JP6973070B2 - Etching mask resist composition, substrate manufacturing method using it, and light emitting element manufacturing method - Google Patents

Description

The present invention relates to a mask resist composition for etching, a method for manufacturing a substrate using the same, and a method for manufacturing a light emitting element (diode).

Light emitting diodes (LEDs: Light Emitting Devices) are a type of element that converts electrical energy into light energy by utilizing the characteristics of semiconductors. Since LEDs have good energy conversion efficiency and long life, they are becoming widespread as applications for various lighting devices, illuminations, displays, and other electronic devices. Therefore, in recent years, there has been a demand for higher brightness of light emitting elements used in LEDs.

The light emitting element used for such an LED has a structure in which an n-type semiconductor layer such as an n-type GaN layer, a light emitting layer such as an InGaN layer, and a p-type semiconductor layer such as a p-type GaN layer are sequentially formed on a substrate. It has a structure in which light is generated by recombination of electrons injected from the n-type semiconductor layer and holes injected from the p-type semiconductor layer in the light emitting layer.

In a light emitting device having such a structure, a technique for forming a GaN-based semiconductor layer by an epixical growth method in which a GaN-based semiconductor is arranged on a crystal of a substrate so as to be aligned with the crystal plane of the underlying substrate and crystal growth is performed is known. There is. As the crystal growth substrate, a single crystal sapphire substrate having excellent mechanical properties, thermal properties, chemical stability, and light transmission is often used.

However, when a GaN layer is crystal-grown on a single crystal sapphire substrate, there is a difference between the crystal lattice constant of sapphire and the crystal lattice constant of GaN, so that the arrangement of GaN crystals is disturbed during growth and defects occur. was there. In addition, since there is a difference between the refractive index of the sapphire substrate and the refractive index of the GaN-based semiconductor layer, the light generated in the light emitting layer causes total reflection at the layer interface of the sapphire-GaN-based semiconductor, and the light is confined in the GaN-based semiconductor layer. There was a problem of being able to. Due to these problems, the problem is that the amount of light that can be taken out to the outside is reduced.

As a method for increasing the efficiency of light extraction from the light emitting layer, a method of forming a resist pattern on a sapphire substrate and dry-etching the sapphire substrate using this as a mask to form a convex pattern on the surface of the sapphire substrate is known. (For example, see Patent Documents 1 to 3). Due to the formation of the convex pattern, dislocations of crystals proceed along the convex pattern when the GaN-based semiconductor layer is formed, so that the defects of the GaN layer are reduced as compared with the case of using a smooth sapphire substrate. Further, by scattering and diffracting the light generated in the light emitting layer, total reflection at the layer interface can be suppressed.

Japanese Patent No. 3595277 Japanese Unexamined Patent Publication No. 2011-19374 Japanese Unexamined Patent Publication No. 2014-191002

However, in the resist described in Patent Document 1, if dry etching is performed at high output in order to shorten the process, the temperature of the substrate rises and resist burning or carbonization occurs, so that a desired sapphire pattern cannot be obtained. There was a problem.

In the resist described in Patent Document 2, a process of suppressing resist burning and carbonization has been proposed, but since it is necessary to add a process of UV curing while performing heat treatment after the photolithography process and further performing post-baking. , There was a problem that the shortening of the process was insufficient.

The resist described in Patent Document 3 requires resist curing at 300 ° C. or higher in order to obtain sufficient etching resistance, and resist curing at 250 ° C. or lower causes the etching rate to vary in the substrate surface during etching, resulting in in-plane etching. There was a problem that a highly uniform sapphire pattern could not be obtained.

INDUSTRIAL APPLICABILITY According to the present invention, resist burning and charring do not occur even in a high-power dry etching process at a high temperature of 100 ° C to 300 ° C, and high etching resistance is obtained even when resist curing is performed at a low temperature, and in-plane uniformity is obtained. It is an object of the present invention to provide a mask resist composition for etching which can obtain a high sapphire pattern.

The present invention is a composition containing (A) a polyimide containing a structural unit represented by the general formula (1) as a main component, and (B) a photoacid generator, wherein the polyimide (A) has an imide group equivalent. It is a mask resist composition for etching characterized by being 0.0025 mol / g or more.

(In the general formula (1), R ¹ represents a divalent organic group ^{having 2 to 50 carbon atoms, R 2} represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms, and m ¹ represents 0 or 1 integer, ^{c 1} is an integer of 0 or ^1, and ^c 1 = 0 when ^c 1 = ^{1, m} 1 = 1 when ^m 1 = 0.)

The mask resist composition for etching of the present invention does not cause resist burning or charring even in a high-power dry etching process at a high temperature of 100 ° C to 300 ° C, and has high etching resistance even when the resist is cured at a low temperature. can get. Therefore, it is possible to obtain a sapphire pattern with high in-plane uniformity.

The mask resist composition for etching of the present invention contains (A) a structural unit represented by the general formula (1) as a main component, a polyimide having an imide group equivalent of 0.0025 mol / g or more, and (B) light. Contains acid generator.

Each component of the mask resist composition for etching of the present invention will be described in detail below. The following is an example, and the present invention is not limited to the following.

<(A) Polyimide>
(A) Polyimide is a resin component in the mask resist composition for etching of the present invention. In the present invention, (A) polyimide contains a structural unit represented by the general formula (1) as a main component.

In the general formula (1), R ¹ represents a divalent organic group having 2 to 50 carbon atoms. R ² represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms. m ¹ is 0 or 1, ^{c 1} is 0 or ^1, and ^c 1 = 0 when ^c 1 = ^{1, m} 1 = 1 when ^m 1 = 0.

The main component referred to here means that the (A) polyimide occupies 60% by weight or more, preferably 80% by weight or more. (A) The polyimide may be a polyimide composed of a structural unit represented by the general formula (1). It should be noted that the "polyimide composed of structural units represented by the general formula (1)" does not exclude the inclusion of other structural units as long as the effects of the present invention are not impaired.

The content of the structural unit represented by the general formula (1) is the obtained resin as it is by infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), thermal weight measurement-mass spectrometry (TG-MS). , Analysis by flight time type secondary ion mass spectrometry (TOF-SIMS), or after decomposing the resin into each component, gas chromatography (GC), high performance liquid chromatography (HPLC), mass spectrometry (MS), FT -It can be estimated by a method such as analysis by IR, NMR, or further, analysis by elemental analysis after incineration of the resin at a high temperature.

(Diamine residue)
In the general formula (1), R ¹ represents a diamine residue. The diamine residue is preferably a diamine residue having a hydroxyl group from the viewpoint of solubility in an alkaline aqueous solution as a developing solution and photosensitive performance.

Examples of the amine component that gives a diamine residue having a hydroxyl group include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino-4-hydroxyphenyl). Hydroxyphenyl) Propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4) -Hydroxyphenyl) fluorene, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) propane, bis (4) -Amino-3-hydroxyphenyl) methylene, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3-hydroxy) biphenyl, bis (4-amino-3-hydroxyphenyl) fluorene, etc. However, it is not limited to these.

From the viewpoint of dry etching resistance after resist curing, the diamine residue (R ¹ ) has a more preferable structure represented by the following general formula (8).

Shown in the general formula (8), R ¹⁷ is a single _bond, a _{C (CF 3) 2, C} (CH 3) 2, SO 2, O, S, an organic group represented by at least one selected from CH ₂ .. More preferably, it is C (CF ₃ ) ₂ and SO ₂ , and most preferably SO ₂ .

