JP2007297531A - Polyamide resin, photosensitive resin composition using resin and preparation method of semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin which can be used for manufacturing a relief structure with heat-resistance and of forming a membrane with high heat-resistance and a large elongation at break; to provide a photosensitive resin composition using the same; and to provide a manufacturing method of a semiconductor device. <P>SOLUTION: The polyamide resin has a repeating unit wherein an aromatic ring and an aromatic ring are linked with a group having a double bond. The photosensitive resin composition contains the resin. The manufacturing method of a semiconductor device uses the composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyamide resin and a photosensitive resin composition. More specifically, the present invention is suitable for applications in the field of microelectronic technology, and uses a positive photosensitive resin composition that can be developed with an aqueous alkaline solution and the composition. The present invention relates to a method for manufacturing a semiconductor device.

  In the application of microelectronic technology, a polymer exhibiting durability at high temperatures as in Patent Document 1 is generally widely known. Precursors of such polymers such as polyimide and polybenzoxazole (PBO) can be made photoreactive with suitable additives. This precursor is converted to the desired polymer by known techniques such as exposure to high temperatures. Accordingly, polymer precursors have been used to produce protective layers, thermal insulation layers, and highly heat-resistant polymer relief structures.

  A film formed from such a heat-resistant resin composition is desired to have a large elongation at break as well as heat resistance.

JP 2005-250462 A

  Provided are a polyamide resin and a photosensitive resin composition capable of producing a relief structure having heat resistance and capable of forming a film having high heat resistance and high elongation at break, and a method for producing a semiconductor device using the composition .

The above problems have been achieved by the following configuration.
(1) A polyamide resin containing at least one structure represented by the following general formula (1-1) or (1-2).

R ₁ independently represents a hydrogen atom or an alkyl group.
R ₂ and R ₃ each independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
k and l each independently represents 0 or 1.
m and n each independently represents 0, 1 or 2.
(2) It contains at least one of the structure represented by the general formula (1-1) where k = 1 and the structure represented by the general formula (1-2) where l = 0. Polyamide resin as described in said (1).
(3) The photosensitive resin composition containing the polyamide resin as described in said (1) or (2).

(4) A semiconductor device obtained by applying the photosensitive resin composition according to any one of (1) to (3) above on a semiconductor element, prebaking, exposing, developing, and heating. Production method.

  With the polyamide resin and photosensitive resin composition of the present invention, a relief structure having heat resistance can be produced, and a film having high heat resistance and a large elongation at break can be formed, and the heat resistance, mechanical properties, electrical properties, A relief structure excellent in chemical properties can be produced, and can be suitably used for semiconductor applications, particularly as a buffer coat.

[1] Polyamide resin The polyamide resin used in the present invention is, for example, a polybenzoxazole precursor structure, a polyimide structure, a polyimide precursor structure, or a polyamic acid ester structure, and a hydroxyl group, a carboxyl group, Or the resin which has a sulfonic acid group is mentioned, and contains at least 1 sort (s) of the structure represented by the following general formula (1-1) or (1-2).

R ₁ independently represents a hydrogen atom or an alkyl group.
R ₂ and R ₃ each independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
k and l each independently represents 0 or 1.
m and n each independently represents 0, 1 or 2.
Two R ₁ may be the same or different.
Each of R ₂ and R ₃ may be the same or different when a plurality of R ₂ and R ₃ are present.

The alkyl group is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group. , Neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and the like. The cyclic alkyl group may be monocyclic or polycyclic. The monocyclic type is preferably a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cyclic alkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, and a camphanyl group.
As the alkyl group, an alkyl group substituted with a halogen atom (haloalkyl group) is also preferable.
The alkoxy group is preferably a linear or branched alkoxy group having 1 to 15 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t- Examples include butoxy, hexyloxy, heptyloxy, octyloxy, and nonyloxy groups.
The aryl group is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a phenanthryl group, and a pyrenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Although the specific example of the repeating unit of the polyamide resin which is a polyimide precursor is given, it is not limited to these.

  Although the specific example of the repeating unit of the polyamide resin which is a PBO precursor is given, it is not limited to these.

