JP2007199606A - Photosensitive resin composition and manufacturing method of semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is used for producing a heat resistant relief structure, has high sensitivity, improves adhesion and suppresses occurrence of a residue on development, and also to provide a method of manufacturing a semiconductor device using the composition. <P>SOLUTION: The positive photosensitive resin composition contains a polybenzoxazole precursor having a specific alkoxysilane group in a side chain and/or at a terminal and a photosensitizer. The method of manufacturing a semiconductor device using the composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention is suitable for applications in the field of microelectronic technology, and is capable of developing with an alkaline aqueous solution and a semiconductor device using the composition. It relates to the manufacturing method.

  For the application of microelectronics, polymers that exhibit durability at high temperatures are generally well 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.

Patent Documents 1 and 2 (Japanese Patent Laid-Open Nos. 10-10727 and 10-10740) describe a positive material containing polyamide, a photosensitive diazoquinone compound, and a specific organosilicon compound in order to improve adhesion to a substrate. Type photosensitive resin composition is proposed.
Patent Document 3 (Japanese Patent Application Laid-Open No. 2002-293933) discloses that an alkoxy group-containing compound is provided to provide a transparent polyimide-silica hybrid cured product that is excellent in heat resistance, mechanical strength, and insulation, and that does not warp or crack. A silane-modified polyamic acid resin composition containing a silane-modified polyamic acid and a polar solvent is proposed.

  Also for photosensitive resin compositions containing PBO precursors, it is desired to solve the problems of adhesion and development residue.

Japanese Patent Laid-Open No. 10-10727 Japanese Patent Laid-Open No. 10-10740 JP 2002-293933 A

  A photosensitive resin composition capable of producing a relief structure having heat resistance, having high sensitivity, improved adhesion, and suppressed development residue, and production of a semiconductor device using the composition Provide a method.

The above problems have been achieved by the following configuration.
(1) A positive photosensitive resin composition containing a polybenzoxazole precursor (A1) having the following structure A at the side chain and / or terminal and a photosensitizer.

  R represents an alkyl group each independently, and m represents an integer of 2 to 10.

(2) The positive photosensitive resin composition as described in (1) above, which comprises a polybenzoxazole precursor (A2) not having the structure A.
(3) A method for producing a semiconductor device, which is obtained by applying the photosensitive resin composition according to the above (1) or (2) on a semiconductor element, prebaking, exposing, developing, and heating.

  The photosensitive resin composition of the present invention can produce a relief structure excellent in heat resistance, mechanical properties, electrical properties, and chemical resistance based on polyamide resin, having excellent adhesion, suppressing development residue, and being a semiconductor. It can be suitably used as a use, particularly as a buffer coat.

[1] Polybenzoxazole precursor (A1) having the following structure A in the side chain and / or terminal
The photosensitive resin composition of this invention contains the polybenzoxazole precursor (PBO precursor A1) which has the following structure A in a side chain and / or the terminal.

  R represents an alkyl group each independently, and m represents an integer of 2 to 10.

The alkyl group as R generally has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
m is preferably 2-6.

The PBO precursor A1 is, for example, an epoxy group obtained by a dealcoholization reaction of a PBO precursor having a carboxyl group, an epoxy compound (A) having one hydroxyl group in one molecule, and an alkoxysilane partial condensate (B). It can be synthesized by reacting the contained alkoxysilane partial condensate.
Here, the PBO precursor having a carboxyl group is not particularly limited, and, for example, those described for PBO precursors A2 and A3 described later can be used.

  The epoxy group-containing alkoxysilane partial condensate used in the present invention includes an epoxy compound (A) having one hydroxyl group in one molecule (hereinafter simply referred to as an epoxy compound (A)) and an alkoxysilane partial condensate (B). It is obtained by the dealcoholization reaction.

  The number of epoxy groups is not particularly limited as long as the epoxy compound (A) is an epoxy compound having one hydroxyl group in one molecule. In addition, as the epoxy compound (A), the smaller the molecular weight, the better the compatibility with the alkoxysilane partial condensate and the higher the heat resistance and adhesion imparting effect. .