Further, the diamine residue may contain a diamine residue having no hydroxyl group. Examples of the amine component that gives such a diamine residue include carboxyl group-containing diamines such as 3,5-diaminobenzoic acid, 3-carboxy-4,4'-diaminodiphenyl ether, and 3-sulfonic acid-4,4'-diamino. Diphenyl containing sulfonic acid such as diphenyl ether, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine , P-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4, 4'-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4 , 4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or these Examples thereof include compounds in which a part of the hydrogen atom of the aromatic ring of the above is substituted with an alkyl group or a halogen atom, and aliphatic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, but the present invention is not limited thereto.

These diamine residues can also be used as a diamine, or as a diisocyanate compound or a trimethylsilylated diamine in which an isocyanate group or a trimethylsilylated amine is bonded instead of an amino group to the structure of the diamine residue.

Further, the hydrogen atom of the diamine residue based on the diamine exemplified above is an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, and a hydroxyl group. An amino group, a sulfonic acid group, a sulfonic acid amide group or a sulfonic acid ester group, F, Cl, Br, I or the like may be substituted with 1 to 4 groups.

(Acid residue)
In the general formula (1), R ² represents a tri- or tetra-carboxylic acid residue (hereinafter referred to as “acid residue”).

Examples of preferred tricarboxylic acids that provide acid residues include trimesic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid and the like.

Examples of preferred tetracarboxylic acids that provide acid residues are pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2. ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3, 4-Dicarboxyphenyl) Hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) Hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (1,1-bis) 2,3-Dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3, 4-Dicarboxyphenyl) Ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4 , 9,10-Aromatic tetracarboxylic acids such as perylenetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1. ] Heptanetetracarboxylic acid, bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2. ] Aliphatic tetracarboxylic acids such as octanetetracarboxylic acid and adamatanetetracarboxylic acid can be mentioned. These acids can be used alone or in combination of two or more.

Further, the tricarboxylic acid and the hydrogen atom of the carboxylic acid residue based on the tetracarboxylic acid exemplified above are substituted with 1 to 4 hydroxyl groups, amino groups, sulfonic acid groups, sulfonic acid amide groups or sulfonic acid ester groups. May be.

From the viewpoint of heat resistance after resist curing and dry etching resistance, the acid residue (R ² ) preferably contains an aromatic ring and / or an aliphatic ring, and has a structure represented by the following general formulas (9) to (11). It is more preferable to include at least one selected from.

In the general formulas (9) to (11), R ^{12 to} R ¹⁶ independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. b ^{5 to} b ⁷ are independently integers of 0 to 2, and b ^{8 to} b ⁹ are integers of 0 to 3.

The most preferred examples of tricarboxylic acids or tetracarboxylic acids that provide acid residues are pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid. , 2, 2', 3,3'-biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid and the like. These acids can be used alone or in combination of two or more.

Further, if necessary, 1,3-bis (p-carboxyphenyl) -1,1,3,3-tetramethyldisiloxane, 1- (p-carboxyphenyl) 3-phthalic acid-1,1,3 , 3-Tetramethyldisiloxane, 1,3-bisphthalic acid-1,1,3,3-tetramethyldisiloxane and other carboxyl compounds having a siloxane bond can also be used. By containing an acid residue derived from a carboxyl compound having a siloxane bond, the adhesiveness to the substrate can be enhanced, and the dry etching resistance can be further enhanced.

The polyimide (A) used in the present invention has an imide group equivalent of 0.0025 mol / g or more from the viewpoint of improving dry etching resistance. It is preferably 0.003 mol / g or more, more preferably 0.0032 mol / g or more. Most preferably, it is 0.0034 mol / g or more.

This imide group equivalent is calculated as follows. The number of imide groups in the structural unit is A (mol), and the molecular weight of the structural unit is B (g).

For A and B, for example, in the case of the following structural units, A = 2 and B = 534, respectively.

Further, in the case of the following structural units, A = 2 and B = 836.

The imide group equivalent A / B is calculated from these A and B.

Further, in the case of a copolymer of 80 mol% of the polyimide structural unit of A = 2 and B = 534 and 20 mol% of the structural unit other than the polyimide of B = 600, the imide group equivalent is (2 × 0.8) /. It is calculated by (534 × 0.8 + 600 × 0.2).

(End sealant)
The polyimide (A) used in the present invention may have a polymer terminal sealed with an end-capping agent such as an acid anhydride, a monocarboxylic acid compound, an acid chloride compound and a monoamine compound. By sealing the end of the polymer, the dissolution rate of the polymer in an alkaline aqueous solution can be adjusted to a preferable range.

Examples of such acid anhydrides include phthalic anhydride, maleic anhydride, nagic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid anhydride, 1,10-anthracenedicarboxylic acid anhydride, 1, Examples thereof include 2-anthracene dicarboxylic acid anhydride and 2,3-anthracene dicarboxylic acid anhydride.

Examples of monocarboxylic acid compounds are 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene. , 1-Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy- 2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 1-carboxyanthracene, 2-carboxyanthracene, 3 -Carboxyanthracene and the like.

Examples of the acid chloride compound include a monoacid chloride compound in which the carboxyl group of the above-mentioned monocarboxylic acid compound is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, and 5-norbornen-. 2,3-Dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7 Only one carboxyl group of dicarboxylic acids such as −dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene is acid chlorided. Examples thereof include the monoacid chloride compound. Alternatively, an active ester compound obtained by reacting these monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide can also be used.

Examples of monoamine compounds include aniline, naphthylamine, aminopyridine, 3-ethynylaniline, 4-ethynylaniline, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-Amino-8-Hydroxyquinoline, 4-Amino-8-Hydroxyquinoline, 1-Hydroxy-8-Aminonaphthalene, 1-Hydroxy-7-Aminonaphthalene, 1-Hydroxy-6-Aminonaphthalene, 1-Hydroxy-5 -Aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2 -Hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8- Aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1- Carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-amino Naphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5 -Aminosalicylic acid, 6-aminosalicylic acid, 3-amino-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid Acid, 4-aminobenzenesulfonic acid, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6 -Aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphth Talen, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto -4-Aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4- Aminothiophenol, 1-aminoanthracene, 2-aminoanthracene, 3-aminoanthracene and the like can be mentioned.

The terminal encapsulants such as these acid anhydrides, monocarboxylic acid compounds, acid chloride compounds and monoamine compounds can be used alone or in combination of two or more, and other end encapsulants may be used in combination.

An example of a particularly preferable polyimide terminal structure in terms of enhancing dry etching resistance is one containing at least one selected from the following general formulas (2), (3), and (4).

R ^18, R ^19, R ²⁰ represents a fused polycyclic aromatic hydrocarbon group of 9-18 carbon atoms, hydrogen atoms on the condensed polycyclic aromatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms It may be replaced with.

Preferred R ¹⁸ includes, but is not limited to, residues of monoamines such as 1-aminoanthracene, 2-aminoanthracene, 3-aminoanthracene, 1-aminopyrene, 2-aminopyrene and 3-aminopyrene.

Preferred R ^19s include 1,10-anthracene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,2-pyrrange carboxylic acid anhydride, and 2,3-pyrene. Residues of acid anhydrides such as, but not limited to, dicarboxylic acid anhydrides, 3,4-pyrenzic acid anhydrides, and the like.