  Although the specific example of the repeating unit of the polyamide resin which is a polyimide precursor and a PBO precursor is given, it is not limited to these.

  The stilbene compound corresponding to the repeating unit can be synthesized, for example, as follows.

  R represents an arbitrary substituent.

The repeating unit having the structure represented by formula (1-1) or (1-2) is generally 5 to 60 mol%, preferably 10 to 55 mol%, based on all repeating units constituting the resin. It is.
The amount of the resin in the photosensitive resin composition is generally 50 to 97% by mass, preferably 60 to 95% by mass, based on the total solid content of the composition.

  A polyamide resin containing a structure represented by the general formula (2) is preferred.

X represents a divalent to tetravalent organic group.
Y represents a divalent to hexavalent organic group.
R ₂ represents a hydroxyl group, a carboxyl group, or —O—R ₄ .
m represents an integer of 0-2.
R ₃ represents a hydroxyl group, a carboxyl group, —O—R ₄ or —COO—R ₄ .
n represents an integer of 0 to 4.
When there are a plurality of each of R ₂ and R ₃ , they may be the same or different.
R ₄ represents an organic group having 1 to 15 carbon atoms.
Z represents a group shown below.

R ₅ and R ₆ independently represent a divalent organic group.
R ₇ and R ₈ independently represent a monovalent organic group.
a is 60 to 100 mol%, b is 0 to 40 mol%, and a + b = 100 mol%.

The polyamide resin including the structure represented by the general formula (2) includes, for example, a diamine, a dicarboxylic acid, and an acid anhydride.
It is sufficient that at least one of X and Y is a group constituting the structure represented by the general formula (1-1) or (1-2).
In the general formula (2), X constitutes a structure represented by the general formula (1-1) (a group obtained by removing -NH- at both ends from the group represented by the general formula (1-1)). Or whether Y is a group constituting the structure represented by the general formula (1-2) (a group represented by the general formula (1-2) and excluding -CO- at both ends). , At least one is sufficient.

X in the polyamide resin including the structure represented by the general formula (2) represents a divalent to tetravalent organic group, R ₂ is a hydroxyl group, O—R ₄ , m is an integer of 0 to 2, and these are It may be the same or different.
Y represents a divalent to hexavalent organic group, R ₃ represents a hydroxyl group, a carboxyl group, O—R ₄ , or COO—R ₄ , and n represents an integer of 0 to _4, which may be the same or different. Here, R ₄ is an organic group having 1 to 15 carbon atoms.
However, at least one of R ₂ and R ₃ has at least one of a hydroxyl group and a carboxyl group.
Moreover, the hydroxyl group as R < ₂ > may be protected by the quinonediazide group like the below-mentioned PBO precursor (F).

  The polyamide resin containing the structure represented by the general formula (2) is, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, etc., and a structure of Z blended as necessary. And a compound selected from tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative having the structure of Y. Is obtained. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

In the polyamide resin containing the structure represented by the general formula _{(2), O-R 4} , COO-R 4 as a substituent of O-R _4, Y as a substituent of X is a hydroxyl group, an alkaline aqueous solution of the carboxyl group Is a group protected with an organic group having 1 to 15 carbon atoms for the purpose of adjusting the solubility in the solvent, and a hydroxyl group and a carboxyl group may be protected as necessary. Examples of R ₄ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.
When this polyamide resin is heated at about 300 to 400 ° C., dehydration ring closure occurs, and a heat resistant resin is obtained in the form of polyimide, polybenzoxazole, or copolymerization of both.

  When X in the general formula (2) is not a group constituting the structure represented by the general formula (1-1), examples include the following groups. Two or more kinds may be used.

In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, Or it is a single bond.
R ₁₃ represents an alkyl group, an alkyl ester group, or a halogen atom. r represents an integer of 0-2. A plurality of R ₁₃ may be the same or different.
R ₁₄ represents a hydrogen atom, an alkyl group, an alkyl ester group, or a halogen atom.

  Among these, the following groups are particularly preferable.

R ₉ represents an alkyl group, an alkyl ester group, or a halogen atom. r represents an integer of 0-2. A plurality of R ₉ may be the same or different.

  In the general formula (2), when Y is not a group constituting the structure represented by the general formula (1-2), examples include the following groups. Two or more kinds may be used.

