition for pattern formation of the present invention may contain a sensitizer, a dissolution inhibitor and the like, if necessary. Further, the photosensitive resin composition for forming a pattern of the present invention, if necessary, contains a carboxylic acid compound represented by propiobutyric acid, 2-methylpropanoic acid, etc. for increasing the dissolution rate in an alkaline aqueous solution. Is also good.

In the pattern forming method of the present invention, the above-mentioned photosensitive resin composition is applied on a substrate in the form of a solution or a dispersion by a spin coating method or a dipping method, and then is heated under vacuum, under heating, or under heating. Drying under vacuum forms a photosensitive resin layer. As the substrate used here, for example,
Silicon wafers, glass, various polymer films, these substrates with various insulating films, electrodes, and wirings formed on the surface, blank masks, GaAs, AlGaAs, etc. III
To V group compound semiconductor wafers. Next, pattern exposure is performed by selectively irradiating light (the light in the present invention is defined as including an ultraviolet ray, an electron beam, and an X-ray) through a mask having a desired pattern on the photosensitive resin layer, An acid is generated from a compound which generates an acid by light irradiation contained in the photosensitive resin layer. This acid
It reacts with a substituent decomposed by an acid in the polyamide or the block copolymer in the photosensitive resin layer to change its molecular structure. Due to this change in the molecular structure, the exposed portion becomes soluble in an aqueous alkaline solution containing an alcohol component. Next, the exposed photosensitive resin layer is washed with the alkaline aqueous solution to remove the exposed portion of the photosensitive resin composition, thereby forming a positive pattern. Further, in order to selectively remove the unexposed portions to obtain a negative type, a solvent which dissolves the unexposed portions but does not dissolve the exposed portions can be used. In this case, a vapor of a silylating agent typified by trialkylsilyl chloride is introduced and added to the generated phenolic hydroxyl group to form a silicon-containing polymer layer, which is then negatively treated by treatment with oxygen plasma. It is also possible to form a mold pattern. Further, in the present invention, in order to prevent the formation of a hardly soluble layer on the surface of the photosensitive resin layer, a water-soluble resin film may be provided on the surface of the photosensitive resin layer to perform exposure. Examples of such a water-soluble resin include polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, and polymaleic acid. In the present invention, a conductive layer may be provided on the surface of the photosensitive resin layer in order to prevent displacement of pattern formation due to electron beams due to charge-up.

The ultraviolet light used for the light irradiation includes:
For example, an excimer laser such as KrF, ArF, XeF, or XeCl, or an i-line, an h-line, or a g-line of a mercury lamp can be used. In the pattern exposure step, the photosensitive resin layer may be subjected to pattern exposure directly by scanning with an electron beam, X-ray, or laser without using the mask. Further, the photosensitive resin layer after pattern exposure is 70
By heating to 160 ° C., the reaction between the acid generated in the photosensitive resin layer and the compound having a substituent that is decomposed by the acid in the photosensitive resin layer may be promoted.

After exposing the photosensitive resin layer as described above,
A desired photosensitive resin composition pattern is formed by developing with an alcohol-containing alkali solution. Examples of the alcohol-containing alkaline aqueous solution used in the present invention include, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, an inorganic alkaline aqueous solution such as sodium metasilicate, a tetramethylammonium hydroxide aqueous solution,
An organic alkali aqueous solution such as a trimethylhydroxyammonium hydroxide aqueous solution and a hydrazine aqueous solution can be used. Further, as the alcohol, methanol, ethanol, isopropanol, etc. can be used,
The present invention is not limited to these. Also,
The content and alkalinity of these alcohols can be arbitrarily adjusted depending on the structure of the aromatic polyamide according to the present invention, the concentration of the generated hydroxyl group or carboxyl group, the dissolution rate, and the like.

