JP4969333B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition used as a surface protective film and an interlayer insulating film of a semiconductor device, a method for producing a heat-resistant cured relief pattern using the positive photosensitive resin composition, and the The present invention relates to a semiconductor device having a cured relief pattern.

Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor device. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition. By applying, patterning with actinic rays, development, thermal imidization treatment, etc., a surface protective film and interlayer insulation are formed on a semiconductor device. A film or the like can be easily formed, and the process can be significantly shortened as compared with the conventional non-photosensitive polyimide precursor composition.
However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Solvent measures have been demanded. In response to this, recently, various heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been proposed in the same manner as photoresists.

Among them, a PBO precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as a polybenzoxazole (hereinafter also referred to as PBO) precursor, with a photoactive component such as a photosensitive diazoquinone compound is used as a positive photosensitive resin composition. The method to be used has attracted attention in recent years and is disclosed in, for example, Patent Document 1.
The development mechanism of this positive photosensitive resin composition is that the unexposed photosensitive diazoquinone compound is insoluble in an alkaline aqueous solution, but the photosensitive diazoquinone compound undergoes a chemical change when exposed to indenecarboxylic acid compound. This makes use of the fact that it becomes soluble in an alkaline aqueous solution. By using the difference in dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern of only the unexposed portion can be created.

The PBO precursor composition described above can form a positive relief pattern by exposure and development with an alkaline aqueous solution, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. It attracts attention as a promising alternative material for solvent-developed polyimide precursors. However, the PBO precursor composition obtained by the methods disclosed so far still has many problems.
For example, when a PBO precursor composition is actually used, a particularly serious problem is the amount of film loss in the unexposed area during development. When the amount of film reduction in the unexposed area is large, the shape of the relief pattern after development is remarkably deteriorated and sufficient performance cannot be obtained. As a countermeasure for this, if the molecular weight of the PBO precursor, which is the base resin, is increased, the amount of film loss in the unexposed area can be reduced. However, in this case, there is a drawback that a development residue (scum) is generated in an exposed portion which should be completely dissolved and removed with a developer, and resolution is deteriorated. There is also a problem that the developing time of the exposed portion becomes long.

In order to solve this problem, Patent Document 2 and Patent Document 3 report that by adding a specific phenol compound to the PBO precursor composition, the amount of film loss in an unexposed portion during development can be suppressed. However, as shown in a comparative example described later, the effect is insufficient, and in particular, when the molecular weight of the PBO precursor is high, there is a demand for an effect that suppresses film thickness reduction without generating a development residue (scum). It was.
In addition, the relief pattern composed of the PBO precursor after development is converted into a cured relief pattern composed of a heat-resistant PBO resin by heat treatment. Depending on the phenol compound to be added, In some cases, the uncured PBO precursor flows and the relief pattern shape changes greatly.

  On the other hand, Patent Document 4 reports an attempt to solve the problem of film loss in unexposed areas and the problem of occurrence of scum by using a photosensitive diazoquinone compound having a specific structure. This technology uses a specific structure for the skeleton part to which the diazoquinone part is bonded, so that the structure changes when the photosensitive diazoquinone compound comes into contact with an alkaline aqueous solution, thereby improving the solubility of the entire photosensitive resin composition. It is. However, as a result of investigation by the present inventors, in this method, when the amount of light irradiated to the exposed portion is small, the molecule that is not chemically changed to indenecarboxylic acid in the photosensitive diazoquinone compound in the exposed portion is an alkaline aqueous solution. The solubility in is low, and a development residue is generated. Furthermore, in the unexposed area, the solubility of the photosensitive diazoquinone compound in contact with the alkaline aqueous solution increases, and the dissolution inhibiting ability in the unexposed area, which is the original function of the photosensitive diazoquinone compound, decreases. As a result, the difference in dissolution rate between the exposed part and the unexposed part is not sufficient, resulting in an increase in the amount of film loss, which is not satisfactory as a photosensitive resin composition.