In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, Or it is a single bond.
R ₁₅ represents an alkyl group or a halogen atom. r represents an integer of 0-2. A plurality of R ₁₅ may be the same or different.

  Among these, the following are particularly preferable.

R ₁₀ represents an alkyl group or a halogen atom. r represents an integer of 0-2. A plurality of R ₁₀ may be the same or different.

  Moreover, it is desirable to seal the terminal from the viewpoint of storage stability. For sealing, a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polyamide represented by the general formula (2). Specifically, a diamine or bis (aminophenol) having a structure of X, a compound selected from 2,4-diaminophenol, a silicone diamine having a structure of Z and a tetracarboxylic having a structure of Y, which are blended as necessary. It is represented by the general formula (2) obtained by reacting with a compound selected from acid anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like. After synthesizing a polyamide resin containing a structure, an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group as the terminal amino group contained in the polyamide resin is used. And capping as an amide. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include the following, It is not limited to these.

  Among these, the following groups are particularly preferable.

  Two or more of these may be used. The method is not limited to this method, and the terminal acid contained in the polyamide resin is capped as an amide using an amine derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. You can also

  Furthermore, Z of the polyamide resin containing the structure represented by the general formula (2) used as necessary includes, for example, the following groups. Two or more kinds may be used.

In particular, as polybenzoxazole precursor (PBO precursor), U.S. Pat. No. 4,371,
In the well-known thing described in the specification of No. 685, Japanese translations of PCT publication No. 2002-52695, etc., it should just have a structure denoted by a general formula (1-1) or (1-2).
For example, the polybenzoxazole precursor polymer (G) which has the following structure can be mentioned.

In the formula, Ar ₁ is a tetravalent aromatic group, an aliphatic group, a heterocyclic group or a mixed group thereof, and Ar ₂ is a divalent aromatic group which may or may not contain silicon in some cases, A heterocyclic group, an alicyclic group or an aliphatic group, and Ar ₃ is a divalent aromatic group, an aliphatic group, a heterocyclic group or a mixture thereof; x represents 5-1000, and y represents 0-900.
At least one of Ar ₁ and Ar ₂ is a group constituting the structure represented by the general formula (1-1), or Ar ₃ constitutes a structure represented by the general formula (1-2). It may be a group or at least one of them.

  The intrinsic viscosity of the PBO precursor is measured at 25 ° C. in a concentration of 0.5 g / dL and NMP, preferably 0.1 to 0.7 dL / g, more preferably 0.12 to 0.6 dL / g.

  The PBO precursor generally has a degree of polymerization of 10 to 1000, and is synthesized by reacting the following monomers (A), (B), and (C) in the presence of a base.

Wherein Ar ₁ , Ar ₂ , Ar ₃ , x and y are as previously defined, W is Cl, OR, or OH, where R is an alkyl or cycloalkyl group, eg, —CH _{3 , -C 2 H 5, n-} C 3 H 7, i-C 3 H 7, n-C 4 H 9, t-C 4 H 9, cyclohexyl, and the like.

  The ratio of [(A) + (B)] / (C) is generally between about 0.9 and 1.1. Monomer (A) is about 10-100 mol% of [(A) + (B)], and monomer (B) is about 0-90 mol% of [(A) + (B)].

  In addition, you may use what made the PBO precursor (F) by which the said polymer (G) was made to react with a diazoquinone, and a part of hydroxyl group was capped with the diazoquinone.

In the formula, Ar ₁ , Ar ₂ and Ar ₃ are as defined above. x represents 5-1000.
y represents 0-900. b represents 0-50.
Examples of Z include the following groups.

  For example, by reacting with about 1 to 35 mol% of diazoquinone, x is 10 to 1000, y is 0 to 900, and b is 0.10 to 350.

In the monomer (A) that is a constituent of the polymers (G) and (F), Ar ₁ is a tetravalent aromatic group, aliphatic group, or heterocyclic group, represented by the general formula (1-1) When it is not a group constituting the structure represented, for example, the following groups can be exemplified.

In the formula, L ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—.
Or, it represents the following group.