Preferred R ²⁰ 1-carboxymethyl-anthracene, 2-carboxyethyl anthracene, although the residue of a monocarboxylic acid, such as 3-carboxy anthracene without limitation.

The content of the terminal encapsulant such as the acid anhydride, monocarboxylic acid compound, acid chloride compound, and monoamine compound described above is 0.1 to 0.1 of the number of moles of the component monomer constituting the carboxylic acid residue and the amine residue. The range of 60 mol% is preferable, and 5 to 50 mol% is more preferable. Within such a range, it is possible to obtain an etching mask resist composition having an appropriate viscosity of the solution at the time of coating and having excellent film physical characteristics.

The (A) polyimide used in the present invention is a polymerization reaction of tricarboxylic acid, tetracarboxylic acid, or anhydrate or acid chloride thereof, active ester, active amide and diamine, or a corresponding diisocyanate compound, trimethylsilylated diamine. You can get it.

The polyimide (A) used in the present invention preferably has a weight average molecular weight of 5000 to 80000. It is more preferably 1000 to 60000, and most preferably 2000 to 40,000. Within such a range, a composition having high dry etching resistance and excellent resist removal property after etching can be obtained.

Further, the polyimide (A) used in the present invention may be obtained by precipitating in a poor solvent for polyimide such as methanol or water after the completion of polymerization, washing and drying. Precipitation has the advantage of improving the heat resistance of the curing pattern because the esterifying agent, condensing agent, by-products of acid chloride, low molecular weight components and the like used during polymerization can be removed.

<(B) Photoacid generator>
The mask resist composition for etching of the present invention contains (B) a photoacid generator. As a result, it is possible to form a positive pattern in which the exposed portion is removed by the alkaline aqueous solution which is a developer.

Examples of the photoacid generator include quinonediazide compounds and onium salt compounds such as sulfonium salts, phosphonium salts, diazonium salts and iodonium salts. The mask resist composition for etching of the present invention preferably contains a quinone diazide compound, and more preferably contains an onium salt in addition to the quinone diazide compound from the viewpoint of improving dry etching resistance.

The quinone-diazide compound includes a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded and / or sulfone. Examples thereof include amide-bonded compounds. In particular, the o-quinone diazide compound, which is these quinone diazido o-quinone diazide, is preferable.

All the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, but it is preferable that 50 mol% or more of all the functional groups are substituted with quinonediazide. When 50 mol% or more is substituted with quinonediazide, there is an advantage that the solubility of the resin film in the alkaline developer becomes good and a fine pattern having high contrast with the unexposed portion can be obtained. By using such a quinone diazide compound, a resin composition having positive photosensitivity that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, can be obtained. be able to.

Specific examples of the polyhydroxy compound include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl. Examples include sulfid.

Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine.

In the present invention, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption up to the g-line region of a mercury lamp and is suitable for g-line exposure.

In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazido sulfonyl ester compound depending on the wavelength to be exposed. Further, it is also possible to obtain a naphthoquinone diazidosulfonyl ester compound in which a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group are used in combination in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound. Can also be used in combination with.

The molecular weight of the quinonediazide compound is preferably 300 or more, more preferably 350 or more. Further, 1500 or less is preferable, and 1200 or less is more preferable. When the molecular weight is 300 or more, the exposure sensitivity is high, and when it is 1500 or less, there is an advantage that the mechanical properties of the heat-resistant film after the heat treatment are improved.

The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazidosulfonyl chloride with a phenol compound in the presence of triethylamine. As a method for synthesizing a phenol compound, there is a method of reacting an α- (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

The onium salt compound used in the present invention is preferably a compound selected from a sulfonium salt, a phosphonium salt, and a diazonium salt. By using these, the resolution of the pattern is remarkably improved. Further, a sulfonium salt is preferably used from the viewpoint of dry etching resistance. Among the sulfonium salts, those having a structure represented by the general formulas (12) to (14) are more preferably used.

^{R 21 to} R ²³ of the general formulas (12) to (14) may be the same or different, respectively, and represent an organic group having 1 to 20 carbon atoms.

Preferred examples are an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and an aryl group such as a phenyl group and a naphthyl group. And so on. Further, 1 to 4 hydrogen atoms of a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group have 1 to 4 carbon atoms such as an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and 1 carbon atom such as a methoxy group and an ethoxy group. With an alkoxy group of ~ 4, a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group, a hydroxyl group, an amino group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, F, Cl, Br or I, etc. Substituted ones may be used.

R ²⁴ and R ²⁵ represent a single bond, an ether group, a thioether group, a sulfone group, and a ketone group. Z ⁻ indicates an anion moiety selected from R ²⁶ SO ₃ ⁻ , R ²⁶ COO ⁻ , and SbF ₆ ^−. R ²⁶ represents an organic group having 1 to 20 carbon atoms.

Preferred examples are an alkyl group having 1 to 18 carbon atoms such as a dodecyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group and a naphthyl group. Examples thereof include an aryl group such as a group, a 7,7-dimethyl-2-oxobicyclo [2.2.1] heptane-1-methylene group and the like. Further, 1 to 4 hydrogen atoms of a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group have 1 to 4 carbon atoms such as an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and 1 carbon atom such as a methoxy group and an ethoxy group. With an alkoxy group of ~ 4, a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group, a hydroxyl group, an amino group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, F, Cl, Br or I, etc. Substituted ones may be used.

Specific examples of the sulfonium salt represented by the general formula (12) are shown below.

Specific examples of the sulfonium salt represented by the general formula (13) are shown below.

Specific examples of the sulfonium salt represented by the general formula (14) are shown below.

A particularly preferable one from the viewpoint of dry etching resistance is a triarylsulfonium salt represented by the general formula (15).

In the formula, R ²⁷ may be the same or different, and indicates either a hydrogen atom or an organic group having 1 to 20 carbon atoms.

Preferred examples are an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group, and a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group. Examples thereof include a group, a hydroxyl group, an amino group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, F, Cl, Br or I.

R ²⁸ represents an organic group having 1 to 20 carbon atoms. Preferred examples are an alkyl group having 1 to 18 carbon atoms such as a dodecyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group and a naphthyl group. Examples thereof include an aryl group such as a group, a 7,7-dimethyl-2-oxobicyclo [2.2.1] heptane-1-methylene group and the like. Further, 1 to 4 hydrogen atoms of a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group have 1 to 4 carbon atoms such as an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and 1 carbon atom such as a methoxy group and an ethoxy group. With an alkoxy group of ~ 4, a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group, a hydroxyl group, an amino group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, F, Cl, Br or I, etc. Substituted ones may be used.

b ^{10 to} b ¹² each indicate an integer of 0 to 5.

Specific examples of the triarylsulfonium salt represented by the general formula (15) are shown below.

The content of the photoacid generator (B) is preferably 1 part by weight or more, more preferably 3 parts by weight or more, based on 100 parts by weight of the entire resin in the mask resist composition for etching. Further, 50 parts by weight or less is preferable, and 40 parts by weight or less is more preferable. Within this range, there is an advantage that the mechanical properties of the heat-resistant coating after heat treatment are improved.