Specific examples thereof include monoglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting epichlorohydrin with water, dihydric alcohol or phenols having two hydroxyl groups; epichlorohydrin; Polyglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting with a trihydric or higher polyhydric alcohol such as glycerin or pentaerythritol; Molecular end obtained by reacting epichlorohydrin with amino monoalcohol And an alicyclic hydrocarbon monoepoxide having one hydroxyl group in the molecule (for example, epoxidized tetrahydrobenzyl alcohol). Among these epoxy compounds, glycidol is most excellent in terms of heat resistance imparting effect, and is most suitable because of its high reactivity with the alkoxysilane partial condensate (B).

As the alkoxysilane partial condensate (B), the general formula (1): R ¹ _m Si (OR ² ) ( _4-m) (wherein m represents an integer of 0 or 1 and R ¹ has 8 or less carbon atoms) And a hydrolyzable alkoxysilane monomer represented by R ² is a lower alkyl group having 4 or less carbon atoms.) In the presence of an acid or base catalyst and water, That are obtained by condensing in a continuous manner.

  Specific examples of the hydrolyzable alkoxysilane monomer that is a constituent material of the alkoxysilane partial condensate (B) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane, Methoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxy And trialkoxysilanes such as silane. Usually, among these, since the reactivity with glycidol is particularly high, the alkoxysilane partial condensate (B) is preferably synthesized using tetramethoxysilane or methyltrimethoxysilane in an amount of 70 mol% or more.

  In addition, as these alkoxysilane partial condensates (B), those exemplified above can be used without particular limitation, but when two or more of these examples are used in combination, the alkoxysilane partial condensate (B) It is preferable to use 70% by mass or more of tetramethoxysilane partial condensate or methyltrimethoxysilane partial condensate in the total amount of

  The number average molecular weight of the alkoxysilane partial condensate (B) is preferably about 230 to 2000, and the average number of Si in one molecule is preferably about 2 to 11. When the average number of Si is less than 2, the amount of alkoxysilanes flowing out of the system together with alcohol increases without reacting during the demethanol reaction with the epoxy compound (A). The reactivity of the epoxy group-containing alkoxysilane partial condensate with the PBO precursor is lowered, and the desired alkoxy group-containing silane-modified PBO precursor is hardly obtained.

The epoxy group-containing alkoxysilane partial condensate is obtained by dealcoholizing the epoxy compound (A) and the alkoxysilane partial condensate (B).
The use ratio of the epoxy compound (A) and the alkoxysilane partial condensate (B) is not particularly limited as long as the alkoxy group substantially remains, but in the resulting epoxy group-containing alkoxysilane partial condensate. The proportion of the epoxy group of the epoxy compound (A) is usually the equivalent of the hydroxyl group of the epoxy compound (A) / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) = 0.01 / 1 to 0.5 / 1, It is preferable to subject the alkoxysilane condensate (B) and the epoxy compound (A) to a dealcoholization reaction. Since the ratio of the alkoxysilane partial condensate (B) that is not epoxy-modified increases when the charging ratio decreases, the polyimide-silica hybrid cured product tends to become opaque, so the charging ratio is 0.03 or more. / 1 is more preferable. Moreover, since the epoxy group of the epoxy group-containing alkoxysilane partial condensate becomes multifunctional and becomes easy to gel during synthesis of the alkoxy group-containing silane-modified polyamic acid when the charge ratio is increased, the charge ratio is 0.4 or less / 1 is more preferable.

  In the reaction of the alkoxysilane partial condensate (B) and the epoxy compound (A), for example, a dealcoholization reaction is carried out while the above components are charged and the alcohol produced by heating is distilled off. The reaction temperature is about 50 to 150 ° C., preferably 70 to 110 ° C., and the total reaction time is about 1 to 15 hours. If the dealcoholization reaction is carried out at a temperature exceeding 110 ° C., the molecular weight of the reaction product increases too much with the condensation of alkoxysilane in the reaction system, and there is a tendency to increase the viscosity or gel. In such a case, viscosity increase and gelation can be prevented by a method such as stopping the dealcoholization reaction during the reaction.

  In the dealcoholization reaction of the above alkoxysilane partial condensate (B) and the epoxy compound (A), among the conventionally known ester-hydroxyl ester exchange catalysts for promoting the reaction, those which do not open the epoxy ring Can be used. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, , These oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate and tin octylate are effective.

  Moreover, the said reaction can also be performed in a solvent. The solvent is not particularly limited as long as it dissolves the alkoxysilane condensate and glycidol and is inert to the epoxy group of the epoxy compound (A). As such an organic solvent, for example, a solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, xylene is preferably used.