Each R ⁰ independently represents an alkyl group or a cycloalkyl group (for example, —CH ₃ , —C ₂ H ₅ , n-C ₃ H ₇ , i-C ₃ H ₇ , n-C ₄ H ₉ , t— C ₄ H ₉ , a cyclohexyl group).

Ar ₁ is not limited to these groups. Furthermore, monomer (A) may be a mixture of two or more monomers.

In monomer (B), which is a constituent of precursor (G) and capped precursor (F), Ar ₂ may or may not contain silicon, a divalent aromatic group, a heterocyclic group, An alicyclic group or an aliphatic group.
When Ar ₂ is not a group constituting the structure represented by the general formula (1-1), the monomer (B) containing Ar ₂ includes, for example, 5 (6) -diamino-1- (4-aminophenyl)- 1,3,3-trimethylindane (DAPI), m-phenylenediamine, p-phenylenediamine, 2,2'-bis (trifluoromethyl) -4,4'-diamino-1,1'-biphenyl, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4-tolylenediamine, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4, 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4 -Diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino-phenoxy) benzene, 1,4-bis (γ-aminopropyl) tetramethyldisiloxane, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, methylenediamine, tetramethylenediamine , Pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethyl Heptamethylenediamine, octamethylenediamine Nonamethylenediamine, 2,5-dimethylnonamethylenediamine, decamethylenediamine, ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine, 1,10-diamino-1,10-dimethyldecane, 2,11-diaminododecane 1,12-diaminooctadecane, 2,17-diaminoeicosane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, bis (4-aminocyclohexyl) methane, 3,3'-diaminodiphenylethane, 4, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,6-diamino-4-trifluoromethylpyridine, 2,5-diamino- 1,3,4-oxadiazole, 1,4-diaminocyclohexane, pipette 4,4'-methylene dianiline, 4,4'-methylene di-bis (o-chloroaniline), 4,4'-methylene-bis (3-methylaniline), 4,4'-methylene-bis ( 2-ethylaniline), 4,4'-methylene-bis (2-methoxyaniline), 4,4'-oxy-dianiline, 4,4'-oxy-bis- (2-methoxyaniline), 4,4 ' -Oxy-bis- (2-chloroaniline), 4,4'-thio-dianiline, 4,4'-thio-bis- (2-methylaniline), 4,4'-thio-bis- (2-methoxy) Aniline), 4,4'-thio-bis- (2-chloroaniline), 3,3'-sulfonyl-dianiline, 3,3'-sulfonyl-dianiline, and mixtures thereof. Is not to be done. However, it should be understood that monomer (B) is not limited thereto.

In the monomer (C) that is a constituent of the PBO precursor (G) and the capped precursor (F), Ar ₃ is a divalent aromatic group, aliphatic group, or heterocyclic group, and has the general formula ( When it is not a group constituting the structure represented by 1-2), the following groups are exemplified.

(In the formula, L ₂ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ — or —N.
HCO-)

Ar ₃ is not limited to these groups. Furthermore, monomer (C) may be a mixture of two or more monomers.

  Examples of the diazoquinone compound to be reacted with the PBO precursor (G) include the following compounds, and a plurality of them may be used.

  Preferred reaction solvents are N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethyl sulfoxide (DMSO), sulfolane, and diglyme. The most preferred solvents are N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). Any conventional reaction can be used to react a dicarboxylic acid or chloride or ester thereof with at least one aromatic and / or heterocyclic dihydroxydiamine, and optionally with at least one diamine. It's okay. Examples of suitable dicarboxylic acids are selected from the group consisting of 4,4'-diphenyl ether dicarboxylic acid, terephthalic acid, isophthalic acid and mixtures thereof. Examples of suitable dihydroxydiamine compounds are 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-dihydroxybenzidine, hexafluoro-2,2-bis-3-amino-4-hydroxyphenylpropane And mixtures thereof. The reaction is generally carried out at about −10 to about 30 ° C. for about 6 to 48 hours. The molar ratio of dicarboxylic acid to (diamine + dihydroxydiamine) is about 0.9 to 1.1: 1.

  A capped PBO precursor can be prepared according to the following reaction.

  (In the formula, Z is as defined above.)

