JP4487177B2 - Positive photosensitive resin composition, pattern manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a heat-resistant positive photosensitive resin composition containing a photosensitive polyoxazole precursor, a pattern production method using the same, and an electronic component.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. However, in recent years, as semiconductor devices have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

  On the other hand, photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used. However, when this is used, the pattern creation process can be simplified and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known. In the negative type, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1 to 4), a soluble polyimide having a photopolymerizable olefin (for example, see Patent Documents 5 to 10) ), A self-sensitized polyimide having a benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (see, for example, Patent Documents 11 and 12).

  Since the above negative type requires an organic solvent such as N-methylpyrrolidone for development, a positive photosensitive resin that can be developed with an aqueous alkaline solution has recently been proposed. In the positive type, a method in which an o-nitrobenzyl group is introduced into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a method in which a naphthoquinonediazide compound is mixed in a soluble hydroxylimide or polyoxazole precursor (for example, Patent Documents 13 and 14), a method of introducing naphthoquinone diazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2), and a method in which naphthoquinone diazide is mixed into a polyimide precursor (for example, see Patent Document 15) and so on.

  However, the negative type has a problem in resolution due to its function, and in some applications, there is a problem in that the yield in manufacturing is reduced. In addition, since the structure of the polymer to be used is limited in the above, the physical properties of the finally obtained film are limited, which is not suitable for multipurpose use. On the other hand, the positive type also has the same problems because the sensitivity and resolution are low and the structure is limited due to the problem with the absorption wavelength of the photosensitive agent as described above.

  Also, carboxylic acids such as polybenzoxazole precursor mixed with a diazonaphthoquinone compound (see, for example, Patent Document 16), or polyamic acid having a phenol moiety introduced via an ester bond (for example, see Patent Document 17). Instead of these, phenolic hydroxyl groups have been introduced, but these have insufficient developability, resulting in film loss at unexposed areas and peeling of the resin from the substrate. For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (for example, see Patent Documents 18 and 19). Storage stability deteriorates due to use. In addition, for the purpose of improving storage stability and adhesion, amine end groups sealed with a polymerizable group (see, for example, Patent Documents 20 to 22) have also been proposed. Since a diazoquinone compound containing a large number of aromatic rings is used as a low-sensitivity, it is necessary to increase the addition amount of the diazoquinone compound, and there is a problem that the mechanical properties after thermosetting are remarkably lowered, and it is difficult to say that the material is at a practical level. Is.

  In order to improve the problems of the diazoquinone compound, those using various chemical amplification systems have been proposed. Chemically amplified polyimides (for example, see Patent Document 23), chemically amplified polyimides or polybenzoxazole precursors (for example, see Patent Documents 24 to 30) are mentioned. The deterioration of the induced film characteristics, which are excellent in the film characteristics, show a decrease in sensitivity due to insufficient solubility due to the high molecular weight, and it is difficult to say that both are materials at a practical level. Therefore, in reality, none of them is sufficient for practical use.

Japanese Patent Laid-Open No. 49-11541 Japanese Patent Laid-Open No. 50-40922 JP 54-145794 A JP-A-56-38038, etc. JP 59-108031 A

JP 59-220730 A JP 59-232122 A Japanese Unexamined Patent Publication No. 60-6729 JP-A-60-72925 JP 61-57620 A, etc.

JP 59-219330 A JP-A-231533 Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482 JP 52-13315 A

JP-A-1-46862 JP-A-10-307393 JP-A-4-31861 Japanese Patent Laid-Open No. 4-46345 JP-A-5-197153

JP-A-9-183846 JP 2001-183835 A Japanese Patent Laid-Open No. 3-763 JP 7-219228 A Japanese Patent Laid-Open No. 10-186664

Japanese Patent Laid-Open No. 11-202489 JP 2000-56559 A JP 2001-194791 A JP 2002-526793 A US Pat. No. 6,143,467

J. et al. Macromol. Sci. Chem. , A24, 10, 1407, 1987 Macromolecules, 23, 1990

  The present invention is excellent in sensitivity and resolution by using a specific solvent and additive, and can sufficiently cope with any structure of the polybenzoxazole precursor that imparts photosensitivity. It is an object of the present invention to provide a positive-type photosensitive resin composition that solves the above-described problems and that has excellent adhesion and heat resistance.

  The present invention also provides a method for producing a pattern that can be developed with an alkaline aqueous solution by using the above composition and that has a good sensitivity, resolution, and heat resistance, and that has a good shape. In addition, the present invention provides a highly reliable electronic component by having a pattern having a good shape and characteristics.