Further, the mask resist composition for etching of the present invention can also contain the compound having a phenolic hydroxyl group shown above without esterification. By containing such a compound having a phenolic hydroxyl group, the obtained mask resist composition for etching has improved solubility in an alkaline aqueous solution in an exposed portion. Further, in the unexposed portion, the naphthoquinone diazide compound and the compound having a phenolic hydroxyl group form hydrogen bonds, so that the solubility in an alkaline aqueous solution is lowered. Therefore, high sensitivity can be achieved.

The content of the compound having a phenolic hydroxyl group is preferably 1 to 40 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the entire resin in the mask resist composition for etching. The compound having a phenolic hydroxyl group may contain two or more kinds, and when two or more kinds are contained, the total amount thereof is preferably in the above range.

<(C) Compound represented by general formulas (5) and (6)>
Further, the mask resist composition for etching of the present invention preferably contains at least one of the compounds represented by the following (C) general formulas (5) and (6) from the viewpoint of etching resistance and resist removing property after etching.

In the general formulas (5) and (6), R ³ , R ⁵ and R ⁷ indicate a hydrogen atom or a group of a structure represented by the following general formula (7). 30-100 mol% of R ³ is a group having a structure represented by the following general formula (7). From the viewpoint of dry etching resistance, it is preferably 40 to 90 mol%, more preferably 50 to 80 mol%. Further, ^{30 to 100 mol% of the total amount of R 5} and R ⁷ is the basis of the structure represented by the following general formula (7). From the viewpoint of dry etching resistance, it is preferably 40 to 90 mol%, more preferably 50 to 80 mol%.

R ^{4, R 6} and ^{R 8} represents an organic group having 1 to 6 carbon atoms. X ¹ is a single bond, O, S, NH, SO ₂ , CO, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure in which two or more of them are linked. a ¹ , a ² , a ³ , b ¹ , b ² and b ³ indicate integers of 1 or more, d ¹ , d ² and d ³ indicate integers of 0 or more, and a ¹ + b ¹ + d ¹ ≤ 6, a ² + B ² + d ² ≤ 5 and a ³ + b ³ + d ³ ≤ 5.

In the general formula (7), R ⁹ represents a divalent organic group having 1 to 6 carbon atoms. Preferred examples are an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group, and a group in which they are linked via an ether, a thioether, an amide or an ester, a trifluoromethyl group and the like. Examples thereof include 1 to 6 fluoroalkyl groups, groups in which they are linked via ethers, thioethers, amides and esters, cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and phenyl groups.

R ¹⁰ and R ¹¹ represent organic groups having 1 to 8 carbon atoms. Preferred examples are an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group and a propyl group, a fluoroalkyl group having 1 to 8 carbon atoms such as a trifluoromethyl group, and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Groups, phenyl groups, methoxyphenyl groups and the like can be mentioned.

a ⁴ indicates an integer of 1 or more, b ⁴ indicates an integer of 0 or more, and a ⁴ + b ⁴ = 3.

Specific examples of preferred (5) and (6) include, but are not limited to, those having the structures shown below.

(C) The content of the compounds represented by the general formulas (5) and (6) is preferably 1 part by weight or more, more preferably 3 parts by weight or more, based on 100 parts by weight of the entire resin in the mask resist composition for etching. .. Further, 20 parts by weight or less is preferable, and 10 parts by weight or less is more preferable. Within this range, there is an advantage that the mechanical properties of the heat-resistant coating after heat treatment are improved.

<Other resins>
The mask resist composition for etching of the present invention may contain an alkali-soluble resin other than polyimide. Specifically, acrylic polymers copolymerized with acrylic acid, phenol resins, siloxane resins, polyhydroxystyrenes, resins in which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups are introduced, and copolymerized polymers thereof. And so on.

From the viewpoint of dry etching resistance, it is preferable to contain at least one selected from (D) phenol resin and polyhydroxystyrene. The phenol resin and polyhydroxystyrene referred to here include a resin in which a cross-linking group such as a methylol group, an alkoxymethyl group or an epoxy group is introduced therein. It also contains a copolymerized polymer of phenolic resin and polyhydroxystyrene.

Such resins are soluble in alkaline aqueous solutions such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide and sodium carbonate. By containing these alkali-soluble resins, the characteristics of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the heat-resistant film.

Preferred phenolic resins include novolak resins and resol resins, which can be obtained by polycondensing various phenols alone or a mixture of a plurality of them with an aldehyde such as formalin.

Examples of the phenols constituting the novolak resin and the resol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2, 4-dimethylphenol, 2, 5-dimethylphenol, and 2 , 6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4 , 5-trimethylphenol, methylenebisphenol, methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α Examples include −naphthol, β-naphthol, etc., which can be used alone or as a mixture of multiples.

In addition to formalin, examples of the aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, which can be used alone or as a mixture of a plurality.

Further, the phenol resin used in the present invention contains 1 to 4 hydrogen atoms added to the aromatic ring as an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group and a cyano group. It may have a structure substituted with a fluorine atom or a chlorine atom.

The weight average molecular weight of the phenol resin used in the present invention may be in the range of 2,000 to 50,000, preferably 3,000 to 30,000 in terms of polystyrene using gel permeation chromatography (GPC). preferable. When the molecular weight is 2,000 or more, the pattern shape, resolution, developability, and heat resistance are excellent, and when the molecular weight is 50,000 or less, sufficient sensitivity can be maintained.

Preferred polyhydroxystyrenes include aromatics having phenolic hydroxyl groups such as, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol. Polymers or copolymers obtained by polymerizing a vinyl compound alone or by polymerizing two or more kinds by a known method, and aromatic vinyls such as styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. A polymer or copolymer obtained by subjecting a part of a polymer or copolymer obtained by polymerizing a compound alone or two or more kinds by a known method to an alkoxy group by a known method. Coalescence is mentioned.

Further, the polyhydroxystyrene used in the present invention contains 1 to 4 hydrogen atoms added to the aromatic ring as an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group and a cyano group. , A structure substituted with a fluorine atom or a chlorine atom, or the like.

The weight average molecular weight of the polyhydroxystyrene used in the present invention is preferably in the range of 3,000 to 60,000 in terms of polystyrene by using gel permeation chromatography (GPC), and is 3,000 to 25,000. It is more preferable that the range is. When the molecular weight is 3,000 or more, the pattern shape, resolution, developability, and heat resistance are excellent, and when the molecular weight is 60,000 or less, sufficient sensitivity can be maintained.

The content of these phenol resins and polyhydroxystyrenes in the etching mask resist composition is preferably 5 to 50 parts by weight, preferably 10 to 40 parts by weight, out of 100 parts by weight of the entire resin in the etching mask resist composition. It is more preferable that it is a portion. When it is 50 parts by weight or less, the heat resistance and strength of the heat-resistant film after the heat treatment can be maintained, and when it is 10 parts by weight or more, the pattern forming property of the resin film is further improved.

<Other ingredients>
The mask resist composition for etching of the present invention may contain a silane coupling agent, if necessary. By containing the silane coupling agent, the adhesion to the underlying substrate can be enhanced when the cured film is formed.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glyce. Sidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, Examples thereof include silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-isocyanuspropyltriethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, and 4-ethoxyphenyltrimethoxysilane. Two or more of these may be contained.

The content of the silane coupling agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the entire resin in the mask resist composition for etching.
It is more preferably 0.2 to 5 parts by weight, still more preferably 0.3 to 3 parts by weight.