It may is used any method suitable for reacting polybenzoxazole with photoactive moiety Cl-SO ₂ -Z. Generally, the reaction is carried out at about 0 to about 30 ° C. for about 3 to 24 hours in the presence of a base such as pyridine, trialkylamine, methylpyridine, lutidine, n-methylmorpholine and the like. The most preferred base is triethylamine.
The b / x ratio is generally from 0.01 to 0.35, preferably from 0.02 to 0.20.
~ 0.05 is most preferred.

  The addition amount of the PBO precursor is generally 50 to 99 mass with respect to the total solid content of the photosensitive resin composition of the present invention (total amount of components constituting the finally obtained cured product excluding the solvent). %, Preferably 60 to 95% by mass.

[2] Quinonediazide photosensitizer The quinonediazide photosensitizer is not particularly limited, and a known quinonediazide photosensitizer can be used.

  The o-quinonediazide photosensitizer can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent.

  Examples of the o-quinonediazidesulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, and bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the positive photosensitive resin composition of the present invention, the compounding amount of the quinonediazide photosensitizer is based on the difference in dissolution rate between the exposed part and the unexposed part, and the allowable range of sensitivity, with respect to 100 parts by mass of the PBO precursor. 5-100 mass parts is preferable and 8-40 mass parts is more preferable.

  Examples of quinonediazide photosensitizers include compounds having the following structures.

（式中、Ｄは、独立して、Ｈまたは以下の基のいずれかである。）

(Wherein D is independently H or any of the following groups)

However, at least one D in each compound may be a quinonediazide group.
As the quinonediazide photosensitizer, a commercially available one may be used, or it may be synthesized by a known method.

[3] Solvent The photosensitive resin composition of the present invention is prepared as a preferred coating solution by using at least a photosensitive agent and a resin as a solution dissolved in a solvent.

Solvents include N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylacetamide (DMAc), dimethyl-2-piperidone, N, N-dimethylformamide (DMF), dimethyl sulfoxide, 2- Methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran, etc. However, it is not limited to these.
Suitable solvents include N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylacetamide (DMAc), dimethyl-2-piperidone, N, N-dimethylformamide (DMF), and these There are organic solvents such as, but not limited to, mixtures. Preferred solvents are γ-butyrolactone and N-methylpyrrolidone. Most preferred is γ-butyrolactone.

  The total solid concentration (corresponding to the total solid content constituting the dried film) in the photosensitive resin composition of the present invention is generally 15 to 50% by mass, preferably 25 to 45% by mass.

[4] Adhesion promoter The photosensitive resin composition of the present invention may contain an adhesion promoter. Suitable adhesion promoters include, for example, dianhydride / DAPI / bis (3-aminopropyl) tetramethylsiloxane (BATS) polyamic acid copolymer, aminosilane, and mixtures thereof. Addition of dianhydride / DAPI / BATS polyamic acid copolymer increases adhesion properties.

  The dianhydride / DAPI / BATS polyamic acid copolymer can be synthesized in a reaction solvent by reaction of tetracarboxylic dianhydride (J), BATS diamine and DAPI diamine according to the following reaction.

  (In the formula, R ′ is a tetravalent group.)

Tetracarboxylic dianhydride (J) is pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-perfluoroisopropyridine diphthalic dianhydride, 4,4'-oxydiphthalic anhydride, Bis (3,4-dicarboxyl) tetramethyldisiloxane dianhydride, bis (3,4-dicarboxylphenyl) dimethylsilane dianhydride, butanetetracarboxylic dianhydride, 1,4,5,8-naphthalene It may be tetracarboxylic dianhydride and a mixture thereof, but is not limited thereto.
The DAPI / BATS molar ratio is about 0.1 / 99.9 to 99.9 / 0.1. A preferred molar ratio is about 10/90 to 40/60, and a most preferred molar ratio is about 15/85 to 30/70.

  Preferred reaction solvents are N-methyl-2-pyrrolidinone (NMP), γ-butyrolactone (GBL), N, N-dimethylformamide (DMP), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), sulfolane. And diglyme. The most preferred reaction solvents are N-methyl-2-pyrrolidinone (NMP) and γ-butyrolactone (GBL).

