JP2014224855A - Photosensitive resin composition, method of producing patterned cured film, and semiconductor device having said patterned cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which allows development with an alkali aqueous solution and can satisfy all of good resolution, good breaking elongation and good heat resistance, a method of producing a patterned cured film using the same, and a semiconductor device having the patterned cured film.SOLUTION: A photosensitive resin composition contains (a) a polyamide-imide resin having a structural unit represented by the general formula (1) in the figure, (b) a compound that generates acid in response to light, (c) a thermal crosslinking agent, and (d) a solvent. (In the general formula (1), Ris one of divalent organic groups represented by the general formula (2), nis an integer between 1 and 20, nis an integer between 1 and 50, nis an integer between 1 and 70, nis an integer between 1 and 5, nis an integer between 1 and 10, nis an integer between 1 and 5, and Ris a divalent organic group.

Description

  The present invention relates to a photosensitive resin composition having good mechanical properties and heat resistance. Moreover, it is related with the manufacturing method of the pattern cured film using this photosensitive resin composition, and the semiconductor device which has this pattern cured film.

  In recent years, with high integration and large size of semiconductor devices, as a material for forming interlayer insulation layers, surface protective layers, and rewiring layers of semiconductor devices, photosensitivity, excellent electrical characteristics, heat resistance, mechanical characteristics, etc. There is a need for materials that have both. Conventionally, a photosensitive resin composition containing a polyimide precursor resin having high heat resistance has been used as such a material (for example, Patent Document 1).

However, a film formed from a polyimide precursor resin undergoes volume shrinkage due to dehydration (imidization) of the polyimide precursor during curing, resulting in a change in film thickness and a decrease in dimensional accuracy. Further, when the polyimide precursor resin is cured at a low temperature, imidization is incomplete, so that the cured film is brittle and mechanical properties and heat resistance may be lowered.
Therefore, there is no volume shrinkage due to dehydration during curing, and polyamideimide resins that can be used for low-temperature processes are already being studied because they have already been imidized, and further contain positive photosensitive polyamideimide resins that have been imparted with photosensitive properties. Compositions are known (see, for example, Patent Documents 2 to 4).

JP 59-219330 A Japanese Patent No. 2524240 Japanese Patent No. 2524241 Japanese Patent No. 2902761

  However, a polyamideimide resin-containing composition that has good photosensitivity and adhesion of the resin film to the substrate during development and can be developed with an aqueous alkaline solution has not yet been obtained. Moreover, since the semiconductor device is requested | required of further reliability, the high fracture | rupture elongation is calculated | required from a viewpoint of improving crack tolerance, such as an impact resistance test, for example. Moreover, favorable heat resistance is calculated | required from a viewpoint of tolerance with respect to the various high temperature process in the manufacturing process of the semiconductor device after pattern cured film formation.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition that can be developed with an alkaline aqueous solution and can satisfy all of good resolution, elongation at break and heat resistance. Moreover, it aims at providing the manufacturing method of the pattern cured film using the same, and the semiconductor device which has a pattern cured film.

The present invention is as follows.
<1> (a) a polyamideimide resin having a structural unit represented by the following general formula (1), (b) a compound that generates an acid by light, (c) a thermal crosslinking agent, (d) a solvent, And a photosensitive resin composition.

（一般式（１）中、Ｒ^１は、下記一般式（２）で表される二価の有機基のいずれかであり、ｎ^１は１〜２０、ｎ^２は１〜５０、ｎ^３は１〜７０、ｎ^４は１〜５、ｎ^５は１〜１０、ｎ^６は１〜５を示す。Ｒ^２は二価の有機基である。）

(In General Formula (1), R ¹ is ^one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, n ⁶ is 1 to 5. R ² is a divalent organic group.

＜２＞（ｂ）成分の光により酸を発生する化合物が、ｏ−キノンジアジド化合物である、前記感光性樹脂組成物。
＜３＞（ｃ）成分の熱架橋剤が、ヒドロキシメチルアミノ基を有する化合物又はエポキシ基を有する化合物である前記感光性樹脂組成物。
＜４＞（ａ）成分のポリアミドイミド樹脂が、一般式（３）で表わされる構造単位を有するポリアミドイミド樹脂である、前記感光性樹脂組成物。

<2> The photosensitive resin composition, wherein the compound that generates an acid by the light of the component (b) is an o-quinonediazide compound.
<3> The photosensitive resin composition, wherein the thermal crosslinking agent as the component (c) is a compound having a hydroxymethylamino group or a compound having an epoxy group.
<4> The photosensitive resin composition, wherein the polyamideimide resin as the component (a) is a polyamideimide resin having a structural unit represented by the general formula (3).

（一般式（３）中、Ｒ^１は、下記一般式（２）で表される二価の有機基のいずれかであり、ｎ^１は１〜２０、ｎ^２は１〜５０、ｎ^３は１〜７０、ｎ^４は１〜５、ｎ^５は１〜１０、ｎ^６は１〜５を示す。Ｒ^３は、水素、メチル基、又はエチル基のいずれかである。）

(In General Formula (3), R ¹ is any one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, and n ⁶ is 1 to 5. R ³ is hydrogen, a methyl group, or an ethyl group.

＜５＞（ａ）成分のポリアミドイミド樹脂が、さらに一般式（４）で表わされる構造単位を有するポリアミドイミド樹脂である、前記感光性樹脂組成物。

<5> The photosensitive resin composition, wherein the polyamideimide resin as the component (a) is a polyamideimide resin further having a structural unit represented by the general formula (4).