The mask resist composition for etching of the present invention may contain a solvent. Examples of the solvent include polar aprotonic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether and the like. Examples include ethers, acetone, methyl ethyl ketone, diisobutyl ketone, ketones such as diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

The content of the solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 5000 parts by weight or less, based on 100 parts by weight of the entire resin in the mask resist composition for etching. It is preferably 3000 parts by weight or less.

The mask resist composition for etching of the present invention may contain a surfactant. By containing a surfactant, uneven coating is improved and a uniform coating film can be obtained. Fluorine-based surfactants and silicone-based surfactants are preferably used.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1) , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorodecan, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctane sulfonamide) propyl] -N, N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis phosphate (N-perfluorooctylsulfonyl-N-ethylaminoethyl) , Monoperfluoroalkyl ethyl Phosphate, etc. Examples thereof include a fluorine-based surfactant consisting of a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain.

Commercially available products include Megafuck F142D, F172, F173, F183, F444, F477 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), Ftop EF301, 303, and 352 (Shin-Akita). Kasei Co., Ltd.), Florard FC-430, FC-431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218, DFX-18 ( There are fluorine-based surfactants such as (manufactured by Neos Co., Ltd.).

Examples of commercially available silicone-based surfactants include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), and the like. Be done.

The content of the surfactant is generally 0.0001 to 1% by weight in the mask resist composition for etching.

The mask resist composition for etching of the present invention may contain a compound having absorption in an ultraviolet region used as an exposure wavelength and not fading by the light. By containing such a compound, when the obtained positive photosensitive resin composition is exposed to form a pattern, the exposure wavelength emitted from the photofinishing machine is absorbed, so that the excess due to the reflected light from the substrate is excessive. It is possible to prevent exposure and diffraction, and to improve the adhesiveness of the unexposed portion during development.

Examples of the compound having the above-mentioned absorption characteristics include a coumarin derivative, a benzotriazole derivative, a hydroxybenzophenone derivative, an anthraquinone derivative, an acenaften derivative and the like. Qumarin derivatives include coumarin, coumarin-4 (trade name, manufactured by Sigma Aldrich Japan Co., Ltd.), 4-hydroxycoumarin, 7-hydroxycoumarin (above, manufactured by Tokyo Kasei Kogyo Co., Ltd.), and benzotriazole derivatives. , Sumisorb 200, Sumisorb 250, Sumisorb 320, Sumisorb 340, Sumisorb 350 (trade name, manufactured by Sumitomo Chemical Industry Co., Ltd.), and as hydroxybenzophenone derivatives, Sumisorb 130, Sumisorb 140 (above product name, Sumitomo Chemical Industry Co., Ltd.) (Manufactured by Co., Ltd.), Dislyzer M, Dislyzer O (trade name, manufactured by Sankyo Kasei Co., Ltd.), Seesorb 103 (manufactured by Cipro Kasei Co., Ltd.), as anthraquinone derivatives, 1-hydroxyanthraquinone, 2-hydroxyanthraquinone, 3 -Hydroxyanthraquinone, 1-hydroxy-2-methoxyanthraquinone, 1,2-dihydroxyanthraquinone, 1,3-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1,8-dihydroxyanthraquinone, 1, 3-Dihydroxy-3-methylanthraquinone, 1,5-dihydroxy-3-methylanthraquinone, 1,6-dihydroxy-3-methylanthraquinone, 1,7-dihydroxy-3-methylanthraquinone, 1,8-dihydroxy-3- Methylanthraquinone, 1,8-dihydroxy-2-methylanthraquinone, 1,3-dihydroxy-2-methoxyanthraquinone, 2,4-dihydroxy-1-methoxyanthraquinone, 2,5-dihydroxy-1-methoxyanthraquinone, 2,8 -Dihydroxy-1-methoxyanthraquinone, 1,8-dihydroxy-3-methoxy-6-methylanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,3,5-trihydroxyanthraquinone, 2-aminoanthraquinone, 2- Amino-1-nitroanthraquinone, 2,6-diaminoanthraquinone, 1-methoxyanthraquinone, 2-methoxyanthraquinone, 1,8-dimethoxyanthraquinone, 1-acetylaminoanthraquinone, 2-acetylaminoanthraquinone, 2-tert-butyl anthraquinone, Examples of the anthraquinone compound include 5-nitroacenaphthene and the like.

Further, the etching mask resist composition of the present invention is added with a cross-linking agent, a cross-linking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a stabilizer, an antifoaming agent and the like, if necessary. It can also contain an agent.

<Manufacturing method of mask resist composition for etching>
The method for producing the mask resist composition for etching of the present invention will be described. Resin components such as polyimide and phenolic resin, photoacid generators, and other additives are added to the solvent to dissolve them. The order is preferably to dissolve the resin component and then the other components. The melting temperature is −5 to 60 ° C., preferably 10 to 50 ° C., more preferably 20 to 40 ° C. If necessary, add solvent to dilute and adjust the viscosity of the composition. Then, the mixture is allowed to stand at room temperature for 1 to 24 hours to defoam, and then filtered through a filter having a pore size of 0.1 to 10 μm to remove foreign substances.

<Manufacturing method of patterned substrate>
The method for producing a patterned substrate using the etching mask resist composition of the present invention includes a step of providing a coating film of the above-mentioned etching mask resist composition, a step of forming a curing pattern of the coating film, and a step of forming the coating film. It has a step of patterning a substrate by etching using a curing pattern as a mask, and a step of removing the curing pattern of the coating film.

First, the mask resist composition for etching of the present invention is applied onto a substrate by a known method such as a spin coating method or a slit coating method.

The substrate may be a substrate containing at least one element selected from the group consisting of aluminum, silicon, titanium, tantalum, gallium, germanium, iron, nickel, zinc, indium, boron, manganese, phosphorus, cobalt and zirconium, or those. A substrate formed on the coated surface or the like is used, but the present invention is not limited thereto. Among these, sapphire (Al ₂ O ₃ ), silicon (Si), silicon oxide (SiO ₂ ), silicon nitride (SiN), gallium nitride (GaN), silicon carbide (SiC), gallium arsenide (GaAs), phosphorus. A group consisting of indium carbide (InP), aluminum nitride (AlN), tantalum nitride (TaN), lithium tantalate (LiTaO ₃ ), boron nitride (BN), titanium nitride (TiN), and barium titanate (BaTIO _3). The substrate selected from the above is preferable.

As a coating method, there are methods such as rotary coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the film thickness after drying is 0.1 to 150 μm.

The substrate can also be pretreated with the above-mentioned silane coupling agent in order to enhance the adhesiveness between the substrate such as a silicon wafer and the mask resist composition for etching. For example, a solution in which a silane coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by weight is prepared. Surface treatment by spin coating, dipping, spray coating, steam treatment, etc. In some cases, heat treatment is then performed at 50 ° C to 300 ° C to allow the reaction between the substrate and the silane coupling agent to proceed.

Next, the substrate coated with the mask resist composition for etching is dried to obtain a resin composition film. Drying is preferably carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like.

Next, the film of the mask resist composition for etching is irradiated with chemical rays through a mask having a desired pattern and exposed. Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, light having a wavelength of 350 nm or more and 450 nm or less is preferable, and i-line (wavelength 365 nm) and h-line (wavelength 405 nm) of a mercury lamp are preferable. ), G-ray (wavelength 436 nm) is preferably used.