[0025]

The photosensitive resin composition of the present invention contains an aromatic polyamide containing a repeating unit represented by the above general formula (1), and the aromatic ring of this polyamide is easily converted into a hydroxyl group or a carboxyl group. These groups are converted to a hydroxyl group or a carboxyl group by reacting with an acid generated by exposure from a compound that generates an acid by light irradiation that coexists in the photosensitive resin composition. To be. As a result, the photosensitive resin composition containing the aromatic polyamide changes from hydrophobic to hydrophilic, and a difference in solvent solubility occurs between an exposed portion and an unexposed portion. By utilizing this difference in solvent solubility, pattern formation becomes possible. That is, after the film formed from the photosensitive resin composition is exposed in a pattern, the portion that has been hydrophilized with an alcohol-containing alkali aqueous solution is etched to obtain a positive pattern. Further, in the present invention, an aromatic polyamide containing a repeating unit represented by the general formula (1) and a polybutadiene having an amino group, a carboxyl group, an epoxy group or a hydroxyl group at both terminals, a polybutadiene acrylonitrile copolymer, a hydrogenated polybutadiene or a polybutadiene When a block copolymer with a liquid rubber selected from siloxane is used, various flexibility, adhesion and adhesion can be imparted to the substrate by selecting the liquid rubber. The block copolymer is prepared by appropriately selecting the type according to the type of the resin, thereby making it possible to obtain a more excellent photosensitive resin composition for pattern formation. Such a block copolymer has a sea-island structure in which the aromatic polyamide is turned into a sea.
Since the size is about 0 Å, sufficient pattern accuracy can be maintained even when a fine pattern is formed. Further, in the present invention, when the photosensitive resin composition contains a dye or pigment and is colored, it is advantageous in that it can be applied to visualization of a formed pattern, optical detection, a fine light filter, and the like. There is.

[0026]

EXAMPLES Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Example 1 5-t-butoxyisophthalic acid 28.59 g (120 mmol), m-diaminobenzene 12.98 g (120
Mmol), 2.8 g of lithium chloride, 8.7 g of calcium chloride, 74.4 g of triphenyl phosphite, 350 ml of N-methyl-2-pyrrolidone and 35 ml of pyridine.
After placing in a 00 ml three-necked round-bottomed flask and reacting at 100 ° C. for 2 hours while stirring under a nitrogen stream, the mixture was poured into a large amount of methanol to form an aromatic polyamide having a 5-t-butoxy group. Was. The precipitated polymer was purified by repeating refluxing with methanol three times to obtain a target polymer. 2 g of this polymer and 0.4 g of toluenesulfonic acid-2,2-dinitrobenzyl ester were dissolved in 10 g of dimethylformamide and filtered through a 0.2 μm filter to obtain a photosensitive resin composition of the present invention. This composition was spin-coated on a glass substrate and prebaked on a hot plate at 70 ° C. for about 1 hour under vacuum to form a photosensitive resin layer having a thickness of 1.0 μm. Subsequently, after pattern exposure was performed with a KrF excimer stepper (NA 0.45), 120
After baking for 5 minutes on a hot plate at ℃, immersed in an aqueous solution containing a mixture of 150 g of methanol, 350 g of water and 5 g of sodium hydroxide for 30 seconds, developed, washed and dried, and scanned the cross-sectional shape of the formed pattern. 0.5μm with sharp edges when examined with a scanning electron microscope
It was confirmed that a width pattern was obtained.

