JP4650018B2 - Polyamide resin, positive photosensitive resin composition, and semiconductor device and display element using the same - Google Patents

Description

  The present invention relates to a polyamide resin and a positive photosensitive resin composition, and a semiconductor device and a display element using the same.

Conventionally, a polybenzoxazole resin or a polyimide resin having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. On the other hand, in order to simplify the process, a positive photosensitive resin in which the polybenzoxazole resin or polyimide resin is combined with a diazoquinone compound as a photosensitive material is also used (Patent Document 1).
In recent years, semiconductor devices have been processed with various chemicals in the wafer process process due to downsizing of semiconductor elements, multilayer wiring by high integration, shift to chip size package (CSP), wafer level package (WLP), etc. It has come to be done. These new packages have moved from conventional wire bonding to bump-based configurations.
Japanese Examined Patent Publication No. 1-46862

However, the prior art described in the above literature has room for improvement in the following points.
First, when mounting bumps, the flux is used to pass through the reflow. At this time, the cured film of the positive type photosensitive resin is in direct contact with the flux. There is a problem that wrinkles and cracks are generated in the cured film of the positive photosensitive resin, and there is a problem that it is necessary to develop a positive photosensitive resin composition having excellent reflow resistance.

  Second, WLP uses Ti as a barrier metal, etc., and hydrofluoric acid is often used as the Ti etchant, and these positive photosensitive resins often peel off from the substrate during etching. was there. Therefore, in order to solve the peeling, it has been studied to add a silane coupling agent or an adhesion aid, but the effect is weak and a positive photosensitive resin having further resistance to hydrofluoric acid is desired. It was.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyimide resin excellent in reflow resistance and a positive photosensitive resin composition excellent in development characteristics using the resin. is there. Another object of the present invention is to provide a polyimide resin having excellent adhesion and a positive photosensitive resin composition having excellent development characteristics using the resin.

Such an object is achieved by the inventions described in [1] to [15] below.
[1] A polyamide resin containing structural units (I) and (II) represented by the following formula:

（式中、Ｙ_１がシロキサン結合を有する有機基、Ｙ_２が三重結合を有する有機基である。Ｘは２〜４価の有機基、Ｙ_１、Ｙ_２は２〜６価の有機基を表す。樹脂中のＸ、Ｙ_１及びＹ_２はそれぞれ同一でも異なっても良い。ａは０〜２の整数、ｂは０〜４の整数である。Ｒ^１は水酸基、または−Ｏ−Ｒ^３を表す。Ｒ^２は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかを表す。Ｒ^３は炭素数１〜１５の有機基を表す。Ｒ^１、Ｒ^２は繰り返しにおいて、それぞれ同一であっても異なってもよい。）
［２］式（１）で表される構造で表されるポリアミド樹脂。

(In the formula, Y ₁ is an organic group having a siloxane bond, Y ₂ is an organic group having a triple bond. X is a divalent to tetravalent organic group, Y ₁ and Y ₂ are divalent to hexavalent organic groups. X, Y ₁ and Y ₂ in the resin may be the same or different, a is an integer of 0 to 2, b is an integer of 0 to 4. R ¹ is a hydroxyl group, or —O—R ^3. R ² represents one of a hydroxyl group, a carboxyl group, —O—R ³ , and —COO—R ^3. R ³ represents an organic group having 1 to 15 carbon atoms, and R ¹ and R ² are repeated. Each may be the same or different.)
[2] A polyamide resin represented by the structure represented by the formula (1).

