JP2012247762A - Positive photosensitive resin composition, cured film, protective film, insulating film, semiconductor device and display body device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having high sensitivity, high resolution and excellent removing property of development scum, and to provide a cured film, a protective film, an insulating film, a semiconductor device and a display body device.SOLUTION: The positive photosensitive resin composition includes an alkali-soluble resin (A), a photosensitive agent (B) and a compound (C) having a phenolic hydroxy group and an amide group in the structure of one molecule. The cured film comprises a cured product of the positive photosensitive resin composition. The semiconductor device and the display device include the cured film.

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device, and a display device.

Conventionally, polybenzoxazole resins, polyimide resins, and the like that are excellent in heat resistance and have excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. On the other hand, in order to simplify the process, a positive photosensitive resin composition in which a polyazoxazole resin, a polyimide resin, or the like is combined with a diazoquinone compound as a photosensitive agent is also used.
This photosensitive resin composition becomes hardly soluble in an alkaline aqueous solution in an unexposed portion due to the effect of inhibiting the dissolution of a diazoquinone compound in a resin such as polybenzoxazole resin or polyimide resin. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change, and the photosensitive resin composition becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion and dissolving and removing the exposed portion with an alkaline aqueous solution, it becomes possible to create a coating film pattern of only the unexposed portion.

  When the positive photosensitive resin composition described above is actually used, the sensitivity of the photosensitive resin composition is particularly important. If the sensitivity is low, the exposure time becomes long and the throughput (processing speed per unit time) decreases. Therefore, it has been reported that the sensitivity is improved by adding a specific phenol compound to improve the sensitivity of the photosensitive resin composition (Patent Document 1). However, the effect is inadequate. In particular, when the molecular weight of the resin component is high, there has been a demand for a material with high sensitivity without generating a development residue (scum).

Japanese Patent No. 4128116

  The present invention provides a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device, and a display device that have high sensitivity and high resolution and are excellent in removal of development residue (scum). It is.

Such an object is achieved by the present inventions [1] to [12] below.
[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and a compound (C) having a phenolic hydroxyl group and an amide group in one molecular structure.
[2] The positive photosensitive resin composition according to [1], wherein the alkali-soluble resin (A) is a polyamide-based resin having a repeating unit represented by the following general formula (1).

（式中、Ｘ、Ｙは有機基である。Ｒ_１は水酸基、−Ｏ−Ｒ_３、アルキル基、アシルオキシ基、シクロアルキル基であり、同一でも異なっても良い。Ｒ_２は水酸基、カルボキシル基、−Ｏ−Ｒ_３、−ＣＯＯ−Ｒ_３のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ_３は炭素数１〜１５の有機基である。ここで、Ｒ_１が複数ある場合は、それぞれ異なっていても同じでもよい。Ｒ_１として水酸基がない場合は、Ｒ_２は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_２としてカルボキシル基がない場合、Ｒ_１は少なくとも１つは水酸基でなければならない。）
［３］ 前記化合物（Ｃ）が１分子構造中に２つ以上のフェノール性水酸基を有することを特徴とする前記［１］または［２］に記載のポジ型感光性樹脂組成物。
［４］ 前記化合物（Ｃ）中のアミド基を含む部分の構造が環状構造を有する前記［１］ないし［３］のいずれか１項に記載のポジ型感光性組樹脂成物。
［５］ 前記化合物（Ｃ）が下記式（２）で表せられるとこを特徴とする前記［１］ないし［５］のいずれか１項に記載のポジ型感光性樹脂組成物。

(In the formula, X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₂ is a hydroxyl group or a carboxyl group. , —O—R ₃ , —COO—R ₃ , which may be the same or different, m is an integer of 0 to 8, n is an integer of 0 to 8. R ₃ is an integer of 1 to Here, when there are a plurality of R _{1 s} , they may be different or the same, and when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. In addition, when R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group.
[3] The positive photosensitive resin composition as described in [1] or [2] above, wherein the compound (C) has two or more phenolic hydroxyl groups in one molecular structure.
[4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the structure of the portion containing the amide group in the compound (C) has a cyclic structure.
[5] The positive photosensitive resin composition as described in any one of [1] to [5], wherein the compound (C) is represented by the following formula (2).