  The production of the alkoxy group-containing silane-modified PBO precursor is carried out, for example, by charging each of the above components and heating in a substantially anhydrous state. The main purpose of this reaction is to react the carboxylic acid group of the PBO precursor with the epoxy group of the epoxy group-containing alkoxysilane partial condensate. During this reaction, the sol of the alkoxysilyl moiety of the epoxy group-containing alkoxysilane partial condensate is used. -It is necessary to suppress the formation of silica by gel reaction and the ring-closing reaction to the imide group of polyamic acid. Therefore, the reaction temperature is about 50 to 120 ° C., preferably 60 to 100 ° C., and the total reaction time is preferably about 1 to 30 hours.

  In the above dealcoholization reaction, a catalyst used for reacting a conventionally known epoxy group with a carboxylic acid can be used to promote the reaction. Tertiary amines such as 1,8-diaza-bicyclo [5,4,0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and benzimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine Class: Tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate And the like tetraphenyl boron salts and the like. The reaction catalyst is preferably used at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyimide-based solid residue of polyamic acid.

In addition, it is preferable to perform the said reaction in a solvent. The solvent is not particularly limited as long as it is a solvent that dissolves the PBO precursor and the epoxy group-containing alkoxysilane partial condensate. Examples of such a solvent include those used at the time of producing the PBO precursor.

The proportion of the structure A in the PBO precursor A1 is generally 0.1 to 40% by mass, preferably 0.5 to 20% by mass.
The addition amount of the PBO precursor A1 is generally 0.1% by mass or more, preferably 0.5% by mass or more in the total resin components of the photosensitive resin composition of the present invention.

[2] Polybenzoxazole precursor (A2) having no structure A
The photosensitive resin composition of the present invention preferably contains a polybenzoxazole precursor (PBO precursor A2) that does not have structure A.
As the PBO precursor A2, a known PBO precursor can be used as long as it does not have the structure A.

  Examples of the PBO precursor A2 include known ones described in, for example, U.S. Pat. No. 4,371,685, JP 2002-52695 A, and the like, and a polybenzoxazole precursor having the following structure A polymer (G) can be mentioned.

In the formula, Ar ₁ is a tetravalent aromatic group, aliphatic group, heterocyclic group or a mixed group thereof, and A 1
r ₂ may be a divalent aromatic group, a heterocyclic group, an alicyclic group or an aliphatic group which may or may not contain silicon, and Ar ₃ is a divalent aromatic group or an aliphatic group. A heterocyclic group or a mixed group thereof. x represents 5-1000, and y represents 0-900.
The intrinsic viscosity of the PBO precursor is measured in NMP at a concentration of 0.5 g / dL at 25 ° C., preferably 0.1 to 0.7 dL / g, more preferably 0.12 to 0.6 dL / g.

  The PBO precursor A2 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.

In the formula, Ar ₁ , Ar ₂ , Ar ₃ , x and y are as defined above, and W is Cl, O
R or OH, and wherein R is an alkyl group or a cycloalkyl group, _{e.g., -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, and examples thereof include the following groups: Can do.

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.
Examples of the monomer (B) containing Ar ₂ include 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'
-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 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, hepta Methylenediamine, 2,5-dimethylheptamethylenediamine, 3-
Methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 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'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 2,6-diaminopyridine, 2,5-diaminopyridine, 2, 6-Diamino-4-trifluoromethyl Pyridine, 2,5-diamino-1,3,4-oxadiazole, 1,4-diaminocyclohexane, piperazine, 4,4'-methylenedianiline, 4,4'-methylenedi-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-methoxyaniline), 4,4'-thio-bis- (2-chloroaniline), 3,3'-sulfonyl-dianiline, 3,3'-sulfonyl-dianiline, and these However, it is not limited to these. However, it should be understood that monomer (B) is not limited thereto.

In monomer (C), which is a constituent of PBO precursor (G) and capped precursor (F), Ar ₃ is a divalent aromatic group, aliphatic group, or heterocyclic group, For example, the following groups are mentioned.

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

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 A2 is generally 99.9% by mass or less and preferably 99.5% by mass or less in the total resin components of the photosensitive resin composition of the present invention.

  The total amount of the PBO precursors A1 and A2 is generally 50 to 97% by mass, preferably 70 to 95% by mass, in the photosensitive resin composition of the present invention.