（一般式（４）中、Ｒ^４は、二価の有機基をしめす。）
＜６＞前記感光性樹脂組成物を基板上に塗布して樹脂膜を形成する工程と、前記樹脂膜に露光及び現像を行い、パターン樹脂膜を形成する工程と、前記パターン樹脂膜を加熱する工程とを含有する、パターン硬化膜の製造方法。
＜７＞パターン樹脂膜を加熱する工程を２５０℃以下で行う、前記パターン硬化膜の製造方法。
＜８＞前記パターン硬化膜の製造方法により形成されるパターン硬化膜を層間絶縁膜又は表面保護層として有する半導体装置。

(In the general formula (4), R ⁴ represents a divalent organic group.)
<6> Applying the photosensitive resin composition on a substrate to form a resin film, exposing and developing the resin film to form a pattern resin film, and heating the pattern resin film The manufacturing method of a pattern cured film containing a process.
<7> The method for producing a patterned cured film, wherein the step of heating the patterned resin film is performed at 250 ° C. or lower.
<8> A semiconductor device having a patterned cured film formed by the method for producing a patterned cured film as an interlayer insulating film or a surface protective layer.

  According to the present invention, it is possible to provide a photosensitive resin composition that can be developed with an aqueous alkaline solution and that can satisfy all of good resolution, elongation at break and heat resistance. Moreover, the manufacturing method of the pattern cured film using this, and the semiconductor device which has a pattern cured film can be provided.

It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing which shows one Embodiment of an electronic component (semiconductor device). It is a schematic sectional drawing which shows one Embodiment of an electronic component (semiconductor device).

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In addition, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention includes (a) a polyamideimide resin having a structural unit represented by the following general formula (1), (b) a compound that generates an acid by light, and (c) a thermal crosslinking agent. And (d) a solvent.

（一般式（１）中、Ｒ^１は、下記一般式（２）で表される二価の有機基のいずれかであり、ｎ^１は１〜２０、ｎ^２は１〜５０、ｎ^３は１〜７０、ｎ^４は１〜５、ｎ^５は１〜１０、ｎ^６は１〜５を示す。Ｒ^２は二価の有機基である。）

(In General Formula (1), R ¹ is ^one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, n ⁶ is 1 to 5. R ² is a divalent organic group.

以下、本発明の感光性樹脂組成物に用いられる各成分について説明する。

Hereinafter, each component used for the photosensitive resin composition of this invention is demonstrated.

((A) Polyamideimide resin having a structural unit represented by the general formula (1))
The photosensitive resin composition of the present invention is (a) a polyamideimide resin having a structural unit represented by the following general formula (1).

（一般式（１）中、Ｒ^１は、下記一般式（２）で表される二価の有機基のいずれかであり、ｎ^１は１〜２０、ｎ^２は１〜５０、ｎ^３は１〜７０、ｎ^４は１〜５、ｎ^５は１〜１０、ｎ^６は１〜５を示す。Ｒ^２は二価の有機基である。）

(In General Formula (1), R ¹ is ^one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, n ⁶ is 1 to 5. R ² is a divalent organic group.

一般式（１）で表される構造単位を有するポリアミドイミド樹脂は、脂肪族ジアミン化合物由来の２価の直鎖の有機基を含有するため、ポリアミドイミド樹脂が柔軟なポリマーとなり、破断伸びに優れる感光性樹脂組成物を提供することができる。なお、ｎ^１〜ｎ^６は構成単位の構成単位数を示す。従って単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構成単位の構成単位数については同様に定義する。

Since the polyamideimide resin having the structural unit represented by the general formula (1) contains a divalent linear organic group derived from an aliphatic diamine compound, the polyamideimide resin becomes a flexible polymer and has excellent elongation at break. A photosensitive resin composition can be provided. N ^{1 to} n ⁶ represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the number of structural units is defined similarly.

  The component (a) is a polyamideimide resin having a structural unit represented by the general formula (3). It is preferable.

（一般式（３）中、Ｒ^１は、上記一般式（２）で表される二価の有機基のいずれかであり、ｎ^１は１〜２０、ｎ^２は１〜５０、ｎ^３は１〜７０、ｎ^４は１〜５、ｎ^５は１〜１０、ｎ^６は１〜５を示す。Ｒ^３は、水素、メチル基、又はエチル基のいずれかである。）
（ａ）成分のポリアミドイミド樹脂は、一般式（１）で表される構造単位を有するポリアミドイミド樹脂であれば制限はないが、ポリアミドイミド樹脂中に一般式（１）で表される構造単位を１０〜７０モル％含有することが好ましく、２０〜５０モル％含有することがより好ましく、２５〜４５モル％含有することがさらに好ましい。

(In General Formula (3), R ¹ is any one of the divalent organic groups represented by General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, and n ⁶ is 1 to 5. R ³ is hydrogen, a methyl group, or an ethyl group.
The polyamideimide resin of component (a) is not limited as long as it is a polyamideimide resin having a structural unit represented by the general formula (1), but the structural unit represented by the general formula (1) in the polyamideimide resin. It is preferable to contain 10-70 mol%, It is more preferable to contain 20-50 mol%, It is more preferable to contain 25-45 mol%.

  The polyamideimide resin represented by the general formula (1) reacts a diimide dicarboxylic acid obtained by reacting a diamine represented by the following general formula (5) with tricarboxylic acid monoanhydride and diisocyanates. Can be obtained.

（一般式（５）中、Ｒ^１は、下記一般式（２）で表される二価の有機基のいずれかであり、ｎ^１は１〜２０、ｎ^２は１〜５０、ｎ^３は１〜７０、ｎ^４は１〜５、ｎ^５は１〜１０、ｎ^６は１〜５を示す。）

(In General Formula (5), R ¹ is any one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, and n ⁶ is 1 to 5.

  Examples of such diamines (aliphatic diamines) include ethylene diamine, tetramethylene diamine, hexamethylene diamine, 4,9-dioxadodecane-1,12-diamine, polyoxytetramethylene diamine, polyoxyethylene diamine, polyoxy Examples include propylene diamine and polyoxytetramethylene-polyoxypropylene copolymer diamine. From the viewpoints of flexibility and heat resistance, it is preferable to use polyoxypropylene diamine. These diamines are used alone or in combination of two or more.