Japanese Examined Patent Publication No. 63-096162 JP 09-302221 A JP 2000-292913 A JP 2001-133975 A

  The present invention provides a novel positive photosensitive resin composition excellent in sensitivity, residue removal property and adhesiveness even when used in a short development time, a method for producing a cured relief pattern using the composition, and the curing An object is to provide a semiconductor device having a relief pattern.

  As a result of intensive studies in order to solve the above problems, the present inventor has combined a hydroxy polyamide having a specific structure with a compound having a carbonyl group having a specific structure to solve the above problem. The inventors have found that a photosensitive resin composition can be obtained, and have reached the present invention.

That is, the first of the present invention is represented by the following general formulas (2), (3), and (4) with respect to 100 parts by mass of the hydroxy polyamide having a repeating unit represented by the following general formula (1). A positive photosensitive resin composition comprising 0.1-30 parts by mass of a compound having at least one carbonyl group selected from the group of compounds and 1-100 parts by mass of a photosensitive diazoquinone compound, It is.
(Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ , Y ₁ and Y ₂ are divalent organic groups having at least 2 carbon atoms, m is 2 to 2) An integer of 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and Y ₂ are (The order of arrangement of the n diamide units contained is not limited.)

(In the formula, L represents a divalent organic group having 1 to 12 carbon atoms, R represents a hydroxy group or an organic group having 1 to 9 carbon atoms.)

Moreover, in the positive photosensitive resin composition composition of this invention, the compound which has a carbonyl group is selected from the compound group represented by following General formula (3), (4), and (5). Preferably it is at least one compound.
(In the formula, L represents a divalent organic group having 1 to 12 carbon atoms.)

Furthermore, in the positive photosensitive resin composition of the present invention, the compound having a carbonyl group is more preferably at least one compound selected from the group shown below.

In the second aspect of the present invention, (1) the above-mentioned positive photosensitive resin composition is formed on a substrate in the form of a layer or a film, and (2) it is exposed to actinic radiation through a mask, or light, electron A method for producing a cured relief pattern, comprising directly irradiating a line or an ion beam, (3) eluting or removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern.
The third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the above-described method for producing a cured relief pattern.

  According to the present invention, a positive photosensitive resin composition excellent in sensitivity, residue removal property, and adhesiveness, a method for producing a cured relief pattern using the positive photosensitive resin composition, and the cured relief pattern A semiconductor device is provided.

<Positive photosensitive resin composition>
Each component constituting the positive photosensitive resin composition of the present invention will be specifically described below. (A) Hydroxypolyamide The hydroxypolyamide, which is the base polymer of the positive photosensitive resin composition of the present invention, is a polymer containing m dihydroxydiamide units of the following general formula (1). The dihydroxydiamide unit consists of a bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ and a dicarboxylic acid having a structure of Y ₁ (COOH) ₂ . Here, the two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position, and the hydroxypolyamide is closed by heating at about 300 to 400 ° C., and is a heat resistant resin. Changes to polybenzoxazole. m is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20. If necessary, the hydroxypolyamide may be condensed with n diamide units of the following general formula (1). The diamide unit is composed of a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of Y ₂ (COOH) ₂ . n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. If the ratio of the diamide unit in the hydroxy polyamide is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of m / (m + n) is preferably 0.5 or more, 0.7 More preferably, it is more preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- ( -Amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3 '-Dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3- And diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Particularly preferred among these bisaminophenols is when X ₁ is an aromatic group selected from the following.

As the diamine having a structure of X ₂ (NH _{2) 2,} an aromatic diamine, such as silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Ruoropuropan, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,

1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2 -Pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2 , 4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4, 4′-diaminoazobenzene, 4,4′-diaminodiphenylurea, 4,4′-bis (4-aminophenoxy) biphenyl,

2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-amino Phenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4 ′ -Bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4′-diaminobenzophenone, phenylindanediamine, 3,3′-dimethoxy-4 , 4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, o-toluidine sulfone, 2,2- (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4- Aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4,4′-diaminobenzanilide, and aromatic diamines thereof And a compound in which the hydrogen atom of the aromatic nucleus is substituted with at least one group or atom selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group.

  Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( γ-aminopropyl) tetraphenyldisiloxane and the like.

Moreover, as a preferable dicarboxylic acid having a structure of Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ , a case where Y ₁ and Y ₂ are aromatic groups selected from the following can be mentioned.
Wherein A is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Means a group of
Among these, examples of the dicarboxylic acid include 4,4′-diphenyl ether dicarboxylic acid, and 4,4′-diphenyl ether dicarbonyl chloride obtained by chlorinating the dicarboxylic acid is a positive photosensitive resin. Used in the composition.

In the hydroxypolyamide having the repeating unit represented by the general formula (1), it is also included in the scope of the present invention to seal the terminal group with a specific organic group.
Examples of such a blocking group include a group having an unsaturated bond as described in JP-A No. 05-197153, or 4-methylcyclohexyl-1,2-dicarboxylic anhydride. When sealed with these, it is expected that the mechanical properties (particularly elongation) of the coating film after heat curing and the cured relief pattern shape will be good. Preferred examples of such a sealing group include the following groups.

(B) Compound having carbonyl group In the positive photosensitive resin composition of the present invention, at least one selected from the group of compounds represented by the following general formulas (2), (3) and (4) It is important to include a compound having a carbonyl group.
(In the formula, L represents a divalent organic group having 1 to 12 carbon atoms, and R represents a hydroxy group or an organic group having 1 to 9 carbon atoms.)

L in the general formulas (2), (3) and (4) is preferably a divalent organic group having 2 to 12 carbon atoms, and a divalent organic group having 2 to 7 carbon atoms. It is more preferable that it is a divalent organic group having 6 to 7 carbon atoms.
Examples of the compound having a carbonyl group include succinimide, maleimide, glutarimide, phthalimide, 1,8-naphthalimide, 1,2,4,5-benzenetetracarboxydiimide, 1,4,5,8-naphthalenetetra. Imide compounds such as carboxydiimide, N-hydroxysuccinimides, N-hydroxyphthalimides, N-hydroxyimide compounds such as N-hydroxy-5-norbornene-2,3-dicarboxylic imides, ninhydrin, hydrin dantine, alloxanthin And the like.

Among these, the compound having the carbonyl group is more preferably a compound represented by at least one selected from the group consisting of the following general formulas (3), (4), and (5).
(In the formula, L represents a divalent organic group having 1 to 12 carbon atoms.)

Further, the compound having the carbonyl group is most preferably at least one compound selected from the group shown below.

When the above-mentioned compound having a carbonyl group is added to the positive photosensitive resin composition composed of the above-mentioned hydroxypolyamide and the photosensitive diazoquinone compound described later, the dissolution rate in the exposed area is increased and the sensitivity is improved. Further, the amount of film loss in the unexposed area as seen when the molecular weight of the PBO precursor as the base resin is reduced to increase the sensitivity is very small (that is, the dissolution rate of the unexposed area is not greatly increased). . In addition, when the molecular weight of the PBO precursor is increased to reduce the amount of film loss in the unexposed area, the development residue (scum) in the exposed area is almost seen when the compound having the carbonyl group is added. And resolution is greatly improved.
The addition amount of the compound having a carbonyl group is preferably 0.1 to 30 parts by mass and more preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. If the addition amount is less than 0.1 parts by mass, the effects of high sensitivity and high resolution cannot be obtained. On the other hand, if the addition amount exceeds 30 parts by mass, the film loss during development increases and the practicality is lacking.

(C) Photosensitive diazoquinone compound The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, and is described in U.S. Pat. No. 2,772,972. It is a known substance according to the specifications of 2,797,213 and 3,669,658. As an example of a preferable thing, the following are mentioned, for example.
(In the formula, Q is a hydrogen atom or a naphthoquinonediazide sulfonic acid ester group shown below, and all Qs are not hydrogen atoms at the same time.)