[3] Polybenzoxazole precursor (A3) having a carboxyl group at the side chain and / or terminal
Moreover, it is preferable that the photosensitive resin composition of this invention contains the polybenzoxazole precursor (PBO precursor A3) which has a carboxyl group in a side chain and / or the terminal.
The PBO precursor A3 is not limited as long as it is a PBO precursor having a carboxyl group at the side chain and / or terminal, and the PBO precursor A1 or A2 described above has a carboxyl group at the side chain and / or terminal. Also good.
As a method for introducing a carboxyl group into the side chain of the PBO precursor, for example, there is a method in which a phenolic hydroxyl group in the side chain of the PBO precursor is reacted with a bromoacetic acid derivative.
As a method of introducing a carboxyl group at the terminal, there is a method of using a dicarboxylic acid in the reaction with a diamino compound in the synthesis of the PBO precursor.

  Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxydiphenyl ether, 4,4′- Dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5- Aromatic dicarboxylic acids such as chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, And aliphatic dicarboxylic acids such as succinic acid. It can be used alone or in combination of two or more. Of these, aromatic dicarboxylic acids are preferred from the viewpoint of heat resistance.

  A preferred ratio (molar ratio) between the diamine compound and the dicarboxylic acid compound is in the range of 0.8 / 1 to 0.99 / 1 in the former / the latter. In polybenzoxazole synthesized by setting within this range, a carboxylic acid group can be arranged at the molecular end. In this case, a preferable reaction temperature is −30 to 40 ° C., and a preferable reaction time is 5 minutes to 10 hours.

The polybenzoxazole precursor is, for example, Polymer Letter. , Vol. 2, pp 655-659 (1964) can be obtained by reacting dicarboxylic acid dihalide (chloride, bromide) with dihydroxydiamine. In this case, the reaction is preferably performed in an organic solvent in the presence of a dehalogenation acid catalyst. Dicarboxylic acid dichloride can be obtained by reacting dicarboxylic acid with thionyl chloride. At this time, it is effective to make the molar ratio of thionyl chloride to dicarboxylic acid less than an equal amount so as to be a carboxylic acid group terminal.

  The ratio of the carboxyl group in the PBO precursor A3 is generally 0.1 to 40% by mass, preferably 0.5 to 20% by mass.

[4] Photosensitizer The photosensitizer is not particularly limited, and for example, 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 naphthoquinonediazide group.
As the quinonediazide photosensitizer, a commercially available one may be used, or it may be synthesized by a known method.

[5] Solvent The photosensitive resin composition of the present invention is prepared as a solution in which at least a photosensitizer and a PBO precursor are dissolved in a solvent.

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.
A solvent containing γ-butyrolactone in an amount of 50% by mass or more is preferable. Examples of the solvent used in combination with γ-butyrolactone include N-methylpyrrolidone, propylene glycol monoalkyl ether acetate (for example, propylene glycol monomethyl ether acetate), propylene glycol mono Alkyl ether (for example, propylene glycol monomethyl ether) and alkyl lactate (for example, ethyl lactate) are preferable.

  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.

[6] 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-naphthalenetetracarboxylic dianhydride, and mixtures thereof. It is not limited.
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.

[7] 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 (TMAH). 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]

(1) Synthesis of Resin A (Polybenzoxazole Precursor Having Carboxyl Group at Terminal) In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and N -After charging 90 g of methylpyrrolidone and cooling the flask to 5 ° C, 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4'-diphenyl ether tetracarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and stirred. After dissolution, 8.53 g of pyridine was added, and while maintaining the temperature at -20 to -25 ° C, a solution of 4,4'-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 5 liters of water, and the precipitate was collected, washed 3 times with pure water, and then dried under reduced pressure to obtain polyhydroxyamide. The weight average molecular weight calculated | required by standard polystyrene conversion was 16130, and dispersion degree was 2.0.