To form the pattern of the mask resist composition film for etching, the exposed portion is removed using a developing solution after the exposure. As the developing solution, an alkaline developing solution is preferable, and tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, An aqueous solution of an alkaline compound such as dimethylaminoethanol, dimethylaminoethylmethacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable. In some cases, these alkaline aqueous solutions may be mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination. good. After development, it is preferable to rinse with water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.

A cured pattern can be obtained by curing the obtained mask resist composition coating pattern for etching. For example, a curing pattern is formed by curing in a heating device such as a hot plate or an oven at 100 to 450 ° C. for about 30 seconds to 2 hours. It is preferably 120 ° C to 250 ° C, more preferably 180 to 230 ° C.

The cross-sectional shape of the curing pattern is preferably curved rather than rectangular, and particularly preferably semicircular. The semicircular shape increases light scattering and improves the light extraction efficiency of the light emitting element.

The term "semicircle" as used herein means a state in which the height of the pattern in the cross-sectional shape is equal to or less than the length of the base of the pattern, and the cross-sectional shape is formed by a curve of convex protrusions.

By performing an etching process using the cured pattern formed by the mask resist composition for etching of the present invention as a mask, a desired uneven pattern can be provided on the substrate.

Etching methods include wet etching with a solution and dry etching with a gas, but dry etching is preferably used from the viewpoint of in-plane uniformity of the obtained uneven pattern.

Regarding the gas used for the dry etching process, boron trichloride (BCl ₃ ), chlorine (Cl ₂ ), carbon tetrafluoride (CF ₄ ), methane trifluoride (CHF ₃ ), 4- (difluoromethylene) -2, 3 , 3-Trifluoro-1- (trifluoromethyl) cyclobutene (C ₆ F ₈ ), hexafluoroantimon (SbF ₆ ), oxygen (O ₂ ), argon (Ar), etc. are used, but the etching stability of the substrate is stable. From the viewpoint of sex, it is preferable to use chlorine or boron trichloride.

Further, in order to increase the dry etching rate of the substrate, the temperature at the time of dry etching is preferably 100 ° C to 250 ° C, more preferably 120 ° C to 230 ° C, and most preferably 150 ° C to 200 ° C. preferable.

The cross-sectional shape of the uneven pattern of the substrate after etching is preferably curved rather than rectangular, and particularly preferably semicircular. The semicircular shape increases light scattering and improves the light extraction efficiency of the light emitting element.

The term "semicircle" as used herein means a state in which the height of the pattern in the cross-sectional shape is equal to or less than the length of the base of the pattern, and the cross-sectional shape is formed by a curve of convex protrusions.

In particular, it is preferable that the cross-sectional shape of the curing pattern serving as a mask is semi-circular, so that the cross-sectional shape of the uneven pattern of the substrate after etching can also be semi-circular.

The curing pattern formed by the mask resist composition for etching of the present invention and the resist residue after the dry etching treatment are removed after the dry etching using a resist stripping solution.

As a removing method, it is preferable to immerse the resist stripping solution in a resist stripping solution at room temperature to 100 ° C. for 5 seconds to 24 hours by a method such as shower, dip, or paddle.

As the resist stripping solution, a known resist stripping solution can be used, and specific examples thereof include a stripping solution 104, a stripping solution 105, a stripping solution 106, and SST-3 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). , EKC-265, EKC-270, EKC-270T (above, trade name, manufactured by DuPont Co., Ltd.), N-300, N-321 (above, trade name, manufactured by Nagase ChemteX Corporation) and the like. ..

After removal, it is preferable to rinse with water or an organic solvent, and if necessary, a drying bake can be performed in the range of 50 ° C. to 150 ° C. with a heating device such as a hot plate or an oven.

<Manufacturing method of light emitting element (diode)>
A light emitting diode can be manufactured by forming a light emitting layer on an uneven surface of a substrate on which an uneven pattern processed by using the mask resist composition for etching of the present invention is formed.

As the light emitting layer, at least one layer selected from the group consisting of a buffer layer made of GaN or AlN, an n-type GaN layer, an InGaN light emitting layer or a clad layer made of p-type AlGaN, and a p-type GaN contact layer is given as a preferable example. Be done.

For example, the processed sapphire substrate is mounted on an organometallic vapor layer growth apparatus (MOCVD apparatus, Metalorganic Chemical Vapar Deposition), and is subjected to thermal cleaning at a high temperature of 1000 ° C. or higher under a nitrogen gas main component atmosphere, and a GaN low temperature buffer is performed. The layer, the n-GaN layer, the InGaN layer, the p-AlGaN layer, and the p-GaN layer are grown in this order. After that, n-GaN is exposed by etching to form electrodes on the n-GaN layer and the p-GaN layer, respectively. The substrate on which the electrodes are formed can be made into an LED light emitting element by separating the elements by dicing.

The resin composition of the present invention is also suitably used as a photoresist for dry etching for the purpose of exposing the above-mentioned n-GaN layer.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Of the compounds used, those using abbreviations are shown below.

NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone Each evaluation was performed by the following method.

(1) Calculation of imide group equivalent The imide group equivalent is calculated as follows. The number of imide groups in the structural unit is A (mol), and the molecular weight of the structural unit is B (g).

For A and B, for example, in the case of the following structural units, A = 2 and B = 534, respectively.

Further, in the case of the following structural units, A = 2 and B = 836.

The imide group equivalent is a value represented by A / B.

(2) Weight average molecular weight Using a GPC (gel permeation chromatography) device Waters2690-996 (manufactured by Japan Waters Corp.), the developing solvent was measured as N-methyl-2-pyrrolidone, and the weight average molecular weight (polystyrene equivalent). Mw) was calculated.

(3) Film thickness of resist film after pre-baking, resist curing pattern film, and curing pattern film before and after dry etching Refractive index using an optical interference type film thickness meter (Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.) It was measured at 1.629.

(4) Photosensitivity Sensitivity The etching mask resist composition is spin-coated on a single crystal sapphire wafer having a diameter of 2 inches using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation speed, and then a hot plate (AS ONE) is used. HP-1SA manufactured by Co., Ltd.) was used for prebaking at 120 ° C. for 3 minutes to prepare an etching mask resist composition film having a film thickness of 3.0 μm.

The composition film produced by using the i-line stepper (Nikon Corporation Ltd. NSR-2009i9C), exposed with 20 mJ / cm ² steps by the exposure amount of 0~500mJ / cm ^2. The reticle used for the exposure was a line and space pattern having a line and space pattern of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, and 100 μm.

After the exposure, the shower was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), and then rinsed with water for 30 seconds. The exposure amount at which a 3 μm line-and-space pattern opens after pattern development was defined as the photosensitive sensitivity.

(5) Shape of curing pattern after curing (4) Development is performed by the same method, and this substrate is cured using a hot plate (HP-1SA manufactured by AS ONE Co., Ltd.) at a predetermined temperature and time to form a curing pattern. Was done. The cross section of the line pattern of 3 μm at the exposure amount of photosensitive sensitivity + 20 mJ / cm ² was observed by SEM, and if the cross section was semicircular, it was considered good, otherwise it was considered defective.

(6) Dry etching resistance The curing pattern is formed by the same method as in (5), and this patterned sapphire substrate is subjected to a dry etching apparatus (RIE-200NL-101iPH manufactured by SAMCO Co., Ltd.) under a predetermined temperature. Etched with boron trichloride.