（式中、Ｙ_１がシロキサン結合を有する有機基、Ｙ_２が三重結合を有する有機基、Ｙ_３がシロキサン結合も不飽和結合も有しない有機基であるポリアミド樹脂である。Ｘは２〜４価の有機基、Ｙ_１、Ｙ_２及びＹ_３は２〜６価の有機基を表す。樹脂中のＸ、Ｙ_１、Ｙ_２及びＹ_３はそれぞれ同一でも異なっても良い。ｌ、ｍ、ｎは構造単位のモル比であって、ｌ＋ｍ＋ｎ＝１００、ｌ、ｍ＞０、ｎ≧０である。ａは０〜２の整数、ｂは０〜４の整数である。Ｒ^１は水酸基、または−Ｏ−Ｒ^３を表す。Ｒ^２は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかを表す。Ｒ^３は炭素数１〜１５の有機基を表す。Ｒ^１、Ｒ^２は繰り返しにおいて、それぞれ同一であっても異なってもよい。）
［３］前記シロキサン結合が下記式で表される構造である［１］または［２］記載のポリアミド樹脂。

Wherein Y ₁ is an organic group having a siloxane bond, Y ₂ is an organic group having a triple bond, and Y ₃ is an organic group having neither a siloxane bond nor an unsaturated bond. X is 2 to 4. A valent organic group, Y ₁ , Y ₂ and Y ₃ represent a divalent to 6-valent organic group, and X, Y ₁ , Y ₂ and Y ₃ in the resin may be the same or different. n is a molar ratio of structural units, and l + m + n = 100, l, m> 0, n ≧ 0, a is an integer of 0 to 2, b is an integer of 0 to 4, R ¹ is a hydroxyl group, Or represents -O-R ^3. R ² represents one of a hydroxyl group, a carboxyl group, -O-R ³ , and -COO-R ^3. R ³ represents an organic group having 1 to 15 carbon atoms, R ^1. , R ² may be the same or different in the repetition.)
[3] The polyamide resin according to [1] or [2], wherein the siloxane bond is a structure represented by the following formula.

（式中、Ｒ^４、Ｒ^５は２価の有機基、Ｒ^６、Ｒ^７は１価の有機基をそれぞれ表す。ｎは０〜２０を示す。）
［４］［１］乃至［３］のいずれかに記載のポリアミド樹脂であって、当該樹脂の両末端が、不飽和結合を有する酸無水物によって封止されていることを特徴とするポリアミド樹脂。
［５］［１］乃至［３］のいずれかに記載のポリアミド樹脂であって、当該樹脂の両末端が、
分子内に二重結合を有する酸無水物、及び、
分子内に三重結合を有する酸無水物、
によって封止されていることを特徴とするポリアミド樹脂。
［６］（Ａ）［１］乃至［５］のいずれかに記載のポリアミド樹脂、
（Ｂ）感光性ジアゾキノン化合物、
を含んでなるポジ型感光性樹脂組成物。
［７］［６］記載のポジ型感光性樹脂組成物が、更に（Ｃ）フェノール性水酸基を有する化合物を含むことを特徴とするポジ型感光性樹脂組成物。
［８］前記（Ｃ）フェノール性水酸基を有する化合物が、下記式で表される構造である［７］記載のポジ型感光性樹脂組成物。

(In the formula, R ⁴ and R ⁵ each represent a divalent organic group, R ⁶ and R ⁷ each represent a monovalent organic group, and n represents 0 to 20.)
[ 4 ] The polyamide resin according to any one of [1] to [ 3 ], wherein both ends of the resin are sealed with an acid anhydride having an unsaturated bond .
[ 5 ] The polyamide resin according to any one of [1] to [ 3 ], wherein both ends of the resin are
An acid anhydride having a double bond in the molecule; and
An acid anhydride having a triple bond in the molecule;
A polyamide resin characterized by being sealed by.
[ 6 ] (A) The polyamide resin according to any one of [1] to [ 5 ],
(B) a photosensitive diazoquinone compound,
A positive photosensitive resin composition comprising:
[ 7 ] A positive photosensitive resin composition, wherein the positive photosensitive resin composition according to [ 6 ] further comprises (C) a compound having a phenolic hydroxyl group.
[ 8 ] The positive photosensitive resin composition according to [ 7 ], wherein the compound (C) having a phenolic hydroxyl group has a structure represented by the following formula.