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す）で表される繰り返し単位を
有するアルカリ水溶液可溶性のポリアミド、（ｂ）光により酸を発生する化合物、及び、
（ｃ）溶剤を含有してなり、
前記（ｃ）成分が、分子内に少なくとも一つのエステル結合と少なくとも一つの水酸基を有する化合物、及び、一般式（ＩＩ）

（式中、Ｒ ^１ 及びＲ ^２ は各々独立に一価の有機基で、ｌは０〜５の整数）で表される化合物、から選択される化合物を含むポジ型感光性樹脂組成物（但し、（ａ）アルカリ可溶性耐熱性樹脂と、（ｂ）エステル化したキノンジアジド化合物と、（ｃ）（ｃ１）染料、（ｃ２）無機顔料、（ｃ３）有機顔料から選ばれる少なくとも１種の着色剤、を必須成分とすることを特徴とするポジ型感光性樹脂組成物であって、溶媒として乳酸エチルを用いているものを除く。）。 The present invention relates to the following.
[1] (a) General formula (I)

(Wherein U represents a tetravalent organic group and V represents a divalent organic group), an aqueous alkali-soluble polyamide having a repeating unit represented by (b) a compound capable of generating an acid by light, and ,
(C) comprising a solvent,
The component (c) is a compound having at least one ester bond and at least one hydroxyl group in the molecule, and the general formula (II)

(Wherein, a monovalent organic group each independently R ¹ and R ^2, l is an integer of 0 to 5) The positive photosensitive resin composition comprising a compound selected from the compounds represented by (wherein At least one colorant selected from (a) an alkali-soluble heat-resistant resin, (b) an esterified quinonediazide compound, (c) (c1) a dye, (c2) an inorganic pigment, and (c3) an organic pigment, Except for those using ethyl lactate as a solvent .

[2] The positive photosensitive resin composition according to the above [1], wherein the component (c) is a compound having at least one ester bond and at least one hydroxyl group in the molecule .

[3] The positive photosensitive resin composition according to [1] , wherein the component (c) is a compound represented by the general formula (II).
[4] Any one of the above [1] to [3], further comprising (d) a compound having a phenolic hydroxyl group and (e) a compound that inhibits dissolution of the component (a) in the alkaline aqueous solution The positive photosensitive resin composition described in 1.

（式中、Ｘは単結合又は２価の有機基を示し、Ｒ^３〜Ｒ^６は各々独立に水素原子または一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である）で表される化合物である前記［４］に記載のポジ型感光性樹脂組成物。 [5] The component (d) is represented by the general formula (III)

(Wherein X represents a single bond or a divalent organic group, R ^{3 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and m and n are each independently an integer of 1 to 3) And p and q are each independently an integer of 0 to 4, and the positive photosensitive resin composition according to the above [4].

（式中、２つのＡは各々独立に水素原子又は炭素原子数１〜１０のアルキル基で酸素原子、フッ素原子を含んでいても良い）である前記［５］記載のポジ型感光性樹脂組成物。 [6] The group represented by X is

(Wherein, two A's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom), object.

（式中、Ｘ⁻は対陰イオンを示し、Ｒ^７及びＲ^８は各々独立に一価の有機基を示し、ａ及びｂは各々独立に０〜５の整数である）で表されるジアリールヨードニウム塩を含む前記［４］〜［６］のいずれかに記載のポジ型感光性樹脂組成物。 [7] The component (e) is represented by the general formula (IV)

Diaryl ^- (wherein, X represents a counter anion, R ⁷ and R ⁸ each independently represent a monovalent organic group, a and b are the are each independently an integer of 0-5) is represented by The positive photosensitive resin composition according to any one of [4] to [6], which contains an iodonium salt.

[8] (b) component 5 to 100 parts by weight, (d) component 1 to 30 parts by weight, and (e) component 0.01 to 15 parts by weight with respect to 100 parts by weight of component (a) The positive photosensitive resin composition according to any one of [4] to [7].
[9] A step of applying and drying the positive photosensitive resin composition according to any one of [1] to [8] on a support substrate, and a step of exposing the photosensitive resin film obtained by the drying step. A pattern including a step of heating the photosensitive resin film after the exposure, a step of developing the photosensitive resin film after the heating using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development Production method.
[10] An electronic component having an electronic device having a pattern layer obtained by the manufacturing method according to [9], wherein the pattern layer is an interlayer insulating film layer or a surface protection layer in the electronic device. An electronic component provided as a film layer.