Among these, the following are particularly preferable.
1-100 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity to the hydroxy polyamide of a photosensitive diazoquinone compound, 10-30 mass parts is more preferable. If the blending amount of the photosensitive diazoquinone compound is less than 1 part by mass, the patterning property of the resin is poor. On the contrary, if it exceeds 100 parts by mass, the tensile elongation of the cured film is remarkably lowered, and the development residue ( Scum) becomes extremely intense.

(D) Other components In the positive photosensitive resin composition of the present invention, if necessary, conventionally used as an additive of a photosensitive resin composition, a dye, a surfactant, and adhesion to a substrate. It is also possible to add an adhesion aid and a crosslinking agent for increasing the viscosity.
The additives will be described more specifically. Examples of the dye include methyl violet, crystal violet, and malachite green.
As addition amount of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.
Examples of the surfactant include non-ionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether, or derivatives thereof, such as Fluorard (trade name, manufactured by Sumitomo 3M), Megafuck ( Fluorosurfactants such as trade name, Dainippon Ink & Chemicals, Inc. or Sulflon (trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation ) And granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
As addition amount of surfactant, 0.01-10 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.

Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.
Specific preferred examples of the silane coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyl. Trialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkyl Silane and acid anhydride or acid dianhydride reactant, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group And the like of. In this case, methyl group, ethyl group, butyl group, etc. as the alkyl group, maleic anhydride, phthalic anhydride, etc. as the acid anhydride, pyromellitic dianhydride as the acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc., t-butoxycarbonylamino group as a urethane group, phenylamino as a urea group Examples thereof include a carbonylamino group.
The addition amount of the adhesion assistant is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the hydroxy polyamide.

Examples of the crosslinking agent include 1,1,2,2-tetra (p-hydroxyphenyl) ethane, tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy ) Epoxy compounds such as naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone magnesium (II) ) Salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, Metal chelating agents such as fluoroacetylacetone magnesium (II) salt and trifluoroacetylacetone nickel (II) salt, Nicalak MW-30MH, MW-100LH (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, Cymel 303 (trade name, And alkylated melamine resins such as Mitsui Cytec).
As addition amount of a crosslinking agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.

(E) Solvent In the present invention, these components are dissolved in a solvent to form a varnish, which is used as a positive photosensitive resin composition. Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3- Methoxypropionate or the like can be used alone or in combination. Of these solvents, non-amide solvents are preferable from the viewpoint of little influence on photoresists, and specific more preferable examples include γ-butyrolactone, cyclopentanone, cyclohexanone, isophorone and the like.
As addition amount of a solvent, 50-1000 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, a method for producing a cured relief pattern by applying the positive photosensitive resin composition of the present invention to a substrate will be specifically described below.
First, the positive photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner or a roll coater. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent.
Second, exposure with actinic radiation is performed through a mask using a contact aligner or a stepper, or light, electron beam, or ion beam is directly irradiated.
Third, the irradiated portion is dissolved and removed with a developer, and then rinsed with a rinse solution to obtain a desired relief pattern. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.

The developer used for developing the photosensitive resin film formed with the positive photosensitive resin composition of the present invention is an alkaline aqueous solution in which an alkali-soluble polymer is dissolved and removed, and an alkali compound is dissolved. is required. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.
Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.

Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

Finally, the obtained relief pattern can be heat-treated at a temperature of 300 to 400 ° C. for about 5 to 120 minutes to form a heat-resistant cured relief pattern having a polybenzoxazole structure.
The cured relief pattern created by the above-described manufacturing method is used to manufacture a known semiconductor device as a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a protective film for a device having a bump structure. A semiconductor device can be manufactured by combining with the method. It is also useful as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.

The present invention will be described more specifically based on reference examples, examples, and comparative examples, but the present invention is not limited to these examples. <Synthesis of Hydroxy Polyamide> [Reference Example 1] In a separable flask having a volume of 2 l, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75 of pyridine 75 .9 g (0.96 mol) and 692 g of N, N-dimethylacetamide (hereinafter referred to as “DMAc”) were mixed and stirred at room temperature (25 ° C.) to dissolve. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of diethylene glycol dimethyl ether (hereinafter referred to as “DMDG”) separately was added dropwise to the dropping funnel. . The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.

Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropping, the above reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water and dehydrated appropriately, followed by vacuum drying to obtain hydroxypolyamide P-1. Obtained. The weight average molecular weight of the hydroxypolyamide thus synthesized by gel permeation chromatography (hereinafter also referred to as “GPC”) was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd., trade name: Shodex, KF-807 / KF-806M / K F-806M / KF-802.5; In-line Separation: Tetrahydrofuran, 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex RI-101

  [Reference Example 2] In a separable flask having a volume of 3 l, 173.1 g (0.473 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 605.7 g of DMAc, 71. 2 g (0.9 mol) was mixed and stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 132.80 g (0.45 mol) of 4,4'-diphenyl terdicarbonyl chloride in 531.2 g of DMDG was added dropwise thereto from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for the dropping was 60 minutes, and the temperature of the reaction solution was 30 ° C. at the maximum.

Three hours after the completion of the dropwise addition, 7.6 g (0.045 mol) of 4-methylcyclohexyl-1,2-dicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours. 99% of was sealed with 2-carboxy-4-methylcyclohexylamide group. The reaction rate at this time can be easily calculated by monitoring the remaining amount of 4-methylcyclohexyl-1,2-dicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the above reaction solution was dropped into 20 l of water under high-speed stirring to disperse and precipitate the polymer, and this was collected, washed with water, dehydrated, and then vacuum-dried. The weight average molecular weight measured by GPC method was 30000 (polystyrene conversion). ) Hydroxypolyamide P-2.
In addition, when further purification of the polymer is necessary, it can be carried out by the following method. That is, after redissolving the polymer obtained above in DMDG, this was treated with a cation exchange resin and an anion exchange resin, and the solution obtained thereby was poured into ion exchange water, and then the precipitated polymer was removed. A purified polymer can be obtained by filtration, washing with water, and vacuum drying.

<Synthesis of photosensitive diazoquinone compound>
[Reference Example 3]
In a 1 l separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g (0.6 mol) of pyridine. Into this, 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. The reaction solution was added dropwise to 1 liter of ion-exchanged water with stirring, and the precipitate was separated by filtration. To this, 500 mL of THF was added and dissolved by stirring. This homogeneous solution was dissolved in cation exchange resin: Amberlyst 15 (manufactured by Organo) ) The remaining pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 l of ion-exchanged water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.
The product is imidized, it is not characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1 appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum is present, and NMR spectrum This was confirmed by the absence of amide and carboxylic acid proton peaks.

Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was added dropwise to 5 l of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 l of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like material obtained was vacuum-dried at 40 ° C. for 24 hours to obtain photosensitive diazoquinone compound Q-1.

[Reference Example 4]
102.4 g (0.92 mol) of resorcinol and 92.0 g (0.92 mol) of hexanal were dissolved in 920 ml of ethanol. This was cooled to 0 ° C. and 148 ml of 12N hydrochloric acid was added dropwise and stirred. The mixture was then stirred at 70 ° C. for 10 hours under a nitrogen atmosphere. After reaching room temperature, the precipitate was removed by filtration. The solid obtained by washing the filtrate with water at 80 ° C. and drying was recrystallized with a mixed solvent of methanol, hexane and acetone. Thereafter, vacuum drying was performed to obtain a resorcin cyclic tetramer with a yield of 50%.
Next, 76.9 g (0.1 mol) of the resorcin cyclic tetramer synthesized earlier, 134.3 g (0.5 mol of naphthoquinone diazide sulfonic acid esterification rate of 62. 1-naphthoquinone diazide-4-sulfonyl chloride). 5%) and 1057 g of tetrahydrofuran were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 53.1 g (0.525 mol) of triethylamine with 266 g of tetrahydrofuran was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath. After completion of the dropwise addition, the mixture was left to stir at 20 ° C. for another 30 minutes, and then 6.8 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. .
The filtrate obtained at this time was added dropwise to 10 l of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 l of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain the desired photosensitive diazoquinone compound Q-2.