When the film thickness of the curing pattern before and after dry etching is T ₁ and T ₂ , respectively, and the depth of the sapphire substrate etched by dry etching is T ₃ , the etching selection ratio, (T _1- T ₂ ) / T ₃ is set. It was calculated, and the higher the selection ratio, the higher the resistance.

(7) Removability of cured pattern after dry etching The cured pattern after dry etching is immersed in a stripping solution 106 (manufactured by Tokyo Oka Kogyo Co., Ltd., monoethanolamine: dimethylsulfoxide = 70:30) at room temperature, and then with water. Rinsing was performed for 30 seconds. Then, using an optical microscope (OPTISHOT300 manufactured by Nikon Corporation), observe the presence or absence of residual etching mask resist composition coating pattern on the substrate, and the shorter the minimum immersion time required to remove the pattern, the better. It was easy to remove.

(Synthesis Example 1) Synthesis of Polyimide (PI-01) 15.9 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) under a dry nitrogen stream. 0.043 mol), 0.62 g (0.0025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) was dissolved in 130 g of NMP. To this, 15.5 g (0.05 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA manufactured by Manac Inc.) was added together with 50 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. .. Then, 1.09 g (0.01 mol) of 3-aminophenol (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 2 hours. Further, stirring was continued at 200 ° C. for 6 hours. After the stirring was completed, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. Further, the mixture was washed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain polyimide (PI-01). The imide group equivalent of PI-01 was 0.0032 mol / g and the weight average molecular weight was 40,000.

(Synthesis Example 2) Synthesis of Polyimide (PI-02) Instead of 15.5 g (0.05 mol) of ODPA, 2,2', 3,3'-biphenyltetracarboxylic dianhydride (manufactured by Torefine Chemical Co., Ltd., Polyimide (PI-02) was obtained in the same manner as in Synthesis Example 1 except that 14.7 g (0.05 mol) of i-BPDA) was added. The imide group equivalent of PI-02 was 0.0033 mol / g and the weight average molecular weight was 35,000.

(Synthesis Example 3) Synthesis of Polyimide (PI-03) 10.9 g (0.05 mol) of pyromellitic anhydride (PMDA manufactured by Daicel Chemical Co., Ltd.) was added instead of 15.5 g (0.05 mol) of ODPA. Polyimide (PI-03) was obtained in the same manner as in Synthesis Example 1 except for the above. The imide group equivalent of PI-03 was 0.0037 mol / g, and the weight average molecular weight was 50,000.

(Synthesis Example 4) Synthesis of Polyimide (PI-04) Instead of 15.5 g (0.05 mol) of ODPA, 1,2,5,6-naphthalenetetracarboxylic dianhydride (manufactured by Tokyo Kasei Co., Ltd.) 13. Polyimide (PI-04) was obtained in the same manner as in Synthesis Example 1 except that 4 g (0.05 mol) was added. The imide group equivalent of PI-04 was 0.0034 mol / g, and the weight average molecular weight was 40,000.

(Synthesis Example 5) Synthesis of Polyimide (PI-05) Instead of 15.5 g (0.05 mol) of ODPA, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (Tokyo) Polyimide (PI-05) was obtained in the same manner as in Synthesis Example 1 except that 26.0 g (0.05 mol) (manufactured by Kasei Co., Ltd.) was added. The imide group equivalent of PI-05 was 0.0024 mol / g and the weight average molecular weight was 45,000.

(Synthesis Example 6) Synthesis of polyimide (PI-06) BAHF 17.4 g (0.047 mol), 3 instead of BAHF 15.9 g (0.043 mol) and 3-aminophenol 1.09 g (0.01 mol). A polyimide (PI-06) was obtained in the same manner as in Synthesis Example 1 except that 0.109 g (0.001 mol) of -aminophenol was added. The imide group equivalent of PI-06 was 0.0032 mol / g, and the weight average molecular weight was 90000.

(Synthesis Example 7) Synthesis of polyimide (PI-07) BAHF 11.1 g (0.03 mol), 3 instead of BAHF 15.9 g (0.043 mol) and 3-aminophenol 1.09 g (0.01 mol). -Polymeride (PI-07) was obtained in the same manner as in Synthesis Example 1 except that 3.82 g (0.035 mol) of aminophenol was added. The imide group equivalent of PI-07 was 0.0033 mol / g and the weight average molecular weight was 4000.

(Synthesis Example) 8 Synthesis of Polyimide (PI-08) Synthesis Example 1 except that 1.93 g (0.01 mol) of 2-aminoanthracene was added instead of 1.09 g (0.01 mol) of 3-aminophenol. Polyimide (PI-08) was obtained in the same manner as above. The imide group equivalent of PI-08 was 0.0032 mol / g and the weight average molecular weight was 41000.

(Synthesis Example 9) Synthesis of Polyimide (PI-09) 1.93 g (0.01 mol) of 2-aminoanthracene instead of 1.09 g (0.01 mol) of 3-aminophenol and 15.5 g (0.05 mol) of ODPA. (Mole), 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride (i-BPDA manufactured by Torefine Chemical Co., Ltd.) 14.7 g (0.05 mol) was added, but it was the same as Synthesis Example 1. Polyimide (PI-09) was obtained in the same manner. The imide group equivalent of PI-09 was 0.0033 mol / g and the weight average molecular weight was 37,000.

(Synthesis Example 10) Synthesis of polyimide precursor (PAE-01) 15.9 g (0.043 mol) of BAHF and 0.62 g (0.0025 mol) of SiDA were dissolved in 200 g of NMP under a dry nitrogen air flow. To this, 15.5 g (0.05 mol) of ODPA was added together with 50 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. Then, 1.09 g (0.01 mol) of 3-aminophenol was added, and the mixture was stirred at 40 ° C. for 2 hours. Further, a solution of 3.57 g (0.03 mol) of dimethylformamide dimethylacetal (DFA manufactured by Mitsubishi Rayon Co., Ltd.) diluted with 5 g of NMP was added dropwise over 10 minutes, and after the addition, the solution was added dropwise at 40 ° C. for 2 hours. Stirring was continued at 100 ° C. for 0.5 hours. After the stirring was completed, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. Further, the mixture was washed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor (PAE-01). The weight average molecular weight of this polyimide precursor was 42000.

(Synthesis Example 11) Synthesis of hydroxyl group-containing diamine compound (DA-01) 18.3 g (0.05 mol) of BAHF was added to 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Kasei Co., Ltd.). It was dissolved and cooled to −15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of the dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

30 g of the obtained white solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of methyl cell solve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (DA-01) represented by the following formula.

(Synthesis Example 12) Synthesis of Polyimide Precursor (PAE-02) 25.7 g (0.043 mol), SiDA 0.62 g of the hydroxyl group-containing diamine compound (DA-01) obtained in Synthesis Example 11 under a dry nitrogen air flow. (0.0025 mol) was dissolved in 200 g of NMP. To this, 15.5 g (0.05 mol) of ODPA was added together with 50 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. Then, 1.17 g (0.01 mol) of 4-ethynylaniline (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 2 hours. Further, a solution of 3.57 g (0.03 mol) of DFA diluted with 5 g of NMP was added dropwise over 10 minutes, and after the addition, stirring was continued at 40 ° C. for 2 hours. After the stirring was completed, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. Further, the mixture was washed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor (PAE-02). The weight average molecular weight of this polyimide precursor was 45,000.