  The positive photosensitive resin composition of the present invention is excellent in sensitivity and resolution by increasing the difference in dissolution rate (dissolution contrast) in the developer between the exposed area and the unexposed area. Further, according to the method for producing a pattern of the present invention, by using the composition, a pattern having a good shape and excellent sensitivity, resolution, adhesiveness and heat resistance can be obtained. In addition, the electronic component of the present invention is highly reliable because it has a good shape and a pattern with excellent adhesion and heat resistance.

  The component (a) having the repeating unit represented by the general formula (I) in the present invention is an aqueous alkaline solution-soluble phenolic hydroxyl group-containing polyamide, which is generally used as a precursor of polyoxazole, preferably polybenzoxazole. Function. In addition, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution. The amide unit containing a hydroxy group represented by the general formula (I) is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure at the time of curing.

  The polyamide having the repeating unit represented by the general formula (I) used in the present invention may have the repeating unit. However, the solubility of the polyamide in an alkaline aqueous solution is an OH group bonded to U (generally phenol). It is preferable that the amide unit containing the OH group is contained in a certain ratio or more.

（式中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが４０〜０モル％である）で表されるポリアミドであることが好ましい。ここで、式中のｊとｋのモル分率は、ｊ＝８０〜１００モル％、ｋ＝２０〜０モル％であることがより好ましい。 That is, the following formula

(In the formula, U represents a tetravalent organic group, V and W represent a divalent organic group, j and k represent a mole fraction, and the sum of j and k is 100 mol%, j Is preferably 60 to 100 mol%, and k is 40 to 0 mol%). Here, the molar fraction of j and k in the formula is more preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

  The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  In the present invention, the polyamide having a repeating unit represented by the general formula (I) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines. As the dihalide derivative, a dichloride derivative is preferable.

  The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorination reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  Here, in the general formula (I), the tetravalent organic group represented by U is generally a residue derived from dihydroxydiamine that reacts with dicarboxylic acid to form a polyamide structure, and is a tetravalent aromatic group. A group having 6 to 40 carbon atoms is preferable, and a tetravalent aromatic group having 6 to 40 carbon atoms is more preferable. As the tetravalent aromatic group, a residue of diamine having a structure in which all four bonding sites are present on the aromatic ring and each of the two hydroxy groups is located at the ortho position of the amine is preferable.

  Such diamines include 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, 2,2-bis (3-amino-) 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In the formula of the polyamide, the divalent organic group represented by W is generally a residue derived from diamine (but other than dihydroxydiamine which forms U) which reacts with dicarboxylic acid to form a polyamide structure. A divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

  Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 Examples of aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a silicone group include LP-7100, X-22 161AS, X-22-161A, X-22 161B, X-22-161C, and X-22-161E (both Shin-Etsu Chemical Co., Ltd., trade name) does not but like limited thereto. These compounds are used alone or in combination of two or more.

  In the general formula (I), the divalent organic group represented by V is a dicarboxylic acid-derived residue that reacts with diamine to form a polyamide structure, and is preferably a divalent aromatic group. The number of carbon atoms is preferably 6 to 40, and more preferably a divalent aromatic group having 6 to 40 carbon atoms. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred.

  Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, Aliphatic systems such as 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid and succinic acid Although such a carboxylic acid is not limited thereto. These compounds can be used alone or in combination of two or more.

  The compound (b) used in the present invention, which generates an acid by light, is a photosensitizer and has a function of generating an acid and increasing the solubility of the light irradiated part in an alkaline aqueous solution. . Examples of the type include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Although there is no particular limitation, o-quinonediazide compounds are preferable because of their high sensitivity.

  The o-quinonediazide compound 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-quinonediazide sulfonyl 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 dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the positive photosensitive resin composition of the present invention, the blending amount of the component (b) is based on the difference in dissolution rate between the exposed and unexposed areas and the allowable range of sensitivity with respect to 100 parts by weight of the component (a). 5 to 100 parts by weight is preferable, and 8 to 40 parts by weight is more preferable.

The solvent as the component (c) used in the present invention is selected from a compound having at least one ester bond and at least one hydroxyl group in the molecule, and a compound represented by the following general formula (II). It shall be the essential component a compound.

Examples of such compounds include ethyl lactate and benzyl acetate. By using these compounds, the difference in dissolution rate (dissolution contrast) between the unexposed and exposed portions of the composition of the present invention increases, and sensitivity and resolution are improved. Will improve .