Any suitable reaction may be used to react the dianhydride with the above two diamines. Generally, the reaction is carried out at about 10 to about 50 ° C. for about 6 to 48 hours. The molar ratio of dianhydride to diamine should be about 0.9 to 1.1: 1.
The photosensitive resin composition of the present invention can further contain other additives such as a leveling agent.

If necessary, an adhesiveness-imparting agent such as an organosilicon compound, a silane coupling agent, and a leveling agent may be added to the positive photosensitive resin composition in the present invention. Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyl. Examples include triethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. When using an adhesiveness imparting agent, 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass of the PBO precursor, and 0.5 to 10 parts by mass is more preferable.

[5] Pattern Forming Method As a method for forming a relief pattern using the photosensitive resin composition of the present invention, (a) a photosensitive resin composition containing a polyamide resin, a photosensitive agent, and a solvent is used as a suitable substrate. Coated on, (b) baked this coated substrate, (c) exposed with actinic light or radiation, (d) developed with aqueous developer, and (e) cured to cure. A relief pattern can be formed.

  The coated and exposed substrate can also be baked at elevated temperatures prior to development. Further, the developed substrate may be rinsed before curing.

  Thus, with the photosensitive resin composition of this invention, it apply | coats on a semiconductor element so that the thickness after heat curing may become predetermined thickness (for example, 0.1-30 micrometers), prebaking, exposure, image development, and heat curing. Thus, a semiconductor device can be manufactured.

  Hereinafter, a method for forming a relief pattern will be described in more detail.

  The photosensitive resin composition of the present invention is coated on a suitable substrate. The substrate is for example a semiconductor material such as a silicon wafer or a ceramic substrate, glass, metal or plastic. Coating methods include, but are not limited to, spray coating, spin coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.

  The coating film is pre-baked for several minutes to half an hour at an elevated temperature of about 70-120 ° C., depending on the method, to evaporate the remaining solvent. Subsequently, the resulting dry film is exposed to actinic rays or radiation in a preferred pattern through a mask. As actinic rays or radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. The most preferred radiation is one having wavelengths of 436 nm (g-line) and 365 nm (i-line).

  Advantageously, the coated and exposed substrate is heated to a temperature of about 70-120 ° C. following exposure to actinic light or radiation. The coated and exposed substrate is heated in this temperature range for a short time, typically a few seconds to a few minutes. This stage of the method is commonly referred to in the art as post-exposure baking.

  The coating film is then developed with an aqueous developer and a relief pattern is formed. Examples of the aqueous developer include inorganic alkali (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amine (eg, ethylamine, n-propylamine), secondary amine (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions such as mixtures thereof There is. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of surfactant may be added to the developer. Development can be carried out by dipping, spraying, paddling, or other similar development methods.

In some cases, the relief pattern is then rinsed using deionized water. Next, in order to obtain a final pattern of a polymer having high heat resistance, an oxazole ring is formed by curing the relief pattern. Curing is carried out by so as to obtain an oxazole ring forming a highly heat resisting final pattern, baking the substrate at a glass transition temperature T _g of the polymer. Generally, temperatures above about 200 ° C. are used. It is preferred to use a temperature of about 250-400 ° C.

  Hereinafter, the present invention will be described specifically by way of examples.

[Preparation of PBO precursor]

(Synthesis of Resin A-1)
The following aminophenol monomer (0.1 mol), pyridine (0.2 mol) and N-methyl-2-pyrrolidone (NMP) were added to 1 L of a three-necked flask to obtain an NMP solution having a solid content concentration of 20%. The solution was stirred at room temperature until all solids were dissolved, then cooled at -20 to -30 ° C in a dry ice / acetone bath. To this solution, a solution of an NMP solution of 1,4-oxydibenzoyl chloride (90 mmol) (solid content concentration 20% by mass) was added dropwise over 2 hours. After the addition was complete, the resulting mixture was stirred at room temperature for 5 hours. The viscous solution was poured into 1.5 L of deionized water with vigorous stirring, the precipitated white powder was collected by filtration and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. . The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain the target resin A-1. The yield was almost quantitative, and the number average molecular weight of Resin A-1 by gel mission chromatography (GPC) was 8400.