(Synthesis Example 13) Synthesis of naphthoquinone diazide compound (QD-01) 21.23 g (0.05 mol) and 4-naphthoquinone diazidosulfonyl acid of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) under a dry nitrogen stream. 37.62 g (0.14 mol) of chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not rise above 35 ° C. After the dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-01) having the following structure.

(Synthesis Example 14) Synthesis of novolak resin (NV-01) Under a dry nitrogen stream, 57 g (0.6 mol) of metacresol, 38 g (0.4 mol) of paracresol, and 75.5 g of 37 wt% formaldehyde aqueous solution (formaldehyde 0). .93 mol), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methylisobutylketone were charged, and then the polycondensation reaction was carried out for 4 hours while immersing the reaction solution in an oil bath and refluxing the reaction solution. rice field. Then, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is reduced to 30 to 50 mmHg to remove volatiles, and the dissolved resin is cooled to room temperature to make it alkaline. 85 g of a soluble polymer solid of novolak resin (NV-01) was obtained.

(Example 1)
10 g (100 parts by weight) of the polyimide (PI-01) obtained in Synthesis Example 1, 2.0 g (20 parts by weight) of the naphthoquinone diazide compound (QD-01) obtained in Synthesis Example 9, and GBL as a solvent 41. After mixing and stirring 3 g, a mask resist composition for etching was prepared by filtering with a filter of 0.5 μm. This composition was evaluated by the evaluation methods (1) to (7) above. The curing conditions (resist curing conditions) for forming the curing pattern were 160 ° C. for 5 minutes, and the temperature during dry etching was 150 ° C. The results are shown in Table 1.

(Examples 2 to 20, Comparative Examples 1 to 4)
The etching mask resist composition was prepared and evaluated in the same manner as in Example 1. Table 1 shows the composition, resist curing conditions, temperature during dry etching, and each evaluation result. The compounds PAG-01 and PHH-01 in Table 1 have the following structures, respectively.

Claims (16)

(A) A polyimide containing a structural unit represented by the general formula (1) as a main component, (B) a photoacid generator, and (C) at least one selected from the general formulas (5) and (6). A composition comprising the mask resist composition for etching, wherein the imide group equivalent of the polyimide (A) is 0.0025 mol / g or more.

(In the general formula (1), R ¹ represents a divalent organic group ^{having 2 to 50 carbon atoms, R 2} represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms, and m ¹ represents 0 or 1 integer, ^{c 1} is an integer of 0 or ^1, and ^c 1 = 0 when ^c 1 = ^{1, m} 1 = 1 when ^m 1 = 0.)

(In the general formulas (5) and (6), R ³ , R ⁵ , and R ⁷ represent hydrogen, at least one organic group selected from the structure represented by the following general formula (7), of which 30 mol% or more. Is a structure represented by the following general formula (7). R ⁴ , R ⁶ , and R ⁸ represent organic groups having 1 to 6 carbon atoms. X ¹ is a single bond, O, S, NH, SO--. _2. CO or a divalent organic group having 1 to 3 carbon atoms or a divalent crosslinked structure in which two or more of them are linked. A ¹ , a ² , a ³ , b ¹ , b ² , b ³ are An integer of 1 or more, d ¹ , d ² , d ³ indicates an integer of 0 or more, and a ¹ + b ¹ + d ¹ ≤ 6, a ² + b ² + d ² ≤ 5, a ³ + b ³ + d ³ ≤ 5. )

(In the general formula (7), R ⁹ represents a divalent organic group having 1 to 6 carbon atoms. R ¹⁰ and R ¹¹ represent an organic group having 1 to 8 carbon atoms. A ⁴ is an integer of 1 or more. b ⁴ indicates an integer of 0 or more, and a ⁴ + b ⁴ = 3). The mask resist composition for etching according to claim 1, wherein the polyimide (A) has a weight average molecular weight of 5000 to 80000. The mask resist composition for etching according to claim 1 or 2, wherein the terminal skeleton of the polyimide (A) contains at least one selected from the following general formulas (2), (3), and (4).

^{(R 18, R 19, R} 20 represents a fused polycyclic aromatic hydrocarbon group of 9-18 carbon atoms, hydrogen atoms on the condensed polycyclic aromatic hydrocarbon groups, an alkyl having 1 to 4 carbon atoms It may be substituted with a group.) (B) The mask resist composition for etching according to any one of claims 1 to 3, wherein the photoacid generator contains a quinodiazide compound and an onium salt. The mask resist composition for etching according to any one of claims 1 to 4, further comprising (D) at least one selected from a phenol resin and polyhydroxystyrene. The mask resist composition for etching according to any one of claims 1 to 5, ^{wherein R 1} in the general formula (1) is composed of the following general formula (8).
(R ¹⁷ is a single _bond, C _{(CF 3)} shows a _{2, C (CH 3) 2} , SO 2, O, S, an organic group represented by at least one selected from CH _2.)

^{The mask resist for etching according to any one of claims 1 to 6, wherein R 2} is represented by at least one selected from the following general formulas (9) to (11) in the general formula (1). Composition.

(In the general formulas (9) to (11), R ^{12 to} R ¹⁶ independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. B ^{5 , b 6} and b ⁷ are 0 to 2. The integers of, b ⁸ and b ⁹ are integers of 0 to 3.) The step of providing a film of the mask resist composition for etching according to any one of claims 1 to 7.
The step of forming the curing pattern of the film,
A process of patterning a substrate by etching using the cured pattern of the coating as a mask.
A method for manufacturing a patterned substrate, which comprises a step of removing the cured pattern of the coating film. The substrate according to claim 8, wherein the substrate contains at least one element selected from the group consisting of aluminum, silicon, titanium, tantalum, gallium, germanium, iron, nickel, zinc, indium, boron, manganese, phosphorus, cobalt and zirconium. Manufacturing method. The substrate is sapphire (Al ₂ O ₃ ), silicon (Si), silicon oxide (SiO ₂ ), silicon nitride (SiN), gallium nitride (GaN), silicon carbide (SiC), gallium arsenide (GaAs), indium phosphate. Selected from the group consisting of (InP), aluminum nitride (AlN), tantalum nitride (TaN), lithium tantalum (LiTaO ₃ ), boron nitride (BN), titanium nitride (TiN), and barium titanate (BaTIO _3). The method for manufacturing a substrate according to claim 9. The method for manufacturing a substrate according to any one of claims 8 to 10, wherein the step of pattern processing the film of the resin composition includes a step of pattern exposure using light having a wavelength of 350 nm or more and 450 nm or less, and a step of developing. The method for manufacturing a substrate according to any one of claims 8 to 11, wherein the cross-sectional shape of the coating pattern of the resin composition is semicircular. The method for manufacturing a substrate according to any one of claims 8 to 12, wherein the etching is dry etching. The method for manufacturing a substrate according to claim 13, wherein the etching gas contains at least one selected from chlorine and boron trichloride. The method for manufacturing a substrate according to claim 13 or 14, wherein the temperature at the time of dry etching is 100 ° C to 250 ° C. A group consisting of a buffer layer made of GaN or AlN, an n-type GaN layer, an InGaN light emitting layer, a p-type AlGaN clad layer, and a p-type GaN contact layer on the substrate obtained by the method according to any one of claims 8 to 15. A method for manufacturing a light emitting device, which comprises a step of forming a film of at least one selected layer.