（式中、Ｒ^１及びＲ^２は各々独立に一価の有機基で、ｌは０〜５の整数）
これらの溶剤は単独で又は２種以上併用して用いることができる。

(Wherein R ¹ and R ² are each independently a monovalent organic group, l is an integer of 0 to 5)
These solvents can be used alone or in combination of two or more.

  Other solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl. Other solvents such as ketones can be used in combination. When using together, it is preferable to use 5 to 99 weight% of the compound which has the said ester bond in all the solvents, and it is especially preferable to use 10 to 90 weight%.

  (C) Although there is no restriction | limiting in particular in the quantity of a solvent, Generally it adjusts so that the ratio of the solvent in a composition may be 20 to 90 weight%.

  The compound having a phenolic hydroxyl group, which is the component (d) used in the present invention, increases the dissolution rate of the exposed area when developing with an alkaline aqueous solution, thereby increasing the sensitivity. During curing, the film can be prevented from melting. Although there is no restriction | limiting in particular in the compound which has a phenolic hydroxyl group which can be used for this invention, Since the melt | dissolution promotion effect of an exposure part will become small when molecular weight becomes large, a compound with a molecular weight of 1,500 or less is generally preferable. Among them, those represented by the following general formula (III) are particularly preferable because of excellent balance between the effect of promoting dissolution of the exposed portion and the effect of preventing melting at the time of curing the film.

（式中、Ｘは単結合又は２価の有機基を示し、Ｒ^３〜Ｒ^６は各々独立に水素原子または一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である）

(Wherein X represents a single bond or a divalent organic group, R ^{3 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and m and n are each independently an integer of 1 to 3) And p and q are each independently an integer of 0 to 4)

（式中、個々のＸ’は、各々独立に、単結合、アルキレン基（例えば炭素原子数が１〜１０のもの）、アルキリデン基（例えば炭素数が２〜１０のもの）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホン基、カルボニル基、エーテル結合、チオエーテル結合、アミド結合等から選択されるものであり、Ｒ^９は水素原子、ヒドロキシ基、アルキル基又はハロアルキル基であり、複数存在する場合は互いに同一でも異なっていてもよく、ｍは１〜１０である）で示される２価の有機基が好ましいものとして挙げられる。 In the general formula (III), the divalent group represented by X is an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group or a propylene group, or an alkylidene having 2 to 10 carbon atoms such as an ethylidene group. Groups, arylene groups having 6 to 30 carbon atoms such as phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfone groups, carbonyl groups, ether bonds, thioethers Bond, amide bond, etc., and the following general formula

(In the formula, each X ′ is independently a single bond, an alkylene group (for example, having 1 to 10 carbon atoms), an alkylidene group (for example, having 2 to 10 carbon atoms), or a hydrogen atom thereof. Are selected from a group in which a part or all of them are substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc., and R ⁹ is a hydrogen atom, a hydroxy group, an alkyl group or a haloalkyl group In the case where there are a plurality of them, they may be the same as or different from each other, and m is 1 to 10).

（式中、２つのＡは各々独立に水素原子又は炭素原子数１〜１０のアルキル基で酸素原子、フッ素原子を含んでいても良い）であるものはその効果が高くさらに好ましいものとして挙げられる。 In general formula (II), a group represented by X is

(In the formula, two A's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom). .

  In the positive photosensitive resin composition of the present invention, the blending amount of the component (d) is 1 to 100 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of the development time and the allowable width of the unexposed part remaining film ratio. 30 parts by weight is preferable, and 3 to 25 parts by weight is more preferable.

  In the present invention, the component (e) used is a compound that inhibits the solubility of the component (a) in an alkaline aqueous solution. As such (e) component, an onium salt, a diaryl compound, and a tetraalkylammonium salt are preferable. Examples of the onium salt include iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts, aryldiazonium salts, and the like. Examples of the diaryl compound include those in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are bonded via a bonding group. Groups are preferred. Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.