（Ｚは、カルボニル基、またはチオカルボニル基を示す。Ｒ_４は水素原子、アルキル基、アルキルエステル基、アルキルエ−テル基、ベンジルエ−テル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｕ＝０〜４,ｖ＝１〜５の
整数である。）
［６］ 前記アルカリ可溶性樹脂（Ａ）１００重量部に対して、上記化合物（Ｃ）を１重量部以上３０重量部以下を含む、前記［１］ないし［５］のいずれか１項に記載のポジ型感光性樹脂組成物。
［７］ 前記感光剤（Ｂ）が、感光性ジアゾキノン化合物である、前記［１］ないし［６］のいずれか１項に記載のポジ型感光性樹脂組成物。
［８］ 前記［１］ないし［７］のいずれか１項に記載のポジ型感光性樹脂組成物の硬化物で構成されている硬化膜。
［９］ 前記［８］に記載の硬化膜で構成されている保護膜。
［１０］ 前記［８］に記載の硬化膜で構成されている絶縁膜。
［１１］ 前記［８］に記載の硬化膜を有している半導体装置。
［１２］ 前記［８］に記載の硬化膜を有している表示体装置。

(Z represents a carbonyl group or a thiocarbonyl group. R ₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom; Each may be the same or different, u = 0 to 4, and v = 1 to 5 integers.)
[6] The method according to any one of [1] to [5], including 1 to 30 parts by weight of the compound (C) with respect to 100 parts by weight of the alkali-soluble resin (A). Positive photosensitive resin composition.
[7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the photosensitive agent (B) is a photosensitive diazoquinone compound.
[8] A cured film composed of a cured product of the positive photosensitive resin composition according to any one of [1] to [7].
[9] A protective film composed of the cured film according to [8].
[10] An insulating film composed of the cured film according to [8].
[11] A semiconductor device having the cured film according to [8].
[12] A display device having the cured film according to [8].

  The positive photosensitive resin composition of the present invention has characteristics of high sensitivity, high resolution film loss, no pattern shape collapse, and no development residue (scum).

The present invention comprises a positive photosensitive resin comprising an alkali-soluble resin (A), a photosensitive agent (B), and a compound (C) having a phenolic hydroxyl group and an amide group in one molecular structure. It is a composition. By using the positive photosensitive resin composition having such a configuration, it has an effect of high sensitivity, high resolution, and excellent development residue (scum) removability.
Hereinafter, the present invention will be described in detail.

  The alkali-soluble resin (A) used in the present invention is not particularly limited, but examples thereof include acrylic resins such as cresol type novolak resin, hydroxystyrene resin, methacrylic acid resin, and methacrylic ester resin, hydroxyl group, and carboxyl. Examples thereof include cyclic olefin resins containing a group and polyamide resins. Among these, polyamide resins are preferred from the viewpoint of excellent heat resistance and good mechanical properties. Specifically, they have at least one of a polybenzoxazole structure and a polyimide structure, and have hydroxyl groups or carboxyl groups in the main chain or side chain. , A resin having an ether group or an ester group, a resin having a polybenzoxazole resin precursor structure, a resin having a polyimide resin precursor structure, a resin having a polyamic acid ester structure, and the like. As such a polyamide-type resin, the polyamide-type resin shown by the said General formula (1) can be mentioned, for example.

In a polyamide resin represented by the general formula (1), _-O-R 3 as a substituent of the _-O-R 3, Y as a substituent of X, _{-COO-R 3} represents a hydroxyl group, a carboxyl group For the purpose of adjusting the solubility in an aqueous alkali solution, it is a group protected by R ₃ which is an organic group having 1 to 15 carbon atoms, and a hydroxyl group or a carboxyl group may be protected if necessary. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.
The polyamide-based resin having the repeating unit represented by the general formula (1) includes, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol, and tetracarboxylic acid containing Y. It is obtained by reacting a compound selected from dianhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, and hydroxydicarboxylic acid derivative.
In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

  Examples of X in the general formula (1) include aromatic compounds such as a benzene ring and a naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles, and furans, and siloxane compounds. More specifically, what is shown by following formula (3) is preferable. These may be used alone or in combination of two or more.