  In addition, in order to adjust the solubility in an alkaline aqueous solution and to obtain better sensitivity, when synthesizing diimidedicarboxylic acid, a diamine having a phenolic hydroxyl group may be contained in addition to the aliphatic diamine. Good. The diamine having a phenolic hydroxyl group is a compound having one or more phenolic hydroxyl groups in the molecule and having two or more amino groups. Examples of such a diamine having a phenolic hydroxyl group include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and 2,2-bis. (3-amino-4-hydroxyphenyl) propane, 2,2-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-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bi {4- (3-amino-4-hydroxyphenoxy) phenyl} fluorene, 1,3-bis (3-amino-4-hydroxyphenyl) adamantane, 1,3-bis {4- (3-amino-4-hydroxy Phenoxy) phenyl} adamantane, 2,2-bis (3-amino-4-hydroxyphenyl) adamantane, 2,2-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, 2- (3- Hydroxy-4-aminophenyl) -2- (3-amino-4-droxyphenyl) hexafluoropropane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-diamino-4,4 '-Dihydroxybenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-diamino-4,4 -Dihydroxydiphenyl ether, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 2,6-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3-hydroxy-4,4'-diamino Biphenyl, 4-hydroxy-3,3'-diaminobiphenyl, 2- (3-amino-4-hydroxyphenyl) -2- (3-aminophenyl) hexafluoropropane, 3-hydroxy-4,4'-diaminodiphenyl Examples include sulfone, 3-hydroxy-4,4′-diaminodiphenyl ether and 3-hydroxy-4,4′-diaminodiphenylmethane. These compounds can be used alone or in combination of two or more.

  Further, when synthesizing diimide dicarboxylic acid, other than the above aliphatic diamine and diamine having a phenolic hydroxyl group, for the purpose of adjusting the solubility in an alkaline aqueous solution and adjusting various physical properties of the composition and the pattern cured film. Diamine may be contained. 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- (4-aminophenoxy) phenyl] ether, aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, LP-7100, X-22-161AS, X-22-161A, X-22-161B , X-22-161C, X-22-161E Both Shin-Etsu Chemical Co., Ltd., and the like diamine having a siloxane skeleton of a trade name), and the like. These compounds are used singly or in combination of two or more.

  In the present invention, when the diamine used for synthesizing the diimide dicarboxylic acid contains the diamine having the phenolic hydroxyl group or the diamine other than the aliphatic diamine, the content of the aliphatic diamine in the diamine is the sum of the diamines 100. It is preferably 10 to 70 mol%, more preferably 20 to 50 mol%, still more preferably 25 to 45 mol% with respect to mol%. When the ratio of the aliphatic diamine is 10 mol% or more, there is a tendency that better elongation at break can be expressed, and when it is 70 mol% or less, the alkali solubility tends to be lowered.

  Examples of tricarboxylic acid monoanhydrides used in the synthesis of diimide dicarboxylic acid include trimellitic acid anhydride (1,2,4-tricarboxybenzene-1,2 anhydride), hemimellitic acid anhydride (1,2,3- Tricarboxybenzene-1,2 anhydride), 2,3,5-tricarboxynaphthalene-2,3-anhydride, 4- (4-carboxyphenoxy) phthalic anhydride, 1,2,4-carboxycyclohexane- 1,2 anhydride, 1,2,3-tricarboxycyclopropane-1,2 anhydride, 1,2,3-tricarboxycyclobutane-1,2 anhydride, aconitic acid anhydride, etc. It is not limited to. These compounds can be used individually by 1 type or in combination of 2 or more types.

  When synthesizing diimide dicarboxylic acid, the mixing ratio of the diamine compound and the tricarboxylic acid monoanhydride is 1.5 to 2.1.5% of the tricarboxylic acid monoanhydride tetracarboxylic acid dianhydride with respect to 1 mol of the total diamine compound. Although it is 5 mol, it is preferable that it is 1.8-2.2 mol, and it is further more preferable that it is 1.9-2.2 mol. When the tricarboxylic acid monoanhydride is 1.5 mol or more, the effect of adjusting the dissolution rate in the alkaline aqueous solution is higher, and when it is 2.5 mol or less, the molecular weight of the oligomer is prevented from being increased, and the dissolution rate in the alkaline aqueous solution is It is possible to prevent further deterioration.

  Diimide dicarboxylic acid can be synthesized by a known method. For example, the diamine and the tricarboxylic acid monoanhydride are mixed with an organic solvent (N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N , N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, toluene, benzene, etc.) to synthesize a diimide dicarboxylic acid precursor and then imidize to obtain diimide dicarboxylic acid.

  For example, imidization may be performed by heating and refluxing using toluene or xylene. 30-300 degreeC is preferable and, as for the reaction temperature of imidation, 50-250 degreeC is more preferable. Moreover, the method etc. which heat in presence of base catalysts, such as a pyridine, are mentioned, -20-200 degreeC is preferable and the reaction temperature in the case of using a catalyst has more preferable 0-150 degreeC. The reaction time for imidization is approximately 10 minutes to 10 hours, and the atmosphere may be either air or an inert gas atmosphere, and can be performed in a pressurized or reduced pressure atmosphere in addition to atmospheric pressure. Here, when synthesizing diimide dicarboxylic acid having a phenolic hydroxyl group, if imidization is performed under heating and reflux using toluene or xylene, the diisocyanate is not purified without purifying the diimide dicarboxylic acid having a phenolic hydroxyl group. Can be reacted, which is preferable.