（式中、Ｒ^８、Ｒ^９、はハロゲン原子、アルキル基、アルコキシ基、アルキルエステル基、シクロアルキル基、シクロアルコキシ基の内から選ばれた１つを表す。ｍ＝０〜５、ｎ＝０〜５である。Ｒ^８、Ｒ^９は同じでも異なっても良い。ｐ＝０〜３の整数、ｑ＝０〜３の整数であり、ｐ＋ｑ≧２である。Ｒ^１０は単結合、メチレン基、アルキレン基、酸素原子、カルボニル基、カルボニルエーテル基、硫黄原子、スルホニル基、アゾ基の内から選ばれた１つを表す。）
［９］［６］乃至［８］のいずれかに記載のポジ型感光性樹脂組成物を基材上に塗布して樹脂層を形成する工程、
当該樹脂層の所望の部分に活性エネルギー線を照射する工程、
前記活性エネルギー線照射後の樹脂層に現像液を接触させ、次いで当該樹脂層を加熱する工程、
を含むことを特徴とするパターン形成方法。
［１０］半導体チップと、その回路面側に積層された保護膜を備える半導体装置であって、
前記保護膜が［６］乃至［８］のいずれかに記載のポジ型感光性樹脂組成物により構成された半導体装置。
［１１］表示素子用基板と、その表面を覆う平坦化膜を備える表示素子であって、
前記平坦化膜が［６］乃至［８］のいずれかに記載のポジ型感光性樹脂組成物を含むものである表示素子。
［１２］前記表示素子が、更に絶縁膜を備えるものであって、当該絶縁膜が［６］乃至［８］のいずれかに記載のポジ型感光性樹脂組成物を含むものである［１１］記載の表示素子。
［１３］半導体チップと、その回路面側に積層された保護膜を備える半導体装置の製造方法であって、
前記半導体チップ上に［６］乃至［８］のいずれかに記載のポジ型感光性樹脂組成物を塗布して樹脂層を形成する工程、
当該樹脂層の所望の部分に活性エネルギー線を照射する工程、
前記活性エネルギー線照射後の当該樹脂層に現像液を接触させ、次いで該樹脂層を加熱することにより前記保護膜を形成する工程、
を含むことを特徴とする半導体装置の製造方法。
［１４］表示素子用基板とその表面を覆う平坦化膜を備える表示素子の製造方法であって、
前記表示素子用基板上に［６］乃至［８］のいずれかに記載のポジ型感光性樹脂組成物を塗布して樹脂層を形成する工程、
当該樹脂層の所望の部分に活性エネルギー線を照射する工程、
活性エネルギー線照射後の当該樹脂層に現像液を接触させ、次いで該樹脂層を加熱することにより前記平坦化膜を形成する工程、
を含むことを特徴とする表示素子の製造方法。