（ここで、＊はＮＨ基に結合することを示す。式中Ａは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_５はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、Ｒ_６はアルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。a＝０〜４の整数であ
る。Ｒ_７〜Ｒ_９は有機基である。）
上記一般式（１）で示すように、ＸにはＲ_１が０〜８個結合される（式（３）において、Ｒ_１は省略）。

(Here, * indicates bonding to an NH group. In the formula, A represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₅ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom. , R ₆ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, and may be the same or different, and is an integer of a = 0 to 4. R _{7 to} R ₉ are organic groups. )
As shown in the general formula (1), 0 to 8 R ₁ are bonded to X (in the formula (3), R ₁ is omitted).

  Preferred examples of the formula (3) include those represented by the following formula (4), which are particularly excellent in heat resistance and mechanical properties.

（式中、＊はＮＨ基に結合することを示す。式(４）中のＡは、−ＣＨ_２−、−ＣＨ（Ｃ
Ｈ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_５はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ_８は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。a＝０〜４、ｂ＝０〜３、ｃ＝０〜２の整数である。）

(In the formula, * indicates binding to the NH group. A in the formula (4) is —CH ₂ —, —CH (C
H ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond. R ₅ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. R ₈ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. It is an integer of a = 0-4, b = 0-3, c = 0-2. )

  Further, among the formulas (4), those represented by the following formula (5) are particularly preferable. When X of the polyamide-based resin represented by the general formula (1) is the following formula (5), the sensitivity is further improved by the combination with the compound (C).

（式中、＊はＮＨ基に結合することを示す。式（５）中のＡは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_８はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｂ＝０〜３の整数である。）

(In the formula, * represents bonding to the NH group. A in the formula (5) is —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, And —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₈ is selected from an alkyl group, an alkyl ester group, and a halogen atom. Each represents the same or different, b is an integer of 0 to 3.)

  Moreover, Y of General formula (1) is an organic group, and the same thing as said X is mentioned. For example, aromatic compounds such as benzene ring and naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles, pyridines and furans, siloxane compounds and the like, more preferably those represented by the following formula (6) Can be mentioned. These may be used alone or in combination of two or more.

（ここで＊はＣ＝Ｏ基に結合することを示す。式中（６）のＢは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_９はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同一でも異なっても良い。また、Ｒ_１０は水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。ｄ＝０〜４の整数である。Ｒ_１１〜Ｒ_１３は有機基である。）
一般式（１）で示すように、Ｙには、Ｒ_２が０〜８個結合される（式（６）において、Ｒ_２は省略した）。

(Here, * indicates bonding to a C═O group. In the formula (6), B represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—). , —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₉ is selected from an alkyl group, an alkyl ester group, and a halogen atom. R ₁₀ may be the same or different, and R ₁₀ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, and d is an integer of 0 to 4. R _{11 to} R ₁₃ are organic groups.)
As represented by the general formula (1), 0 to 8 R ₂ are bonded to Y (R ₂ is omitted in the formula (6)).

  As a preferable thing in Formula (6), what is shown by following formula (7) which is excellent in heat resistance and a mechanical characteristic is mentioned.

（式中、＊はＣ＝Ｏ基に結合することを示す。式（７）中のＢとＤは、−ＳＯ_２−、−ＣＯ−、−Ｏ−、である。Ｒ_９は、アルキル基、アルキルエステル基、アルキルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ_１４は、水素原子または、炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていても良い。ｄ＝０〜４の整数である。）

(In the formula, * indicates bonding to a C═O group. B and D in the formula (7) are —SO ₂ —, —CO—, —O—, and R ₉ is an alkyl group. Represents one selected from an alkyl ester group, an alkyl ether group, and a halogen atom, and may be the same or different, and R ₁₄ is selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms. One of them may be partially substituted, d = 0 to an integer of 0 to 4.)