The polyamide-imide resin used in the photosensitive resin composition of the present invention can be obtained by reacting the diimide dicarboxylic acid obtained by the above method with diisocyanate.
Examples of the diisocyanate include 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,3-bis (isocyanatomethyl) benzene, 1,3-phenylene diisocyanate, and 1,4-diisocyanate. Natobutane, 1,4-phenylene diisocyanate, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 3,3 '-Dimethoxy-4,4'-biphenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, tolylene diisocyanate (2, 4-diisocyanatotolylene, 2,5-diisocyanatotolylene, 2,6-diisocyanatotolylene, α, 4- Isocyanatotolylene alone or in mixture), trans-1,4-cyclohexylene diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 3,3′-dimethyl-4,4 ′ -Biphenylene diisocyanate, 4-bromo-6-methyl-1,3-phenylene diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2-chlorophenylisocyanate), 4 , 4'-methylenebis (2,6-diethylphenyl isocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), 4,4'-oxybis (phenyl isocyanate), 1,3-bis (isocyanatomethyl) Examples include cyclohexane and trimethyl-1,6-diisocyanatohexane, The present invention is not limited to these. These compounds can be used individually by 1 type or in combination of 2 or more types.

  The reaction between the diimide dicarboxylic acid and the diisocyanate can be carried out by a known method. For example, diimide dicarboxylic acid and diisocyanate are reacted in an organic solvent (N-methyl-2-pyrrolidone, N-methyl- 2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, toluene, benzene, etc.). In the polymerization reaction, the carboxyl group of diimidecarboxylic acid is added to the isocyanate group of diisocyanate, and then an amide group is formed by thermal decomposition accompanied by decarboxylation of the carboxycarbonylamino group to be produced. 30-300 degreeC is preferable and, as for the reaction temperature of diimide dicarboxylic acid and diisocyanate, 50-250 degreeC is more preferable. The reaction time is approximately 10 minutes to 10 hours, and the atmosphere may be either air or an inert gas atmosphere, and can be performed in a pressurized or reduced pressure atmosphere in addition to atmospheric pressure. After the reaction, the product may be used as it is as the polyamideimide resin of the present invention, or may be used after reprecipitation of the polyamideimide resin in a poor solvent.

  Furthermore, for the purpose of improving the solubility in an aqueous alkali solution, dicarboxylic acid having a phenolic hydroxyl group other than the above diimide dicarboxylic acid can be added in the synthesis of the polyamideimide resin. Examples of the dicarboxylic acid having a phenolic hydroxyl group include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid, and 2-hydroxyterephthalic acid. These compounds are used singly or in combination of two or more.

  The molecular weight of the polyamide-imide resin as component (a) of the present invention is preferably 3,000 to 200,000 in terms of weight average molecular weight in consideration of the balance between solubility in an alkaline aqueous solution, photosensitive properties and cured film properties. 000-100,000 are more preferable. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

((B) Compound that generates acid by light)
The photosensitive resin composition of the present invention contains (b) a compound that generates an acid by light as a photosensitive agent. Such a component (b) has a function of generating an acid by light irradiation and increasing the solubility of the irradiated portion in an alkaline aqueous solution. As the component (b), a compound generally called a photoacid generator can be used. Specific examples of the component (b) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like. Among these, it is preferable to use an o-quinonediazide compound because of its high sensitivity.

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

  Examples of the o-quinonediazide sulfonyl chloride include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, and the like. It is done.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 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) propa 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris ( 4-hydroxyphenyl) ethane and the like.

  Examples of the amino compound 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) hexafluoro Examples thereof include propane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane.

  Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. Moreover, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.

  Among these, from the absorption wavelength range and reactivity, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1 -Naphthoquinone-2-diazide-5-sulfonyl chloride obtained by condensation reaction, tris (4-hydroxyphenyl) methane or tris (4-hydroxyphenyl) ethane and 1-naphthoquinone-2-diazide-5 -It is preferable to use what was obtained by condensation reaction with sulfonyl chloride.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound are such that the total number of moles of hydroxy group and amino group is 0.5 to 1 mole per mole of o-quinonediazide sulfonyl chloride. It is preferable to mix. A preferable blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 molar equivalent.

  In addition, the preferable reaction temperature of the above-mentioned reaction is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.

  In the photosensitive resin composition of the present invention, the content of the component (b) is preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, with respect to 100 parts by weight of the component (a). Part is more preferred. When the component (b) is 3 to 100 parts by mass with respect to 100 parts by mass of the component (a), the difference in dissolution rate between the exposed part and the unexposed part becomes good, and the tolerance of sensitivity becomes good.

((C) Thermal crosslinking agent))
The photosensitive resin composition of this invention contains the thermal crosslinking agent which is (c) component. The component (c) reacts with the component (a) to form a bridge structure when it is heated after forming the pattern resin film to form a pattern cured film. Thereby, the mechanical strength and chemical resistance of the pattern cured film can be improved. As the component (c), specifically, a compound having a hydroxymethylamino group, a compound having an epoxy group, or the like can be used.

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N- And nitrogen-containing compounds obtained by alkylating all or part of methylol groups such as hydroxymethyl) urea. Here, the alkyl group of the alkyl ether includes a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, and tetrakis (methoxymethyl) urea.

  A conventionally well-known thing can be used as a compound which has an epoxy group. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin, polyalkylene glycol diglycidyl ether. Etc.

  Further, as the component (c), in addition to those described above, hydroxymethyl such as bis [3,4-bis (hydroxymethyl) phenyl] ether and 1,3,5-tris (1-hydroxy-1-methylethyl) benzene Aromatic compounds having a group, compounds having a maleimide group such as bis (4-maleimidophenyl) methane and 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, multifunctional An acrylate compound, a compound having an oxetanyl group, a compound having a vinyl group, or a blocked isocyanate compound can be used.

In the photosensitive resin composition of the present invention, the content of the component (c) is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the component (a), and 3 to 25 Part by mass is more preferable. When the component (c) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (a), the difference in dissolution rate between the exposed part and the unexposed part becomes good, and the tolerance of sensitivity becomes good.
In addition, the thermal crosslinking agent mentioned above is used individually by 1 type or in combination of 2 or more types.