(2) Synthesis of Resin B (Polybenzoxazole Precursor Having Carboxyl Group in Side Chain) To 100 ml of a three-necked flask, 3.85 g (10.5 mmol) of hexafluoro-2,2-
Bis (3-amino-4-hydroxyphenyl) propane, 1.70 g (21 mmol) pyridine and 15 g N-methyl-2-pyrrolidone (NMP) were added. The solution was stirred at room temperature until all solids were dissolved, then cooled at 0-5 ° C. in an ice bath. In this solution 1.
1.4 dissolved in 02 g (5 mmol) isophthaloyl chloride and 10 g NMP.
8 g (5 mmol) of 1,4-oxydibenzoyl chloride was added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 18 hours. The viscous solution was poured into 800 ml 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 at 40 ° C. for 24 hours under vacuum to obtain resin B-1 as an intermediate. The weight average molecular weight calculated | required by standard polystyrene conversion was 14640, and dispersion degree was 2.2.
The obtained resin B-1 was dissolved in acetone to a concentration of 20% by mass. To this, 0.1 equivalent of bromoacetic acid t-butyl ester and an aqueous choline solution (50 mass%) with respect to the hydroxyl group were added and stirred at room temperature for 3 hours, and then the resulting reaction solution was poured into distilled water, White powder was collected. The obtained powder is air-dried, then dissolved again in acetone, p-toluenesulfonic acid is added, heated at 40 ° C. for 3 hours, the reaction solution is poured into distilled water, and the desired white powder is obtained. Was recovered. The obtained powder was dried and analyzed by 1HNMR. As a result, it was confirmed that 10 mol% of the phenolic hydroxyl group was substituted with acetic acid.

(3) Synthesis of Resin a (Reaction Product of Resin A and Alkoxysilane Condensate) According to the method described in JP-A No. 2002-293933, glycidol (trade name “Epiol OH” manufactured by NOF Corporation) and Tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 51”, Si average number 4) was reacted to obtain an epoxy group-containing alkoxysilane partial condensate (2A). Similarly to this, the resin A obtained above is reacted according to the method described in JP-A No. 2002-293933, and by reacting the carboxyl group of the resin A with the glycidyl group of 2A, the target resin a (NMP 10 mass) % Solution).

(4) Synthesis of Resin b (Reaction Product of Resin B and Alkoxysilane Condensate) Resin B and 2A obtained above are reacted according to the method described in Japanese Patent Application Laid-Open No. 2002-293933, and carboxyl of resin B The target product resin b (NMP 10 mass% solution) was obtained by reacting the group with 2A glycidyl group.

[Synthesis of photosensitizer]
(5) Synthesis of photosensitizer (P-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 (P-1) as a dark yellow powder. As a result of analyzing the obtained (P-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).

(6) Synthesis of photosensitizer (P-2) The above synthesis was performed except that the phenol compound used was changed to (BP-2) and the amount of 1,2-naphthoquinonediazide-4-sulfonyl chloride used was doubled. Photosensitizer (P-2) was synthesized in the same manner as in the example. As a result of analyzing the obtained (P-2) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-2) was 97.5% (detection wavelength: 254 nm).

(7) Preparation of photosensitive resin composition The materials listed in Table 1 were dissolved in γ-butyrolactone to prepare a solution having a solid content of 40% by mass, and then filtered through a tetrafluoroethylene cassette-type filter (0.2 µm). A photosensitive resin composition was prepared.

(8) Evaluation of development residue and adhesion The prepared composition 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 10 μm. This film is exposed using an i-line stepper using a 5 micron via hole repetitive pattern mask, then developed with 0.262N aqueous tetramethylammonium hydroxide, followed by deionized water. I'm sorry. The entire surface of the 200 mm wafer was exposed with an exposure amount for reproducing a 5 micron via hole pattern to form a pattern. The wafer was observed using 2360 manufactured by KLA-Tencor, and the number of development residues was counted.
The obtained wafer was heat-cured at 150 ° C. for 30 minutes under nitrogen and at 280 ° C. for 1 hour. Twenty wafers were prepared, and the obtained wafers were immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 1 minute to confirm the presence or absence of pattern peeling. The number of samples peeled out of 10 sheets was counted.

  It can be seen that the composition of the present invention is excellent in both development residue and adhesion.

Claims (3)

A positive photosensitive resin composition comprising a polybenzoxazole precursor (A1) having the following structure A in the side chain and / or terminal and a photosensitizer.

R represents an alkyl group each independently, and m represents an integer of 2 to 10.   The positive photosensitive resin composition according to claim 1, comprising a polybenzoxazole precursor (A2) not having the structure A.   A method for producing a semiconductor device, which is obtained by applying the photosensitive resin composition according to claim 1 or 2 onto a semiconductor element, prebaking, exposing, developing, and heating.