  Further, among the formulas (7), those represented by the following formula (8) are particularly preferable. When Y of the polyamide-based resin represented by the general formula (1) is the following formula (8), the sensitivity is further improved by the combination with the compound (C).

（式中、＊はＣ＝Ｏ基に結合することを示す。式（８）中のＢは、−ＳＯ_２−、−ＣＯ−、−Ｏ−、である。Ｒ_９は、アルキル基、アルキルエステル基、アルキルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｄ＝０〜４の整数である。）

(In the formula, * indicates bonding to a C═O group. B in the formula (8) is —SO ₂ —, —CO—, —O—. R ₉ is an alkyl group, an alkyl group, It represents one selected from an ester group, an alkyl ether group, and a halogen atom, and each may be the same or different, and d is an integer of 0 to 4.)

In addition, the polyamide-based resin having the repeating unit represented by the general formula (1) is an aliphatic group having a terminal of the polyamide-based resin as an amino group, the amino group having at least one alkenyl group or alkynyl group, Alternatively, it is preferable to cap the amide using an acid anhydride containing a cyclic compound group. Thereby, preservability can be improved.
Examples of such a group derived from an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (9) and formula (10 ) And the like. These may be used alone or in combination of two or more.

（上式（９）中のＲ_１５は、水素、またはメチル基を表す。）

(R ₁₅ in the above formula (9) represents hydrogen or a methyl group.)

（式（１０）中のＲ_１６は、水素、またはメチル基を表す。）

(R ₁₆ in the formula (10) represents hydrogen or a methyl group.)

  Among these, a group of the following formula (11) is particularly preferable. Thereby, especially storability can be improved.

  The method is not limited to this method, and the terminal acid contained in the polyamide-based resin is converted into an amide by using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. It can also be capped.

The polyamide-based resin having the repeating unit represented by the general formula (1) may have a nitrogen-containing heterocyclic compound in at least one of the side chain and the other end.
Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved.
The reason for this is that when one end of the polyamide-based resin having the structure of the above formula (1) is an organic group having an unsaturated group, the resin reacts, so that mechanical properties such as tensile elongation of the cured film are excellent. This is because when the nitrogen-containing heterocyclic compound is present in at least one of the side chain and the other end, the nitrogen-containing heterocyclic compound reacts with the metal wiring of copper and a copper alloy, so that adhesion is excellent.

  Examples of the nitrogen-containing heterocyclic compound include 1- (5-1H-triazoyl) methylamine, 3- (1H-pyrazoyl) amine, 4- (1H-pyrazoyl) amine, 5- (1H-pyrazoyl) amine, 1 -(3-1H-pyrazolyl) methylamine, 1- (4-1H-pyrazoyl) methylamine, 1- (5-1H-pyrazoyl) methylamine, (1H-tetrazol-5-yl) amine, 1- (1H -Tetrazol-5-yl) methyl-amine, 3- (1H-tetrazol-5-yl) benz-amine and the like. Thereby, especially adhesiveness with the metal wiring of copper and a copper alloy can be improved more.

The photosensitive agent (B) used in the present invention is a compound that generates an acid by light.
Examples of the compound that generates an acid by light include onium salts such as diphenyliodonium salt and triphenylsulfonium salt, 2-nitrobenzyl esters, N-iminosulfonates, arylsulfonate esters, and halogens such as chlorine. Examples include heterocyclic compounds and photosensitive diazoquinone compounds.
Among these compounds, a photosensitive diazoquinone compound is preferred because it has the highest sensitivity and resolution in the wavelength range of actinic radiation mainly used for exposure.
Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid.
Specific examples include ester compounds represented by formula (12) to formula (16). These may be used alone or in combination of two or more.

（上記式（１２）中のＥは、−Ｃ（ＣＨ_３）_２−、−ＣＯ−である。Ｒ_１７は、水素、またはメチル基を表す。ｈ＝０〜３の整数である。）

(E in the above formula (12) is —C (CH ₃ ) ₂ —, —CO—. R ₁₇ represents hydrogen or a methyl group. H = 0 to 3 is an integer.)