((D) solvent))
The photosensitive resin composition of the present invention contains (d) a solvent in order to dissolve the components (a), (b) and (c). By containing the solvent, it is possible to facilitate application on the substrate and to form a coating film having a uniform thickness. Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N , N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Examples thereof include monobutyl ether and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more.

  Moreover, although content of (d) solvent is not specifically limited, It is preferable to adjust so that the ratio of the solvent in the photosensitive resin composition may be 20-90 mass%.

(Other ingredients)
In addition to the components (a) to (d), the photosensitive resin composition described above includes compounds that generate an acid by heating, dissolution accelerators, dissolution inhibitors, coupling agents, and surfactants or leveling agents. You may contain a component.

(Compound that generates acid by heating)
The photosensitive resin composition of the present invention can generate an acid when the photosensitive resin film is heated by using a compound that generates an acid by heating, and the components (a) and (c) This reaction, that is, thermal crosslinking reaction is promoted, and the heat resistance of the cured film is improved. Moreover, since the compound which produces | generates an acid by heating generate | occur | produces an acid also by light irradiation, the solubility to the alkaline aqueous solution of an exposure part increases. Therefore, the difference in solubility in the alkaline aqueous solution between the unexposed area and the exposed area is further increased, and the resolution is improved.

  It is preferable that the compound which produces | generates an acid by such a heating is what produces | generates an acid by heating to 50-250 degreeC, for example. Specific examples of the compound that generates an acid by heating include a salt formed from a strong acid such as an onium salt and a base, and imide sulfonate.

  Examples of the onium salt include diaryliodonium salts such as aryldiazonium salts and diphenyliodonium salts; di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trialkylsulfonium salts such as trimethylsulfonium salts; Examples include dialkyl monoaryl sulfonium salts such as dimethylphenylsulfonium salt; diaryl monoalkyl iodonium salts such as diphenylmethylsulfonium salt; and triarylsulfonium salts. Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid Dimethylphenylsulfonium salt and diphenylmethylsulfonium salt of toluenesulfonic acid are preferred.

  Moreover, as a salt formed from a strong acid and a base, the salt formed from the following strong acids and a base other than the above-mentioned onium salt, for example, a pyridinium salt can also be used. Strong acids include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, ethanesulfonic acid And alkylsulfonic acids such as butanesulfonic acid. Examples of the base include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.

  As the imide sulfonate, for example, naphthoyl imide sulfonate or phthalimide sulfonate can be used.

  When using the compound which produces | generates an acid by heating, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) component, 0.2-20 mass parts is more preferable, 0.5 More preferably, it is 10 mass parts.

(Dissolution promoter)
By blending the dissolution accelerator in the above-described photosensitive resin composition, the dissolution rate of the exposed area when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. A conventionally well-known thing can be used as a dissolution promoter. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.

  The content in the case of using such a dissolution accelerator can be determined by the dissolution rate with respect to the alkaline aqueous solution, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of component (a). .

(Dissolution inhibitor)
The dissolution inhibitor is a compound that inhibits the solubility of the component (a) in an alkaline aqueous solution, and is used to control the remaining film thickness, development time, and contrast. Specific examples thereof include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like. In the case of using a dissolution inhibitor, the content is preferably 0.01 to 20 parts by weight, and 0.01 to 15 parts by weight with respect to 100 parts by weight of component (a), from the viewpoint of sensitivity and the allowable range of development time. Is more preferable, and 0.05 to 10 parts by mass is particularly preferable.

(Coupling agent)
By mix | blending a coupling agent with the above-mentioned photosensitive resin composition, the adhesiveness with the board | substrate of the cured film formed can be improved. Examples of the coupling agent include organic silane compounds and aluminum chelate compounds.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, 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 (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, and, when using a coupling agent, 0.5-10 mass parts is more preferable.

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent with the above-described photosensitive resin composition, coating properties such as striation (film thickness unevenness) can be prevented, and developability can be improved. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Commercially available products include Megafax F171, F173, R-08 (Dainippon Ink Chemical Co., Ltd., trade name), Fluorad FC430, FC431 (Sumitomo 3M Limited, trade name), organosiloxane polymers KP341, KBM303, KBM403. And KBM803 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  When using surfactant or a leveling agent, 0.001-5 mass parts is preferable with respect to 100 mass parts of (a) component, and 0.01-3 mass parts is more preferable.

  The photosensitive resin composition described above can be developed using an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH). Furthermore, by using the above-described photosensitive resin composition, it is possible to form a cured pattern film having good adhesion and thermal shock resistance with sufficiently high sensitivity and resolution.

<Method for producing patterned cured film>
Next, the manufacturing method of a pattern cured film is demonstrated. The method for producing a patterned cured film of the present invention includes a step of applying a photosensitive resin composition on a substrate to form a resin film, a step of exposing and developing the resin film to form a pattern resin film, And a step of heating the pattern resin film. Hereinafter, although each process is demonstrated in detail, this invention is not limited at all by these description.

<Application / drying (film formation) process>
First, the photosensitive resin composition of the present invention is applied on a support substrate and dried to form a resin film. In this step, the photosensitive resin composition described above is spin-coated using a spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ or SiO ₂ ), or silicon nitride. To form a coating film. The support substrate on which the coating film has been formed is dried using a hot plate, oven, or the like. Thereby, a resin film is formed on the support substrate.

<Exposure process>
Next, in the exposure step, the resin film formed on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the above-described photosensitive resin composition, after exposure, post-exposure heating (PEB) can be performed as necessary. The post-exposure heating temperature is preferably 70 to 140 ° C., and the post-exposure heating time is preferably 1 to 5 minutes.

<Development process>
In the development step, the resin film is patterned by removing the exposed portion of the resin film after the exposure step with a developer. As the developer, for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) is preferably used. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. 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 mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer.