(In the formula, R ⁸ and R ⁹ represent one selected from a halogen atom, an alkyl group, an alkoxy group, an alkyl ester group, a cycloalkyl group, and a cycloalkoxy group. M = 0 to 5, n = 0 to 5. R ⁸ and R ⁹ may be the same or different, p is an integer of 0 to 3, q is an integer of 0 to 3, and p + q is 2. R ¹⁰ is a single bond, methylene Represents one selected from a group, an alkylene group, an oxygen atom, a carbonyl group, a carbonyl ether group, a sulfur atom, a sulfonyl group, and an azo group.)
[ 9 ] A step of applying a positive photosensitive resin composition according to any one of [ 6 ] to [ 8 ] onto a substrate to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
A step of bringing a developer into contact with the resin layer after irradiation with the active energy ray and then heating the resin layer;
A pattern forming method comprising:
[ 10 ] A semiconductor device comprising a semiconductor chip and a protective film laminated on the circuit surface side,
The semiconductor device by which the said protective film was comprised by the positive photosensitive resin composition in any one of [ 6 ] thru | or [ 8 ].
[ 11 ] A display element comprising a display element substrate and a planarizing film covering the surface thereof,
The display element in which the said planarization film | membrane contains the positive photosensitive resin composition in any one of [ 6 ] thru | or [ 8 ].
[12] The display device may be one further comprising an insulating film, the insulating film is one that includes a positive photosensitive resin composition according to any one of [6] to [8] [11] according Display element.
[ 13 ] A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film laminated on the circuit surface side,
Applying the positive photosensitive resin composition according to any one of [ 6 ] to [ 8 ] on the semiconductor chip to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
Forming a protective film by bringing a developer into contact with the resin layer after irradiation with the active energy ray and then heating the resin layer;
A method for manufacturing a semiconductor device, comprising:
[ 14 ] A method for manufacturing a display element comprising a display element substrate and a planarizing film covering the surface thereof,
Applying the positive photosensitive resin composition according to any one of [ 6 ] to [ 8 ] on the display element substrate to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
A step of bringing the developer into contact with the resin layer after irradiation with active energy rays and then heating the resin layer to form the planarizing film;
A method for manufacturing a display element, comprising:

  The present invention relates to a polyamide resin excellent in reflow resistance and adhesion, a positive photosensitive resin composition excellent in development characteristics using the resin, a highly reliable semiconductor device using the resin composition, a display element, and The manufacturing method is provided.

  The first embodiment of the present invention is a polyamide resin containing structural units (I) and (II) represented by the following formula. The following is an example, and the present invention is not limited to the following. The polyamide resin of the present invention will be described in detail below.

  The polyamide resin represented by the general formula (1) includes a random copolymer, a block copolymer, an alternating copolymer, and the like. X in the general formula (1) is a divalent to tetravalent organic group, and examples thereof include those having the following structures.

（式中A³は、−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO₂−、−CO−、−NHCO−、−C(CF₃)₂−、又は単結合である。R¹²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＝０〜２の整数である。また、R¹³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つを表す。）

(Wherein A ³ represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — R ¹² represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, and is an integer of r = 0 to 2. R ¹³ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom.)

  Among these, particularly preferred are those having the following structures, and these may be used in combination of two or more.

（式中A⁴は、−C(CH₃)₂−、−O−、−SO₂−、−C(CF₃)₂−又は単結合である。R¹⁴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＝０〜２の整数である。）

(In the formula, A ⁴ is —C (CH ₃ ) ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ — or a single bond. R ¹⁴ is an alkyl group, an alkyl ester group, a halogen atom. Represents one selected from atoms, and may be the same or different, and r is an integer of 0 to 2.)

Examples of the structure represented by Y ₁ (an organic group having a siloxane bond) in the general formula (1) used in the present invention include the following structures.

  Among these, particularly preferred are those having the structure shown below.

Moreover, as Y < ₂ > (organic group which has an unsaturated bond) in General formula (1) used for this invention, the thing of the following structure is mentioned, for example.

（Rは、水素又は炭素数１から１５の炭化水素で表される有機基の中から選ばれる一価の基を示す。
式中のA¹は、−O−、−SO₂−、−C(CH₃)₂−又は−C(CF₃)₂−である。）

(R represents a monovalent group selected from hydrogen or an organic group represented by a hydrocarbon having 1 to 15 carbon atoms.
A ¹ in the formula is —O—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. )

  Among these, particularly preferred are those having the structure shown below.

（Rは、水素又は炭素数１から１５の炭化水素で表される基の中から選ばれる一価の有機基を示す 。）

(R represents a monovalent organic group selected from hydrogen or a group represented by a hydrocarbon having 1 to 15 carbon atoms.)

In addition to the above, an organic group having a double bond may be used as Y ₂ (an organic group having an unsaturated bond) in the general formula (1) used in the present invention.

Examples of the structure represented by Y ₃ (an organic group having neither a siloxane bond nor an unsaturated bond) in the general formula (1) used in the present invention include the following structures.