（上記式（１３）中のＲ_１８はメチル基、シクロヘキサン環を表し、それぞれ同じでも異なっていてもよい。ｊ＝０〜２、ｋ＝０〜２の整数である。）

(R ₁₈ in the above formula (13) represents a methyl group and a cyclohexane ring, which may be the same or different. J = 0 to 2, k = 0 to 2 are integers.)

（上記式（１４）中のＲ_１９は、水素、またはメチル基を表す。それぞれ同じでも異なってもよい。ｍ＝１〜３、ｎ＝１〜３、ｐ＝１〜２の整数である。）

(R ₁₉ in the above formula (14) represents hydrogen or a methyl group. They may be the same or different. M = 1 to 3, n = 1 to 3, and p = 1 to 2 are integers. )

（上記式（１５）中のＲ_２０は、水素、またはメチル基を表す。ｑ＝１〜３、ｒ＝０〜１
の整数である。）

(R ₂₀ in the above formula (15) represents hydrogen or a methyl group. Q = 1 to 3, r = 0 to 1
Is an integer. )

（上記式（１６）中のＲ_２１は、水素、またはメチル基である。）

(R ₂₁ in the above formula (16) is hydrogen or a methyl group.)

  Q in the formulas (12) to (16) is selected from a hydrogen atom or any one of the following formulas (17) and (18). Here, at least one of Q of each compound is represented by formula (17) or formula (18).

  As for the compounding quantity of the photosensitive agent (B) used for this invention, 1-50 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A). More preferably, it is 10 to 40 parts by weight. When the blending amount is within the above range, the sensitivity is particularly excellent.

In the positive photosensitive resin composition according to the present invention, a compound (C) having a phenolic hydroxyl group and an amide group in one molecular structure is used.
Examples of the amide group of the compound (C) include a carboamide group and a thioamide group. In addition to the phenolic hydroxyl group, the presence of a strongly activated NH group in the amide group portion is considered to exhibit a high sensitivity and high resolution effect.
Among the amide groups, the carboamide group is excellent in that it has high sensitivity and high resolution.
When the compound (C) is used, the dissolution rate of the exposed portion with respect to the developing solution is increased compared to the conventional case, the sensitivity is improved, and the occurrence of scum is suppressed.
Examples of the compound (C) having a phenolic hydroxyl group and an amide group in one molecular structure of the present invention include oxindole derivatives and indoline-2-thione derivatives. For example, if it is an oxindole derivative, the compound shown by following formula (19) etc. are mentioned.

  Examples of indoline-2-thione derivatives include compounds represented by the following formula (20).

  Of these, a compound of the following formula (21) is particularly preferable. As a result, particularly high sensitivity, high resolution, and the effect of eliminating development residue (scum) are improved.

  As for the compounding quantity of the compound (C) which has a phenolic hydroxyl group and an amide group in 1 molecular structure based on this invention, 0.1-50 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A). More preferably, it is 1-30 weight part. When the blending amount is within the above range, sensitivity and resolution are particularly excellent.

[Other ingredients]
(Adhesion aid)
The photosensitive resin composition of the present invention may contain an adhesion assistant.
The adhesion assistant is a component having a function of improving the bonding strength between the coating film obtained by curing the photosensitive resin composition and the substrate on which the coating film is formed.
Examples of such adhesion assistants include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Methoxysi 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples include, but are not limited to, propyltriethoxysilane, a silicon compound obtained by reacting an amino group-containing silicon compound with an acid dianhydride or an acid anhydride, and the like.

The silicon compound having an amino group is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.
The acid dianhydride or acid anhydride is not particularly limited, and examples thereof include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, and phthalic anhydride. These adhesion assistants can be used alone or in combination of two or more.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish.
Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio And the like, and may be used alone or in combination.

  Further, in the photosensitive resin composition of the present invention, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a crosslinking agent, a terminal blocking agent and a sensitizer are added as necessary. May be.

<Method for forming cured film>
Next, a method for forming a cured film (protective film, insulating film) using the photosensitive resin composition of the present invention will be described.
First, the photosensitive resin composition of the present invention is applied to a support (substrate) such as a silicon wafer, a ceramic substrate, or an aluminum substrate. When applied on a silicon wafer (semiconductor element), the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput.
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.