<Heat treatment process>
Next, in the heat treatment step, a patterned cured film can be formed by heat-treating the patterned resin film. The heating temperature in the heat treatment step is desirably 250 ° C. or less, more desirably 225 ° C. or less, and further desirably 150 to 200 ° C. from the viewpoint of sufficiently preventing damage to the electronic device due to heat.

  The heat treatment can be performed using an oven such as a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the process under nitrogen because the oxidation of the pattern can be prevented. Since the above-mentioned desirable heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the electronic device can be suppressed to a small level. Therefore, an electronic device can be manufactured with a good yield by using the method for manufacturing a patterned cured film of the present invention. It also leads to energy savings in the process. Furthermore, according to the photosensitive resin composition of the present invention, since the volume shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide or the like is small, it is possible to prevent a reduction in dimensional accuracy.

  The heat treatment time in the heat treatment step may be a time sufficient for the photosensitive resin composition to cure, but is preferably about 5 hours or less in view of work efficiency.

  The heat treatment can be performed using a microwave curing device or a variable frequency microwave curing device in addition to the above-described oven. By using these apparatuses, it is possible to effectively heat only the resin film while keeping the temperature of the substrate and the electronic device at, for example, 200 ° C. or lower.

  In the variable frequency microwave curing apparatus, the microwave is irradiated in pulses while changing its frequency, so that standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when metal wiring is included as an electronic component to be described later as a substrate, it is possible to prevent the occurrence of electric discharge from the metal by irradiating microwaves in a pulsed manner while changing the frequency. Since it can protect, it is preferable. Furthermore, it is preferable to heat using a frequency-variable microwave because the properties of the cured film do not deteriorate even if the curing temperature is lowered as compared with the case of using an oven.

  According to the method for producing a patterned cured film as described above, a patterned cured film having satisfactory heat resistance can be obtained with sufficiently high sensitivity and resolution.

<Manufacturing process of semiconductor device and semiconductor device>
A semiconductor device refers to a semiconductor package, a semiconductor memory, or the like having a multilayer wiring structure, a rewiring structure, or the like. Here, as an example of the method for manufacturing a semiconductor device of the present invention, a manufacturing process of the semiconductor device will be described with reference to the drawings. 1 to 5 are schematic sectional views showing an embodiment of a manufacturing process of a semiconductor device having a multilayer wiring structure.

  First, the structure 100 shown in FIG. 1 is prepared. The structure 100 includes a semiconductor substrate 1 such as an Si substrate having circuit elements, a protective film 2 such as a silicon oxide film covering the semiconductor substrate 1 having a predetermined pattern from which the circuit elements are exposed, and on the exposed circuit elements. And the interlayer insulating layer 4 made of a polyimide resin or the like formed on the protective film 2 and the first conductor layer 3 by a spin coating method or the like.

  Next, a photosensitive resin layer 5 having a window portion 6A is formed on the interlayer insulating layer 4 to obtain a structure 200 shown in FIG. The photosensitive resin layer 5 is formed, for example, by applying a photosensitive resin composition containing a resin such as a chlorinated rubber, a phenol novolac, a polyhydroxystyrene, a polyacrylate, or the like by a spin coating method. The The window 6A is formed so that a predetermined portion of the interlayer insulating layer 4 is exposed by a known photolithography technique.

  After the interlayer insulating layer 4 is etched to form the window 6B, the photosensitive resin layer 5 is removed to obtain the structure 300 shown in FIG. For etching the interlayer insulating layer 4, dry etching means using a gas such as oxygen or carbon tetrafluoride can be used. By this etching, the portion of the interlayer insulating layer 4 corresponding to the window portion 6A is selectively removed, and the interlayer insulating layer 4 provided with the window portion 6B so that the first conductor layer 3 is exposed is obtained. Next, the photosensitive resin layer 5 is 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.

  Furthermore, the 2nd conductor layer 7 is formed in the part corresponding to the window part 6B, and the structure 400 shown in FIG. 4 is obtained. A known photolithography technique can be used to form the second conductor layer 7. As a result, the second conductor layer 7 and the first conductor layer 3 are electrically connected.

  Finally, the surface protective layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7 to obtain the semiconductor device 500 shown in FIG. In the present embodiment, the surface protective layer 8 is formed as follows. First, the photosensitive resin composition according to the above-described embodiment is applied on the interlayer insulating layer 4 and the second conductor layer 7 by spin coating, and dried to form a photosensitive resin film. Next, after light irradiation through a mask on which a pattern corresponding to the window 6C is drawn at a predetermined portion, the photosensitive resin film is patterned by developing with an alkaline aqueous solution. Thereafter, the photosensitive resin film is cured by heating to form a film as the surface protective layer 8. The surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, α rays, and the like, and the obtained semiconductor device 500 is excellent in reliability.

  In the above-described embodiment, the method for manufacturing a semiconductor device having a two-layer wiring structure is shown. However, when a multilayer wiring structure having three or more layers is formed, the above steps are repeated to form each layer. Can do. That is, it is possible to form a multilayer pattern by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protective layer 8. In the above example, not only the surface protective layer 8 but also the interlayer insulating layer 4 can be formed using the photosensitive resin composition of the present invention.

  1 to 5, the photosensitive resin composition of the present invention can be used as 4, 5, and 8.

  Moreover, since the above-mentioned photosensitive resin composition is excellent also in stress relaxation property, adhesiveness, etc., it can be used also as various structural materials in the package of various structures developed in recent years. 6 and 7 show a cross-sectional structure of an example of such a semiconductor device.