(式中A⁵は、−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO₂−、−CO−、−NHCO−、−C(CF₃)₂−又は単結合である。R¹⁵はアルキル基、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＝０〜２の整数である。)

(In A ⁵ represents the _{formula, -CH 2 -, - C (} CH 3) 2 -, - O -, - S -, - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 - R ¹⁵ represents one selected from an alkyl group and a halogen atom, which may be the same or different, and is an integer of r = 0 to 2.)

（R¹⁶はアルキル基、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＝０〜２の整数である。）

(R ¹⁶ represents one selected from an alkyl group and a halogen atom, and may be the same or different. R is an integer of 0 to 2.)

  Among these, particularly preferred are those having the following structures, and these may be used in combination of two or more.

  The total of the structural unit (I) of dicarboxylic acid and diamine containing an organic group having a siloxane bond and the structural unit (II) of dicarboxylic acid and diamine containing an organic group having an unsaturated bond is the sum of all diamines in the resin. It is preferable that it is 0.1 mol% or more and 70 mol% or less with respect to the structural unit of dicarboxylic acid. When the ratio is 0.1 mol% or more, the effects of reflow resistance, resistance to hydrofluoric acid, and chemical resistance, which are the characteristics of the present invention, are improved, and when it is 70.0 mol% or less, a cured film is obtained. The tensile elongation of reaches a sufficient strength.

  The polyamide resin of the present invention contains dicarboxylic acid (tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, 1-hydroxy-1,2, (Including derivatives of active ester type dicarboxylic acid and the like which have been previously reacted with 3-benzotriazole) and diamine (including aminophenols such as bis (aminophenol) and 2,4-diaminophenol) It is obtained by the reaction of

In the polyamide resin having the structure represented by the general formula (1), —O—R ³ as a substituent of X and —O—R ³ , —COO—R as a substituent of Y ¹ , Y ² , Y ^{3 3} is a group protected with R ³ which is an organic group having 1 to 15 carbon atoms for the purpose of adjusting the solubility of the hydroxyl group and carboxyl group in an alkaline aqueous solution. good. Examples of R ³ include formyl, methyl, ethyl, propyl, isopropyl, tert-butyl, tert-butoxycarbonyl, phenyl, benzyl, tetrahydrofuranyl, tetrahydropyranyl. Groups and the like.

  When the polyamide resin of the present invention is heated at about 250 to 400 ° C., it is dehydrated and closed, and a heat resistant resin is obtained in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both.

  In the present invention, it is desirable to seal the end from the viewpoint of storage stability. For sealing, a carboxylic acid compound having an unsaturated bond (including a carboxylic acid derivative) or an amine compound having an unsaturated bond is reacted with the end of the polyamide represented by the general formula (1) through an amide bond. Can be introduced.

  Examples of the derivative of the carboxylic acid compound having an unsaturated bond include tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, 1-hydroxy-1 , 2,3-benzotriazole and the like, and active ester type dicarboxylic acid derivatives.

  Preferable terminal structures of the carboxylic acid compound having an unsaturated bond include, for example, those having the following structures. The ends represented by the following formula are bonded to the amino groups at both ends of the polyamide resin through amide bonds.

Among these, particularly preferred are those having the following structures, and these may be used in combination of two or more.

  Preferable terminal structures of the amine compound having an unsaturated bond include, for example, those having the following structures. The ends represented by the following formula are bonded to the carboxyl groups at both ends of the polyamide resin through amide bonds.

（R¹⁷ 、R¹⁸ 、R¹⁹は、水素又は炭素数１から１５の炭化水素で表される基の中から選ばれる一価の有機基を示す 。）

(R ¹⁷ , R ¹⁸ and R ¹⁹ represent a monovalent organic group selected from hydrogen or a group represented by a hydrocarbon having 1 to 15 carbon atoms.)

  Among these, particularly preferred are those having the following structures, and these may be used in combination of two or more.