Next, after drying a coating film at 60-130 degreeC, actinic radiation is irradiated to a desired pattern shape (exposure process). As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.
Next, a pattern is obtained by dissolving and removing the irradiated portion with a developer (developing step).
Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An aqueous solution of an alkali such as a quaternary ammonium salt and an aqueous solution in which an appropriate amount of a water-soluble organic solvent or a surfactant such as alcohols such as methanol or ethanol is added thereto can be suitably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

Next, the relief pattern formed by development is rinsed (cleaned) (cleaning step). Distilled water is used as the rinse liquid.
Next, a heat treatment is performed to cause the benzoxazole precursor structure and the imide precursor structure to undergo a cyclization reaction to form a benzoxazole ring and an imide ring, resulting in a final pattern (cured film, protective film, insulating film) excellent in heat resistance. Is obtained (heat treatment step).
The heat treatment temperature is preferably 180 ° C to 380 ° C, more preferably 200 ° C to 350 ° C.

The cured film formed using the photosensitive resin composition of the present invention is used not only for semiconductor devices such as semiconductor elements, but also for display devices such as TFT (Thin Film Transistor) type liquid crystal and organic EL (Electro-Luminescence). It is also useful as an interlayer insulation film for multilayer circuits, a cover coat for flexible copper-clad plates, a solder resist film, and a liquid crystal alignment film.
Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described positive photosensitive resin composition on a semiconductor element, and a cured film of the above-described photosensitive resin composition formed on the passivation film. A protective film such as a buffer coat film, or an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described positive photosensitive resin composition on a circuit formed on a semiconductor element,
In addition, an α-ray blocking film, a planarizing film, a protrusion (resin post), a partition wall, and the like can be given.
Examples of the display device application include a protective film formed by forming a cured film of the photosensitive resin composition of the present invention on a display element, an insulating film or a planarizing film for TFT elements and color filters, MVA ( For example, protrusions for a multi-domain vertical alignment (liquid crystal display) type liquid crystal display device, partition walls for an organic EL element cathode, and the like can be given.

The usage method is based on forming the positive photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method.
High transparency is required for display device applications, particularly for insulating films and flattening films, but a post-exposure step is introduced before the coating film prepared using the photosensitive resin composition of the present invention is cured. Accordingly, a resin layer having excellent transparency can be obtained, which is more preferable in practical use.
The photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device of the present invention have been described above, but the present invention is not limited to these.
For example, the semiconductor device to which the photosensitive resin composition of the present invention is applied is not limited to the one having the above configuration.
The photosensitive resin composition of the present invention can be used not only for forming a protective film or insulating film of a semiconductor element as described above, but also for forming a spacer of a semiconductor element, for example.

Hereinafter, the present invention will be described specifically by way of examples.
<Example 1>
[Synthesis of Alkali-soluble Resin (A-1)]
Dicarboxylic acid obtained by reacting 211.7 g (0.82 mol) of diphenyl ether-4,4′-dicarboxylic acid with 221.6 g (1.64 mol) of 1-hydroxy-1,2,3-benzotriazole Derivative (active ester) 403.8 g (0.82 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 366.3 g (1 mol) were charged with thermometer, stirrer and raw material. The flask was placed in a four-necked separable flask equipped with a dry nitrogen gas inlet tube, and 3000 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 59.1 g (0.36 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 370 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the general formula (1) An alkali-soluble resin represented by the following formula (A-1) containing the structure:

[Synthesis of photosensitizer]
A thermometer containing 11.0 g (0.026 mol) of phenol represented by the formula (P-1), 17.2 g (0.064 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 160 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 7.1 g (0.07 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature, 1.0 g (0.016 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtration of the reaction mixture, the filtrate was poured into a mixed solution of water / acetic acid (900 ml / 9 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and of formula (B-1) A photosensitizer (photosensitive diazoquinone compound) was obtained.