  FIG. 6 is a schematic cross-sectional view showing a wiring structure as an embodiment of the semiconductor device. A semiconductor device 600 shown in FIG. 6 includes a silicon chip 23, an interlayer insulating layer 11 provided on one side of the silicon chip 23, and an Al having a pattern including a pad portion 15 formed on the interlayer insulating layer 11. A wiring layer 12, an insulating layer 13 (for example, a P-SiN layer) and a surface protective layer 14, which are sequentially stacked on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and a surface protective layer 14 in contact with the pad portion 15 in the openings of the insulating layer 13 and the surface protective layer 14 and the surface of the core 18 opposite to the surface protective layer 14. And a rewiring layer 16 extending on the surface protective layer 14. Further, the semiconductor device 600 is formed so as to cover the surface protective layer 14, the core 18, and the rewiring layer 16, and a cover coat layer 19 in which an opening is formed in a portion of the rewiring layer 16 on the core 18. The conductive ball 17 connected to the rewiring layer 16 with the barrier metal 20 interposed therebetween in the opening of the layer 19, the collar 21 that holds the conductive ball, and the cover coat layer 19 around the conductive ball 17 are provided. The underfill 22 is provided. The conductive ball 17 is used as an external connection terminal and is formed of solder, gold or the like. The underfill 22 is provided to relieve stress when the semiconductor device 600 is mounted.

  FIG. 7 is a schematic cross-sectional view showing a wiring structure as one embodiment of a semiconductor device. In the semiconductor device 700 of FIG. 7, an Al wiring layer (not shown) and a pad portion 15 of the Al wiring layer are formed on the silicon chip 23, and an insulating layer 13 is formed on the Al wiring layer. A surface protective layer 14 is formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to an upper portion of the connection portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20.

  6 and 7, the above-described photosensitive resin composition forms not only the interlayer insulating layer 11 and the surface protective layer 14, but also the cover coat layer 19, the core 18, the collar 21, the underfill 22, and the like. Can be used as a material for. The cured body using the above-described photosensitive resin composition is excellent in adhesiveness with a metal layer such as the Al wiring layer 12 and the rewiring layer 16 and a sealing agent, and has a high stress relaxation effect. The semiconductor device used for the surface protective layer 14, the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 22 used in a flip chip or the like has extremely high reliability.

  The photosensitive resin composition of the present invention is particularly preferably used for the surface protective layer 14 and / or the cover coat layer 19 of the semiconductor device having the rewiring layer 16 in FIGS.

  The film thickness of the surface protective layer or the cover coat layer is preferably 3 to 20 μm, and more preferably 5 to 15 μm.

  As described above, by using the above-described photosensitive resin composition, curing using low-temperature heating of 200 ° C. or lower is possible in the heat treatment step that conventionally required 300 ° C. or higher. Moreover, the cured film obtained by heating the photosensitive resin composition of the present invention achieves both good elongation at break and heat resistance. Furthermore, since the photosensitive resin composition of the present invention has a small volume shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide and the like, it can prevent a reduction in dimensional accuracy. The cured film of the photosensitive resin composition has a high glass transition temperature. Accordingly, the surface protective layer or cover coat layer is excellent in heat resistance. As a result, an electronic component such as a semiconductor device having excellent reliability can be obtained with high yield and high yield.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Synthesis of polyamideimide resin A1)
10.1 g of trimellitic anhydride and 10.0 g of polyoxypropylenediamine (weight average molecular weight 400) were dissolved in 60 g of N-methylpyrrolidone. This solution was heated to 80 ° C., reacted for 30 minutes, and further stirred at 160 ° C. for 2 hours. Thereafter, the reaction solution is cooled, and 4.6 g of 5-hydroxyisophthalic acid and 10.1 g of tolylene diisocyanate (a mixture of 2,4-diisocyanatotolylene and 2,6-diisocyanatotolylene) are added at 160 ° C. The reaction was performed for 2 hours. The reaction solution was cooled to room temperature (25 ° C.) to obtain an alkali-soluble polyamideimide resin (hereinafter referred to as “A1”). The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A1 was about 20,000.

In addition, the weight average molecular weight measured the weight average molecular weight of each polymer by GPC with the following apparatuses and conditions.
(Conditions and equipment)
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: 2 columns Gelpack GL-S300MDT-5 (manufactured by Hitachi Chemical Co., Ltd.)
Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

(Synthesis of polyamideimide resin A2)
Further, 2.3 g of 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane was added as a diamine component of A1, and trimellitic anhydride 5. 0 g and 12.3 g of polyoxypropylenediamine (weight average molecular weight 400) were dissolved in 52 g of N-methylpyrrolidone. This solution was heated to 80 ° C., reacted for 30 minutes, and further stirred at 160 ° C. for 2 hours. Thereafter, the reaction solution was cooled, 2.3 g of 5-hydroxyisophthalic acid and 5.1 g of tolylene diisocyanate (a mixture of 2,4-diisocyanatotolylene and 2,6-diisocyanatotolylene) were added, For 2 hours. The reaction solution was cooled to room temperature to obtain an alkali-soluble polyamideimide resin (hereinafter referred to as “A2”). The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A2 was about 29,000.

(Synthesis of Polyamideimide Resin A′3 for Comparative Example)
1.6 g of trimellitic anhydride and 1.5 g of 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane were added to 41 g of N-methylpyrrolidone. Dissolved. This solution was heated to 80 ° C., reacted for 30 minutes, and further stirred at 160 ° C. for 2 hours. Thereafter, the reaction solution is cooled, and 6.6 g of 5-hydroxyisophthalic acid and 8.0 g of tolylene diisocyanate (a mixture of 2,4-diisocyanatotolylene and 2,6-diisocyanatotolylene) are added at 160 ° C. The reaction was performed for 2 hours. The reaction solution was cooled to room temperature to obtain an alkali-soluble polyamideimide resin (hereinafter referred to as “A′3”). The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A'3 was about 17,000.

(Synthesis of Polyimide Resin A′4 for Comparative Example)
7.8 g of 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- 9.2 g of hexafluoropropane was dissolved in 40.0 g of N-methylpyrrolidone. This solution was heated to 80 ° C., reacted for 30 minutes, and further stirred at 160 ° C. for 2 hours. Thereafter, the reaction solution was cooled to obtain an alkali-soluble polyimide resin (hereinafter referred to as “A′4”). The weight average molecular weight determined by standard polystyrene conversion of this A′4 GPC method was about 15,000.
Table 1 shows the amounts of components used for each polymer.