  Among these, those showing a good dissolution inhibiting effect include diaryl iodonium salts, diaryl urea compounds, diaryl sulfone compounds, tetramethyl ammonium halide compounds, etc., and diaryl urea compounds include diphenyl urea, dimethyl diphenyl urea and the like. Examples of the tetramethylammonium halide compound include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

（式中、Ｘ⁻は対陰イオンを示し、Ｒ^７及びＲ^８は各々独立に一価の有機基を示し、ａ及びｂは各々独立に０〜５の整数である）で表されるジアリールヨードニウム塩化合物が好ましい。陰イオンとしては、硝酸イオン、４弗化硼素イオン、過塩素酸イオン、トリフルオロメタンスルホン酸イオン、ｐ−トルエンスルホン酸イオン、チオシアン酸イオン、塩素イオン、臭素イオン、沃素イオン等が挙げられる。 Among them, general formula (IV)

Diaryl ^- (wherein, X represents a counter anion, R ⁷ and R ⁸ each independently represent a monovalent organic group, a and b are the are each independently an integer of 0-5) is represented by Iodonium salt compounds are preferred. Examples of the anion include nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chlorine ion, bromine ion, iodine ion and the like.

  Examples of the diaryliodonium salt include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, and diphenyliodonium. Bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like can be used.

  Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferable because of their high effects.

  The blending amount of the component (e) is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of sensitivity and an allowable range of development time. Preferably, 0.05 to 3 parts by weight is more preferable.

  The positive photosensitive resin composition of the present invention can contain an organic silane compound, an aluminum chelate compound, or the like in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol , N-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldi) Droxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like. When using these adhesion grant agents, 0.1-20 weight part is preferable with respect to 100 weight part of (a) component, and 0.5-10 weight part is more preferable.

  In addition, the positive photosensitive resin composition of the present invention may be added with an appropriate surfactant or leveling agent in order to prevent coating properties such as striation (film thickness unevenness) or improve developability. Can do. Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and the like. Megafax F171 is a commercially available product. , F173, R-08 (Dainippon Ink Chemical Co., Ltd. product name), Florard FC430, FC431 (Sumitomo 3M Co., Ltd. product name), Organosiloxane polymer KP341, KBM303, KBM403, KBM803 (Product made by Shin-Etsu Chemical Co., Ltd.) Name).

The positive-type photosensitive resin composition of the present invention can be formed into a polyoxazole pattern through a step of coating and drying on a support substrate, a step of exposing, a step of developing, and a step of heat treatment. In the step of applying and drying on a support substrate, the photosensitive resin composition is applied to a spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.), silicon nitride, or the like. After spin coating, dry using a hot plate or oven.

  Next, in the exposure step, the photosensitive resin composition that has become a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the development step, the pattern is obtained by removing the exposed portion with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.

  Next, in the heat treatment step, the obtained pattern is preferably subjected to a heat treatment at 150 to 450 ° C., whereby a heat-resistant polyoxazole pattern having an oxazole ring or other functional group is obtained.

  The positive photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film, interlayer insulating film of semiconductor devices, and interlayers of multilayer wiring boards are used. It can be used for forming an insulating film or the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

  An example of the manufacturing process of the semiconductor device of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coat method or the like (step (a)).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 by a spin coating method so that a predetermined portion of the interlayer insulating film layer 4 is exposed by a known photolithography technique. Is provided with a window 6A (step (b)). The interlayer insulating film layer 4 of the window 6A is selectively etched by dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

  Furthermore, the second conductor layer 7 is formed using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

Next, the surface protective film layer 8 is formed. In the example of this figure, this surface protective film is applied with the photosensitive resin composition by a spin coat method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion, and then an alkaline aqueous solution. And developing to form a pattern, followed by heating to form a polyoxazole film. This polyoxazole film protects the conductor layer from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability.
In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be described specifically by way of examples.
Synthesis Example 1 Synthesis of Polybenzoxazole Precursor In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was heated to 5 ° C. After cooling, 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 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer I). The weight average molecular weight of the polymer I determined by GPC standard polystyrene conversion was 14580, and the degree of dispersion was 1.6.

Synthesis example 2
Synthesis was performed under the same conditions as in Synthesis Example 1 except that 50 mol% of 4,4′-diphenyl ether dicarboxylic acid used in Synthesis 1 was replaced with cyclohexane-1,4-dicarboxylic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight determined by standard polystyrene conversion of 18580 and a dispersity of 1.5.

Photosensitive characteristics evaluation The components (b), (d), and (e) were blended in predetermined amounts shown in Table 1 with respect to 100 parts by weight of the polybenzoxazole precursor. The solvent of component (c) was used in a range of 1.5 to 1.8 times by weight with respect to component (a).