  As the terminal blocking agent of the present invention, both a compound having a double bond in the molecule and a compound having a triple bond in the molecule may be used in combination. When a compound having a double bond in the molecule is used as a sealant, chemical resistance is improved, and when a compound having a triple bond in the molecule is used as a sealant, reflow resistance is improved. Therefore, it is considered that a polyamide resin excellent in both chemical resistance and reflow resistance can be obtained by using these together.

  As a 2nd form of this invention, the positive type photosensitive resin composition which contains (A) the polyamide resin of this invention and (B) the photosensitive diazoquinone compound is mentioned.

The photosensitive diazoquinone compound (B) used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is known from US Pat. It is a substance. As a synthesis method, it can be obtained by reacting a phenol compound with 1,2-benzoquinonediazide-5-sulfonic acid chloride or 1,2-naphthoquinonediazidesulfonic acid chloride.
Specific examples of the photosensitive diazoquinone compound (B) used in the present invention include the following.

  Of these, particularly preferred are esters of phenolic compounds and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. . Examples of these include, but are not limited to, the following. Two or more of these may be used.

  The addition amount of the photosensitive diazoquinone compound (B) used in the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin. If it exceeds 1 part by weight, the pattern becomes better, and if it is less than 50 parts by weight, the sensitivity is further improved.

  Further, in the present invention, it is preferable to use a compound (C) having a phenolic hydroxyl group in combination so that it can be patterned with a high sensitivity and a high resolution without developing residue (scum) during development. The compounding amount of the compound having a phenolic hydroxyl group is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin. Preferred phenol compounds are those represented by the following formula.

  Specific examples of the structure shown above include the following.

  Among these, Preferably, it is shown by the following structure.

  The polyamide resin of the present invention is dissolved in a solvent and used in the form of a varnish. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N′-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether. Ter, 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 Examples thereof include 3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and the like, and these may be used alone or in combination.

  In the method of using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 50 μm. If the film thickness is less than the lower limit value, it will be difficult to fully function as a protective surface film for semiconductor elements. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Processing takes time and throughput is reduced. Application methods include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after pre-baking at 60 to 130 ° C. and drying the coating film, actinic radiation is irradiated to a desired pattern shape. 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 relief pattern is obtained by dissolving and removing the irradiated portion with a developer. 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, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An aqueous alkali solution such as a quaternary ammonium salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be suitably used. As a developing method, a spray, paddle, immersion, ultrasonic method, or the like can be used.

  Next, heat treatment is performed to form an oxazole ring and / or an imide ring, and a final pattern having high heat resistance is obtained.

  The positive photosensitive resin composition according to the present invention is used not only for semiconductor applications, but also for interlayer insulation films for multilayer circuits, cover sheets for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and devices for display elements. It is also useful as an interlayer insulating film.

  Examples of specific uses for semiconductors include a passivation film formed by forming the above-described positive photosensitive resin composition film on a semiconductor element, and a passivation film formed on a semiconductor element. A buffer coat film formed by forming the positive photosensitive resin composition film described above, an interlayer insulating film formed by forming the positive photosensitive resin composition film described above on a circuit formed on a semiconductor element, and the like. Can be mentioned.

  Among them, as one application example in which the positive photosensitive resin composition of the present invention is used in a semiconductor device, application to a semiconductor device having bumps will be described with reference to the drawings. FIG. 1 is 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, a passivation film 3 is formed on an input / output Al pad 2 in the silicon wafer 1, and a via hole is formed in the passivation film 3. Further, a positive photosensitive resin (buffer coat film) 4 is formed thereon, and a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and the metal film 5 is Each pad is insulated by etching the periphery of the wiring 6. Barrier metal 8 and solder bumps 9 are formed on the insulated pads.