(Preparation of photosensitive resin composition)
Example 1
10 g of A1 synthesized as a polyamideimide resin having a structural unit represented by the general formula (1), (b) 1,1-bis (4-hydroxyphenyl) -1- [4 as a compound that generates an acid by light -{1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid ester (manufactured by AZ Electronic Materials, trade name “TPPA528”) 1.5 g (C) 1.5 g of hexakis (methoxymethyl) melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-30HM”) as a thermal crosslinking agent was dissolved in 14 g of N-methylpyrrolidone as a solvent (d). A photosensitive resin composition was prepared.

(Example 2)
A photosensitive resin composition was prepared by the same operation method as in Example 1 except that A2 was used instead of A1 described above.

(Comparative Example 1)
A photosensitive resin composition was prepared by the same operation method as in Example 1, except that A1 was changed to A'3 instead of A1 described above.

(Comparative Example 2)
A photosensitive resin composition was prepared by the same operation method as in Example 1, except that A1 was changed to A'4 instead of A1 described above.

(Evaluation of photosensitive resin composition)
[Evaluation of photosensitivity (resolution)]
The photosensitive resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 11 to 12 μm. Next, exposure was performed at 500 mJ / cm ² through a mask using a proximity exposure machine (trade name “PLA-600FA” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it observed using the metal microscope (Olympus Co., Ltd. MX61), and when the through hole pattern of a 100 micrometer square was missing, it judged as "A" and the case where it did not missing was judged and evaluated.

[Evaluation of cured film properties (elongation at break)]
The photosensitive resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of about 11 to 12 μm. . Thereafter, the coating film was exposed at all wavelengths through a mask using a proximity exposure machine (trade name “PLA-600FA” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38% by mass aqueous solution of TMAH to obtain a 10 mm wide rectangular pattern. Then, the coating film was heat-processed for 2 hours at the temperature of 180 degreeC in nitrogen using the vertical type | mold diffusion furnace (The Koyo Thermo System Co., Ltd. make, brand name "micro-TF"). Next, the cured film was peeled from the silicon substrate, and the breaking elongation of the peeled film was measured by “Autograph AGS-H100N” manufactured by Shimadzu Corporation.

[Evaluation of cured film properties (heat resistance)]
The Tg (glass transition temperature) of the films prepared by the same method as the evaluation of the elongation at break of the photosensitive resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was manufactured by Seiko Instruments Inc. Measured by “TMA / SS6000”.

  The results of the measurements and evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2 are summarized in Table 2.

  The cured film obtained by heating the photosensitive resin composition containing the polymer having a specific structural unit as in Examples 1 and 2 had good elongation at break and good heat resistance. . On the other hand, in the case of a polymer not containing the aliphatic diamine represented by the general formula (1) as in Comparative Example 1, it was found that the resolution and the elongation at break of the cured film were lowered. Moreover, since the polyimide of Comparative Example 2 was highly soluble, it could not be resolved and a film could not be obtained.

  When the photosensitive resin composition of the present invention is used, a cured pattern film having good elongation at break and heat resistance can be provided. Moreover, if the photosensitive resin composition of this invention is used, a pattern resin film can be formed with favorable resolution. Moreover, this invention provides the manufacturing method of the pattern cured film using the said photosensitive resin composition, and the semiconductor device which has this pattern cured film.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... 1st conductor layer, 4 ... Interlayer insulation layer, 5 ... Photosensitive resin layer,
6A, 6B, 6C ... windows, 7 ... second conductor layer, 8 ... surface protective layer, 11 ... interlayer insulating layer, 12 ... wiring layer, 13 ... insulating layer, 14 ... surface protective layer, 15 ... pad portion, 16 Redistribution layer, 17 Conductive ball, 18 Core, 19 Cover layer, 20 Barrier metal, 21 Color, 22 Underfill, 23 Silicon chip, 24 Connection,
100, 200, 300, 400 ... structure, 500 ... semiconductor device, 600 ... semiconductor device, 700 ... semiconductor device.

Claims (8)

(A) a polyamideimide resin having a structural unit represented by the following general formula (1);
(B) a compound that generates an acid by light;
(C) a thermal crosslinking agent;
(D) A photosensitive resin composition containing a solvent.

(In General Formula (1), R ¹ is ^one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, n ⁶ is 1 to 5. R ² is a divalent organic group.

  The photosensitive resin composition of Claim 1 whose compound which generate | occur | produces an acid with the light of (b) component is an o-quinonediazide compound.   The photosensitive resin composition according to claim 1 or 2, wherein the thermal crosslinking agent of component (c) is a compound having a hydroxymethylamino group or a compound having an epoxy group. The photosensitive resin composition in any one of Claims 1-3 whose polyamideimide resin of (a) component is a polyamideimide resin which has a structural unit represented by General formula (3).

(In General Formula (3), R ¹ is any one of divalent organic groups represented by the following General Formula (2), n ¹ is 1 to 20, n ² is 1 to 50, and n ³ is 1 to 70, n ⁴ is 1 to 5, n ⁵ is 1 to 10, and n ⁶ is 1 to 5. R ³ is hydrogen, a methyl group, or an ethyl group.

The photosensitive resin composition in any one of Claims 1-4 whose polyamideimide resin of (a) component is a polyamideimide resin which has a structural unit further represented by General formula (4).

(In the general formula (4), R ⁴ represents a divalent organic group.)   Applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form a resin film, exposing and developing the resin film, and forming a pattern resin film; And a step of heating the pattern resin film.   The manufacturing method of the pattern cured film of Claim 6 which performs the process of heating a pattern resin film at 250 degrees C or less.   The semiconductor device which has a pattern cured film formed by the manufacturing method of the pattern cured film of Claim 6 or 7 as an interlayer insulation film or a surface protective layer.

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