[Preparation of positive photosensitive resin composition]
After dissolving 100 g of the synthesized alkali-soluble resin of the formula (A-1), 15 g of the photosensitive diazoquinone compound of the formula (B-1) and 10 g of the compound of the following formula (C-1) in 130 g of γ-butyrolactone, the pore size is 0. The mixture was filtered through a 2 μm Teflon (registered trademark) filter to obtain a positive photosensitive resin composition. The following evaluation was performed using the obtained positive photosensitive resin composition.

[Sensitivity, Resolution (Photosensitivity)]
The positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 8.0 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern with a width of 0.88 to 50 μm are drawn), an i-line stepper (manufactured by Nikon Corporation, 4425i) ) was used to irradiate while changing the exposure dose in 10 mJ / cm ² increments from 100 mJ / cm ² to 780mJ / cm ^2.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution, paddle development was performed by adjusting the development time so that the film thickness difference between the pre-baked and the unexposed areas after development was 1 μm. Then, it rinsed with the pure water for 10 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 350 mJ / cm ² (sensitivity was 350 mJ / cm ² ).
. The resolution at this time was as high as 4 μm.

[Mechanical properties evaluation]
The positive photosensitive resin composition is applied onto a 6-inch silicon wafer using a spin coater, then pre-baked on a hot plate at 120 ° C. for 4 minutes, and a coating film is formed so that the film thickness after curing is 10 μm. Obtained. Next, the silicon wafer with a coating film was heated at 320 ° C./30 minutes using an oven. The obtained silicon wafer with a cured film was cut to a width of 10 mm with a dicing saw (DFD6340, manufactured by Disco Corporation), then immersed in 2% hydrogen fluoride water, and the strip-like cured film was peeled off from the silicon wafer. . The obtained cured film was sufficiently washed with pure water and dried in an oven. Tensilon (RTA-1210, Orientec (
As a result of measuring the tensile strength and the elongation at break using a product manufactured by Kogyo Co., Ltd., the values were 116 MPa and 48%, respectively.

[Evaluation of glass transition temperature (Tg)]
The photosensitive resin composition was applied onto a 6-inch silicon wafer using a spin coater and then pre-baked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a cured film thickness of 10 μm. . Next, the silicon wafer with a coating film was heated at 320 ° C./30 minutes using an oven. Next, the obtained silicon wafer with a cured film was immersed in 2% hydrogen fluoride water, and the cured film was peeled off from the silicon wafer. The obtained cured film was thoroughly washed with pure water and dried in an oven. The cured film after drying was cut into a width of 5 mm to prepare a sample piece, and the glass transition temperature was measured using a thermomechanical analyzer (TMA) SS6000 manufactured by Seiko Instruments Inc. As a result, a high value of 294 ° C. was shown. .

[Fabrication and evaluation of semiconductor devices]
A semiconductor device having bumps was prepared and evaluated using the positive photosensitive resin composition.
FIG. 1 shows an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention.
As shown in FIG. 1, an input / output Al pad 2 is provided on a silicon substrate 1 having a semiconductor element and wiring provided on the surface, and a passivation film 3 is formed thereon, and the passivation film 3 is formed on the passivation film 3. A via hole was formed. On this, the positive photosensitive composition prepared above is applied and dried to form a positive photosensitive resin (buffer coat film) 4, and a metal (Cr, Ti, etc.) film 5 is connected to the Al pad 2. The metal film 5 was etched around the solder bump 9 to insulate the pads. A barrier metal 8 and a solder bump 9 are formed on the insulated pad to obtain a semiconductor device.
The semiconductor device obtained as described above operated without any problem, had a good yield, and exhibited high reliability.

<Example 2>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the compounding amount of the compound of formula (C-1) in Example 1 was changed to 30 g, and photosensitive characteristics (sensitivity and resolution) were evaluated. Mechanical property evaluation and glass transition temperature evaluation were performed.
<Example 3>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the compounding amount of the compound of formula (C-1) in Example 1 was changed to 1 g, and photosensitive characteristics (sensitivity and resolution) were evaluated. Physical property evaluation and glass transition temperature evaluation were performed.
<Example 4>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of the formula (C-1) in Example 1 was changed to the following formula (C-2). Resolution) evaluation, mechanical property evaluation, and glass transition temperature evaluation were performed.