The solution was spin-coated on a silicon wafer to form a coating film having a dry film thickness of 3 to 10 μm, and then exposed to i-line (365 nm) using an ultrahigh pressure mercury lamp through an interference filter. After exposure, heat at 120 ° C. for 3 minutes, develop with a 2.38% aqueous solution of tetramethylammonium hydroxide until the exposed silicon wafer is exposed, then rinse with water to obtain the minimum exposure required for pattern formation. The resolution was determined. Moreover, the dissolution rate ratio (dissolution contrast) of an unexposed part and an exposed part (exposure amount 200 mJ · cm ⁻² ) was determined. The results are shown in Table 2.

以上のように、高感度、高解像度が得られた。

As described above, high sensitivity and high resolution were obtained.

Comparative Example Synthesis Example 3
3.75 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.86 g of 4,4′-diaminodiphenyl ether (DDE) were dissolved in 30 g of N-methylpyrrolidone (NMP). The mixture was stirred at 60 ° C. for 4 hours and then at room temperature overnight to obtain polyamic acid. This solution was poured into 1 liter of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain polyamic acid (polyimide precursor) (hereinafter referred to as polymer III). The weight average molecular weight calculated | required by standard polystyrene conversion of the polymer III was 34580, and dispersion degree was 1.8.

Photosensitive characteristics evaluation Table 3 shows the components (b), (d), and (e) with respect to 100 parts by weight of the polyimide precursor (polymer III) or 100 parts by weight of the polybenzoxazole precursor (polymer I). Formulated in a predetermined amount. The solvent of component (c) was used in a range of 1.5 to 1.8 times by weight with respect to component (a). As a result, as shown in Table 4, in all cases, the dissolution contrast was lower than that in Examples, and a high-definition pattern was not obtained.

It is a manufacturing process figure of the semiconductor device of a multilayer wiring structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... 1st conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window, 7 ... 2nd conductor layer, 8 ... Surface protective film layer.

Claims (10)

(A) General formula (I)

(Wherein U represents a tetravalent organic group and V represents a divalent organic group), an aqueous alkali-soluble polyamide having a repeating unit represented by (b) a compound capable of generating an acid by light, and ,
(C) comprising a solvent,
The component (c) is a compound having at least one ester bond and at least one hydroxyl group in the molecule, and the general formula (II)

(Wherein, a monovalent organic group each independently R ¹ and R ^2, l is an integer of 0 to 5) The positive photosensitive resin composition comprising a compound selected from the compounds represented by (wherein At least one colorant selected from (a) an alkali-soluble heat-resistant resin, (b) an esterified quinonediazide compound, (c) (c1) a dye, (c2) an inorganic pigment, and (c3) an organic pigment, Except for those using ethyl lactate as a solvent . The positive photosensitive resin composition according to claim 1, wherein the component (c) is a compound having at least one ester bond and at least one hydroxyl group in the molecule . The positive photosensitive resin composition according to claim 1 , wherein the component (c) is a compound represented by the general formula (II).   The positive photosensitive resin according to claim 1, further comprising (d) a compound having a phenolic hydroxyl group, and (e) a compound that inhibits dissolution of the component (a) in the alkaline aqueous solution. Resin composition. The component (d) is represented by the general formula (III)

(Wherein X represents a single bond or a divalent organic group, R ^{3 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and m and n are each independently an integer of 1 to 3) The positive photosensitive resin composition according to claim 4, wherein p and q are each independently a compound represented by 0 to 4. A group represented by X is

6. The positive photosensitive resin composition according to claim 5, wherein two A's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom. . (E) the component is represented by the general formula (IV)

Diaryl ^- (wherein, X represents a counter anion, R ⁷ and R ⁸ each independently represent a monovalent organic group, a and b are the are each independently an integer of 0-5) is represented by The positive photosensitive resin composition in any one of Claims 4-6 containing an iodonium salt.   5) 100 parts by weight of component (a), 5 to 100 parts by weight of component (b), 1 to 30 parts by weight of component (d), and 0.01 to 15 parts by weight of component (e). The positive photosensitive resin composition in any one of -7.   The process of apply | coating the positive photosensitive resin composition in any one of Claims 1-8 on a support substrate, and drying, The process of exposing the photosensitive resin film obtained by the said drying process, The photosensitive after the said exposure The pattern manufacturing method including the process of heating the photosensitive resin film | membrane, the process of developing the photosensitive resin film after the heating using alkaline aqueous solution, and the process of heat-processing the photosensitive resin film after the said image development.   An electronic component having an electronic device having a pattern layer obtained by the manufacturing method according to claim 9, wherein the pattern layer is provided as an interlayer insulating film layer or a surface protective film layer in the electronic device. Electronic parts characterized by being made.

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