Example 2 21.86 g (120 mmol) of 5-hydroxyisophthalic acid and 12.98 g (1,1 g) of 2,6-diaminophenol
20 mmol), 2.8 g of lithium chloride, 8.07 g of calcium chloride, 74.4 g of triphenyl phosphite, N-
350 ml of methyl-2-pyrrolidone, 35 ml of pyridine
Was placed in a 500 ml three-necked round-bottomed flask, reacted at 100 ° C. for 2 hours while stirring under a nitrogen stream, and then poured into a large amount of methanol to produce an aromatic polyamide having a 5-hydroxyl group. . The precipitated polymer was purified by refluxing with methanol three times to obtain the desired polyamide having a phenolic hydroxyl group. 30 g of this polyamide was dissolved in 200 ml of pyridine, and 17.63 potassium carbonate was dissolved.
g, 8.4 g of potassium iodide and 24.38 g of t-butyl bromoacetate were added and refluxed for 7 hours while stirring. Subsequently, the insoluble component was removed by filtration, and then dropped into methanol to precipitate a polymer. After washing three times with a mixed solvent of water and methanol, the resultant was vacuum-dried at 50 ° C. ^From the measurement results of the ¹ H-NMR spectrum,
Of the hydroxyl groups in the phenolic hydroxyl group-containing polyamide,
It was found that about 50% was converted to a t-butoxycarbonylmethoxy group. A photosensitive layer was formed on this resin in exactly the same manner as in Example 1, exposed, etched and washed, and the pattern formed was examined with an electron microscope.
It was confirmed that a pattern having a width of 0.4 μm having sharp edges was obtained.

Example 3 5-t-butoxycarbonylmethoxyisophthalic acid 1
4.75 g (47.9 mmol), 6-hydroxy-
6.25 g (50.4 mmol) of 1,3-diaminobenzene, 1.17 g of lithium chloride, 3.6 g of calcium chloride
3 g, triphenyl phosphite 31.2 g, pyridine 14
ml, N-methyl-2-pyrrolidone 150 ml, 30
In a 0 ml three-necked round bottom flask, the mixture was reacted at 100 ° C. for 2 hours while stirring under a nitrogen stream to synthesize a polyamide having an aminoaryl group at both ends, and then a polybutadiene acrylonitrile having a carboxyl group at both ends. A solution obtained by dissolving 9 g of a copolymer (Hycar CTBN 1300 × 8, molecular weight: about 3600, nitrile component content: about 17 mol%, manufactured by Goodrich) in 43 ml of N-methyl-2-pyrrolidone was further added, and further added for 3 hours. Reacted. This reaction solution was poured into a large amount of methanol to precipitate a target polymer. This polymer was dissolved in dimethylacetamide and reprecipitated with methanol.
Block copolymer (polybutadiene-acrylonitrile) of a polyamide having a highly flexible t-butoxycarbonylmethoxy group and a polybutadiene acrylonitrile copolymer by repeating purification and drying three times by refluxing with methanol. Copolymer content: about 30
% By weight). A photosensitive layer was formed from this resin in exactly the same manner as in Example 1, exposed, etched and washed, and the pattern formed was examined with an electron microscope. As a result, a 0.7 μm-wide pattern having sharp edges was obtained. Was confirmed.

Example 4 In Example 3, 5.2 g of a hydrogenated polybutadiene having a carboxyl group at both terminals (CI-1000, molecular weight: about 2100, manufactured by Nippon Soda Co.) was prepared by adding 5.2 g of a polybutadiene-acrylonitrile copolymer to 50 ml of pyridine. In the same manner as above, except that the solution was replaced with a solution dissolved in water, a block copolymer of a highly flexible target polyamide having a t-butoxycarbonylmethoxy group and hydrogenated polybutadiene (content of hydrogenated polybutadiene: About 20% by weight). This resin was used to form a photosensitive layer in exactly the same manner as in Example 1,
After etching and cleaning, and examining the pattern formed with an electron microscope, 0.9μ with sharp edges
It was confirmed that an m-width pattern was obtained.

Example 5 In Example 3, 5.0 g of a polybutadiene-acrylonitrile copolymer having a carboxyl group at both terminals (XF42-508, molecular weight: 2,000, manufactured by Toshiba Silicon Corporation) was dissolved in 50 ml of pyridine. Except that the solution was replaced, the procedure was the same as in the case of t
A block copolymer of a polyamide having a butoxycarbonylmethoxy group and a polysiloxane (content: about 20% by weight) was obtained. A photosensitive layer was formed from this resin in exactly the same manner as in Example 1, exposed, etched and washed, and the pattern formed was examined with an electron microscope. As a result, a 0.6 μm-wide pattern having sharp edges was obtained. Was confirmed. In addition, this resin showed high adhesiveness to a glass substrate.