<Preparation of positive photosensitive resin composition>
[Examples 1 to 4, Comparative Examples 1 and 2]
The photosensitive diazoquinone compound (Q-1 or Q-2) obtained in Reference Examples 3 and 4 above with respect to 100 parts by mass of the hydroxypolyamide (P-1 or P-2) obtained in Reference Examples 1 and 2 above. ) Add 20 parts by mass, and further describe a compound having a carbonyl group represented by the following formula (E-1 to E-4 (all manufactured by Tokyo Chemical Industry Co., Ltd.)) or bisphenol A (E-5) in the table. After adding the amount of GBL and dissolving in 170 parts by weight of GBL, it was filtered through a 0.2 μm filter to prepare positive photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 described in Table 1. did.

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of patterning characteristics The positive photosensitive resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (clean track Mark-8) manufactured by Tokyo Electron, and prebaked at 120 ° C for 180 seconds on a hot plate. And a coating film having a thickness of 10.7 μm was formed. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.
The obtained coating film was exposed with a stepper (NSR2005i8A) manufactured by Nikon Corporation having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern while changing the exposure stepwise. This was developed using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electronic Materials, so that the film thickness after development was 9.1 μm at 23 ° C. Development was carried out by adjusting the time to form a positive relief pattern. Table 2 shows the development time, sensitivity, residue removability, and adhesiveness of the positive photosensitive resin composition.

In addition, the sensitivity, residue removal property, and adhesiveness of the positive photosensitive resin composition were evaluated as follows.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.
[Removability of residue]
The extent to which residues are removed from the resolved pattern. The relief pattern after development was observed with an optical microscope, and when no residue was observed in the exposed area at an exposure amount higher than sensitivity, it was marked as ◯.
[Adhesiveness (μm)]
The minimum pattern size that is bonded to the wafer.
From Table 2, it can be seen that a highly sensitive and highly adhesive relief pattern can be formed by using the positive photosensitive resin composition of the present invention. Furthermore, generation of residues after development is not observed, and there is almost no change in the relief pattern shape due to curing.
On the other hand, the compositions of Comparative Examples 1 and 2 that did not contain the compound having a carbonyl group, which is a requirement of the present invention, had low sensitivity and adhesiveness, and a residue was generated after development.

  The positive photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, and an interlayer of a multilayer circuit. It can be suitably used as an insulating film, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (5)

At least selected from the group of compounds represented by the following general formulas (2), (3), and (4) with respect to 100 parts by mass of the hydroxypolyamide having a repeating unit represented by the following general formula (1) A positive photosensitive resin composition comprising 0.1 to 30 parts by mass of a compound having one carbonyl group and 1 to 100 parts by mass of a photosensitive diazoquinone compound.
Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ , Y ₁ and Y ₂ are divalent organic groups having at least 2 carbon atoms, m is 2 to 2 An integer of 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and Y ₂ are (The order of arrangement of the n diamide units contained is not limited.)
(In the formula, L represents a divalent organic group having 1 to 12 carbon atoms, and R represents a hydroxy group or an organic group having 1 to 9 carbon atoms.) 2. The compound according to claim 1, wherein the compound having a carbonyl group is at least one compound selected from the group of compounds represented by the following general formulas (3), (4), and (5): Positive photosensitive resin composition.
(In the formula, L represents a divalent organic group having 1 to 12 carbon atoms.) The positive photosensitive resin composition according to claim 1 , wherein X ₁ in the general formula (1) is at least one aromatic group selected from the group of compounds shown below. object.

  (1) The positive photosensitive resin composition according to any one of claims 1 to 3 is formed on a substrate in the form of a layer or a film, and (2) exposure with actinic radiation through a mask, A method for producing a cured relief pattern, comprising directly irradiating an electron beam or an ion beam, (3) eluting and removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern.   A semiconductor device comprising a cured relief pattern layer obtained by the method for producing a cured relief pattern according to claim 4.