Hereinafter, the following resins A-2 to A-5 were synthesized in the same manner.
The structure was confirmed by 1HNMR by confirming the presence of vinyl protons (5-7 ppm) and allyl protons (2-3 ppm).

(Synthesis of Photosensitive Agent (B-1) (Synthesis Example (1))
In a three-necked flask, 21.6 g of phenolic compound (BP-1) and 1,4-dioxane 20
0 mL was added and dissolved until uniform. Next, 27 g of 1,2-naphthoquinonediazide-4-sulfonyl chloride was added and dissolved. The reaction vessel was cooled to 10 ° C. with ice water, and then 11.1 g of triethylamine was added dropwise over 1 hour. It stirred for 24 hours after completion | finish of dripping. After completion of the reaction, distilled water was added to dissolve the deposited salt, stirred for 30 minutes, neutralized with dilute hydrochloric acid, and crystallized in 1 L of distilled water. The precipitated dark yellow powder was collected by filtration. The residue was dissolved again in 200 mL of dioxane and crystallized in 1 L of distilled water. The precipitated filtrate was filtered, and the filtrate was washed with 1 L of distilled water and filtered to recover 39 g of the target product (B-1) as a dark yellow powder. As a result of analyzing the obtained (B-1) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-1) was 98% (detection wavelength: 254 nm).

(Preparation of resin solution)
The resin shown in Table 1 and 2% by mass of the following adhesion promoter C (alkoxysilane compound) with respect to the resin were dissolved in the solvent shown in Table to make 100 g of a solution having a solid concentration of 35% by mass, and then tetrafluoro The mixture was filtered through an ethylene cassette type filter (0.2 μm) to prepare a resin solution.

(Elongation at break)
The prepared resin solution is spin-coated on a silicon wafer and baked on a hot plate at 120 ° C. for 3 minutes, and further heat-cured at 150 ° C. for 30 minutes and at 320 ° C. for 1 hour under nitrogen conditions. The resin film was peeled off from the wafer and further cut into a size of 5 mm in width and 5 cm in length.
The obtained sample was pulled at both ends with Tensilon (1 mm / min) at 23 ° C. according to JIS K 6760, and the elongation rate (breaking elongation) until breaking was measured.

(Heat resistance evaluation)
The polymer sample obtained above was measured by TGA, and a temperature at which 5% weight loss was observed was observed.

(Preparation of photosensitive resin composition)
The resin shown in Table 1, photosensitive agent B-1 (12% by weight based on the resin), and 2% by weight of the following adhesion promoter C (alkoxysilane compound) based on the resin were dissolved in γ-butyrolactone. 100 g of a solution having a solid content of 35% by mass was prepared, and then filtered through a tetrafluoroethylene cassette type filter (0.2 μm) to prepare a photosensitive resin composition.
The obtained sample was spin-coated on a silicon wafer and baked on a hot plate at 120 ° C. for 3 minutes to obtain a film having a thickness of 7 μm. The film was exposed using an i-line stepper using an 8 micron via-hole repeating pattern mask, then developed with 0.262N aqueous tetramethylammonium hydroxide (TMAH) solution, followed by removal. Rinse with ion water. The obtained pattern was heat-cured at 150 ° C. for 30 minutes under nitrogen and 1 hour at 320 ° C., and the obtained pattern was observed by SEM, and it was confirmed that the pattern could be formed using any resin.

  The results are shown in Table 2.

  It can be seen that the composition of the present invention can provide a film excellent in both elongation at break and heat resistance.

Claims (4)

A polyamide resin containing at least one structure represented by the following general formula (1-1) or (1-2).

R ₁ independently represents a hydrogen atom or an alkyl group.
R ₂ and R ₃ each independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
k and l each independently represents 0 or 1.
m and n each independently represents 0, 1 or 2.   It contains at least one of the structure represented by the general formula (1-1) in which k = 1 and the structure represented by the general formula (1-2) in which 1 = 0. The polyamide resin described in 1.   A photosensitive resin composition comprising the polyamide resin according to claim 1.   A method for producing a semiconductor device, which is obtained by applying the photosensitive resin composition according to any one of claims 1 to 3 onto a semiconductor element, prebaking, exposing, developing, and heating.