<Example 5>
[Synthesis of alkali-soluble resin (A-2)]
It is obtained by reacting terephthalic acid 149.5 g (0.9 mol), isophthalic acid 16.6 g (0.1 mol) and 1-hydroxy-1,2,3-benzotriazole 270.2 g (2 mol). The dicarboxylic acid derivative (active ester) 328.3 g (0.82 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 366.3 g (1 mol) were thermometer and stirrer. Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 3000 g of N-methyl-2-pyrrolidone was added and dissolved.
Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 59.1 g (0.36 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 370 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction.
After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the formula (A-2 ) Alkali-soluble resin (polyamide resin).

[Synthesis of photosensitizer]
A thermometer containing 15.8 g (0.025 mol) of phenol represented by the formula (P-2), 22.3 g (0.083 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 160 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 8.4 g (0.083 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature, 1 g (0.016 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (900 ml / 9 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and of formula (B-2) A photosensitizer (photosensitive diazoquinone compound) was obtained.

［ポジ型感光性樹脂組成物の作製］
上記合成した式（Ａ−１）のポリアミド樹脂１００ｇ、上記式（Ｂ−２）の感光剤１５ｇ、上記式（Ｃ−１）の化合物１０ｇをγ−ブチロラクトン１３０ｇに溶解した後、０．２μｍのテフロン（登録商標）フィルターで濾過しポジ型感光性樹脂組成物を得た。得られたポジ型感光性樹脂組成物を用いて、実施例１と同様の評価を行った。

[Preparation of positive photosensitive resin composition]
100 g of the synthesized polyamide resin of the formula (A-1), 15 g of the photosensitive agent of the formula (B-2) and 10 g of the compound of the formula (C-1) are dissolved in 130 g of γ-butyrolactone, The mixture was filtered through a Teflon (registered trademark) filter to obtain a positive photosensitive resin composition. Evaluation similar to Example 1 was performed using the obtained positive photosensitive resin composition.

<Comparative Example 1>
A positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the compound of formula (C-1) in Example 1 was omitted.

It is sectional drawing of the pad part of the semiconductor device which shows the Example of this invention.

1 Silicon substrate 2 Al pad 3 Passivation film 4 Buffer coating film 5 Metal (Cr, Ti, etc.) film 6 Wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Solder bump

Claims (12)

  A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and a compound (C) having a phenolic hydroxyl group and an amide group in one molecular structure. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is a polyamide-based resin having a repeating unit represented by the following general formula (1).

(In the formula, X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₂ is a hydroxyl group or a carboxyl group. , —O—R ₃ , —COO—R ₃ , which may be the same or different, m is an integer of 0 to 8, n is an integer of 0 to 8. R ₃ is an integer of 1 to Here, when there are a plurality of R _{1 s} , they may be different or the same, and when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. In addition, when R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group.   The positive photosensitive resin composition according to claim 1 or 2, wherein the compound (C) has two or more phenolic hydroxyl groups in one molecular structure.   The positive photosensitive composite resin composition according to any one of claims 1 to 3, wherein the structure of the portion containing the amide group in the compound (C) has a cyclic structure. The positive photosensitive resin composition according to claim 1, wherein the compound (C) is a compound represented by the following formula (2).

(Z represents a carbonyl group or a thiocarbonyl group. R ₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom; Each may be the same or different, u = 0 to 4, and v = 1 to 5 integers.)   The positive photosensitive resin composition according to any one of claims 1 to 5, comprising 1 to 30 parts by weight of the compound (C) with respect to 100 parts by weight of the alkali-soluble resin (A). . The positive photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a photosensitive diazoquinone compound.   The cured film comprised with the hardened | cured material of the positive photosensitive resin composition of any one of Claim 1 thru | or 7.   A protective film comprising the cured film according to claim 8.   The insulating film comprised with the cured film of Claim 8.   A semiconductor device comprising the cured film according to claim 8. The display body apparatus which has the cured film of Claim 8.

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