  The positive photosensitive resin composition according to the present invention is used not only for semiconductor applications, but also for interlayer insulation of multilayer circuits, cover of flexible copper-clad plates, solder resist films, liquid crystal alignment films, and interlayers of elements in display elements. It is also useful as an insulating film. As other semiconductor device manufacturing methods, known methods can be used.

  Examples of the display device application include an interlayer insulating film for TFT, a TFT element flattening film, a color filter flattening film, a protrusion for an MVA liquid crystal display, and a cathode partition for an organic EL element. The usage method is based on forming the patterned positive photosensitive resin composition layer on the substrate on which the display element and the color filter are formed in accordance with the above-described method. High transparency is required for display device applications, especially interlayer insulation films and planarization films, but by introducing a post-exposure process before curing this positive photosensitive resin composition layer, transparency It is also possible to obtain a resin layer that is excellent in practical use, which is more preferable in practical use.

Example 1
[Synthesis of polyamide resin]
10.6 g (41.0 mmol) of diphenyl ether-4,4′-dicarboxylic acid, 9.3 g (35.0 mmol) of 5-phenylethynylisophthalic acid, 1,3-bis (4-carboxyphenyl)- Reaction of 0.02 g (6.0 mmol) of 1,1 ′, 3,3′-tetramethyldisiloxane with 19.5 g (164.0 mmol) of 1-hydroxy-1,2,3-benzotriazole The mixture (82.0 mmol) of the dicarboxylic acid derivative obtained in this manner and 36.6 g (100.0 mmol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were thermometer and stirrer. Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 254.6 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 4.3 g (25.0 mmol) of 4-ethynylisophthalic anhydride dissolved in 21.1 g of NMP was added and stirred for 1 hour, and then 5-norbornene-2,3-dicarboxylic acid dissolved in 12.3 g of NMP. 2.40 g (14.6 mmol) of acid anhydride was added and further stirred for 3 hours to complete the reaction. After the reaction mixture was filtered, 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 polyamide resin ( A-1) was obtained.

The structure of (A-1) is estimated as shown in the following formula. The NMR spectrum and IR spectrum of this polyamide resin (A-1) are shown in FIGS. In FIG. 3, 2214.1 cm ⁻¹ is a peak derived from a triple bond of 5-phenylethynyl-di (1-benzotriazoyl) isophthalate ester as a monomer. The vicinity of 1700 cm ⁻¹ is a peak derived from an amide bond. The vicinity of 3300 cm ⁻¹ is derived from the hydroxyl group of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane which is a monomer.

[Preparation of resin composition]
After dissolving in 100 g of the synthesized polyamide resin (A-1), 17 g of photosensitive diazoquinone (B-1) and 500 g of γ-butyrolactone, it is filtered through a 0.2 μm fluororesin filter, and a positive photosensitive resin composition Got.

[Developability evaluation]
This positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 10 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern of 0.88 to 50 μm in width and a removed pattern is drawn), Nikon Corporation i-line Exposure was performed using a stepper NSR-4425i with an exposure amount increased from 200 mJ / cm ² to 10 mJ / cm ² . Next, the exposed portion was dissolved and removed by immersing in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 80 seconds, and then rinsed with pure water for 30 seconds. As a result of observing the pattern, it was confirmed that the exposure was 500 mJ / cm ² and the pattern was well opened to a pattern of 7 μm.

[Reflow resistance evaluation]
The patterned wafer was cured at 150 ° C./30 minutes + 350 ° C./30 minutes with a clean oven at an oxygen concentration of 1000 ppm or less. Next, a flux, BF-30, manufactured by Tamura Kaken Co., Ltd. was applied to this wafer with a spinner at 500 rpm / 5 seconds + 1000 rpm / 30 seconds. In a reflow furnace, it was passed continuously twice at 140 to 160 ° C./100 seconds (preheat) and 350 ° C./30 seconds. Next, it was washed with xylene heated to 40 ° C. for 10 minutes, rinsed with isopropyl alcohol and dried. When the film surface from which the flux had been removed was observed with a metallographic microscope, it was satisfactory with no occurrence of cracks, wrinkles and the like.
The reflow resistance test was evaluated by observing the presence or absence of surface wrinkles with a microscope.
○: None on the entire surface of the wrinkle △: Some on the wrinkle ×: On the entire surface of the wrinkle