Example 6 An oily dye (C.I.) was added to the photosensitive resin composition prepared in Example 3.
I. SolventRed 24 5-3088 SS
0.1 g of T EXTRA (Shirato Chemical Co., Ltd.)
After forming a red photosensitive resin layer on a glass substrate by the same method, an ultraviolet ray (EYE GRANDAG) is passed through a mask.
E ESL-310 UV irradiation apparatus, light source: metal halide lamp, light amount: 120 W / cm) for 20 minutes, developed with the same etching aqueous solution, washed and dried to form a patterned resin layer. . When the pattern formed was examined with an electron microscope, it was confirmed that a 1.5 μm-width red pattern having sharp edges was obtained.

Example 7 Yellow iron oxide (CI Pigment Yellow 425-5) was used in place of the oily dye used in Example 3.
163 Anchor FY-766 manufactured by Toho Pigment Co., Ltd.)
Was dispersed in 0.1 g, a yellow photosensitive resin layer was formed on a glass substrate by the same method, and then an electron beam (CUREYRON-EBC-20 manufactured by Nissin High Voltage Co., Ltd.) was passed through a mask.
Using a 0-CB type, irradiation with an accelerating voltage: 150 KV, beam current: 10 mA, absorption dose of 5 MRAD), development with a similar etching aqueous solution, washing and drying, and a yellow patterned resin layer Was formed. When a pattern formed by an electron microscope was examined, it was confirmed that a pattern having a sharp edge and a width of 1.0 μm was formed.

[0033]

The photosensitive resin composition of the present invention is easy to produce and has excellent heat resistance, film formability, photosensitivity, etc., and is therefore widely used as a photoresist for electronic parts, a color filter for liquid crystal, and the like. Useful in the field. According to the pattern forming method of the present invention using this, ultra-fine processing can be performed, which is particularly useful for manufacturing a semiconductor device.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F ^7/ 00-7/18

Claims (4)

(57) [Claims] 1. A pattern forming method comprising: an aromatic polyamide containing a repeating unit represented by the following general formula (1); and a compound capable of generating an acid upon irradiation with ultraviolet rays, X-rays or electron beams. Photosensitive resin composition. Embedded image (Wherein, Ar ¹ and Ar ² each represent an aromatic group, and R ¹ and R ² each represent a hydrogen atom, —OH, —
OR ³ , —OC (O) R ³ , —OC (O) OR ^3, or —OCH ₂ C (O) OR ³ (where R ³ has a substituent
Linear or branched alkyl groups,
Represents a kill group or an alkyl group-containing siloxy group. ) Represent, with the proviso that at least one is -OR in which R ¹ and R ^{2
3, -OC (O) R 3} , -OC (O) OR 3 or -O
Represents CH ₂ C (O) OR ³ and R ¹ is a hydrogen atom or less
When referring to outside group, Ar ¹ represents a single ring aromatic group, R ²
When represents a group other than a hydrogen atom, Ar ² is a monocyclic aromatic group
Represents ) 2. An aromatic polyamide containing a repeating unit represented by the general formula (1), and an amino group at both terminals.
Generates an acid by irradiation with ultraviolet light, X-rays or electron beams, and a block copolymer of a liquid rubber selected from polybutadiene having a carboxyl group, an epoxy group or a hydroxyl group, a polybutadiene-acrylonitrile copolymer, a hydrogenated polybutadiene or a polysiloxane. The photosensitive resin composition for pattern formation according to claim 1, further comprising: 3. The photosensitive resin composition for forming a pattern according to claim 1, wherein the photosensitive resin composition for forming a pattern contains a color pigment or a dye. 4. The photosensitive resin composition for pattern formation according to claim 1, 2 or 3 is applied to a substrate to form a photosensitive resin layer, and the photosensitive resin layer is exposed to a desired pattern. And developing with an alkaline aqueous solution containing alcohol.