[Evaluation of hydrofluoric acid aqueous solution resistance]
The patterned wafer was cured at 150 ° C./30 minutes + 350 ° C./30 minutes with a clean oven at an oxygen concentration of 1000 ppm or less. Next, the obtained pattern was cured with a clean oven at an oxygen concentration of 1000 ppm or less at 150 ° C./30 minutes + 350 ° C./30 minutes. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

[Chemical resistance evaluation]
The patterned wafer was cured at 150 ° C./30 minutes + 350 ° C./30 minutes with a clean oven at an oxygen concentration of 1000 ppm or less. Next, the cured wafer was immersed in STRIPPER-106 manufactured by Tokyo Ohka at room temperature for 5 minutes. Next, it was rinsed with room temperature isopropyl alcohol and dried. When the surface was observed with a metallurgical microscope, it was good with no occurrence of wrinkles or peeling.
Evaluation of the chemical resistance test was performed by judging the change in the appearance of the surface with a microscope.
○: No change △ Some wrinkles × Full wrinkles or peeling

[Create display element]
After forming an ITO film on the glass substrate by vapor deposition, the ITO film was divided into stripes by an ordinary photolithography method using a photoresist. On top of this, the positive photosensitive resin composition obtained in Example 1 was applied to form a resin layer having a thickness of about 2 μm. Next, using a parallel exposure machine (light source: high-pressure mercury lamp), exposure was performed through a glass mask at an exposure intensity of 25 mW / cm ² for 10 seconds. Thereafter, the resin layer was immersed and developed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 20 seconds to expose portions other than the ITO edge on each stripe, and the ITO edge portion and the ITO removed portion. It processed so that a resin layer might be formed only on. Thereafter, the entire resin layer was subjected to post-exposure for 40 seconds at an exposure intensity of 25 mW / cm ² using the parallel exposure machine used at the time of exposure, and then heated at 230 ° C. in air using a hot air circulation dryer. Time-hardening was performed.

After depositing copper phthalocyanine as a hole injection layer and bis-N-ethylcarbazole as a hole transport layer on this substrate under a reduced pressure of 1 × 10 ⁻⁴ Pa or less, N, N′− as a light emitting layer was deposited. Diphenyl-N, N′-m-toluyl-4,4′-diamino-1,1′-biphenyl and tris (8-quinolinolate) aluminum were deposited in this order as an electron injection layer. Further, after an aluminum layer is deposited on the second electrode as a second electrode, the aluminum layer is formed into a stripe shape in a direction perpendicular to the stripe of the ITO film by a normal photolithography method using a photoresist. Divided into After the obtained substrate was dried under reduced pressure, the sealing glass plate was bonded using an epoxy adhesive to produce a display element. This display element was treated at 80 ° C. for 200 hours and then applied to both electrodes to drive sequentially. However, the element emitted light without any problem.

  Experiments of Examples 2 to 10 and Comparative Examples 1 to 3 were performed in the same manner as in Example 1 except that the materials to be blended and the addition amount were changed. The results are summarized in Table 1.

Details of the products listed in Table 1 are as follows.
(1) 6FAP; 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (central glass)
(2) E1; a carboxylic acid derivative obtained by reacting 5-phenylethynyl-isophthalic acid with 1-hydroxy-1,2,3-benzotriazole
(3) E2: a carboxylic acid derivative obtained by reacting 5-ethynylisophthalic acid with 1-hydroxy-1,2,3-benzotriazole
(4) E3: a carboxylic acid derivative obtained by reacting 1,3-bis (carbonylphenyl) -1,1 ′, 3,3′-tetramethyldisiloxane and 1-hydroxy-1,2,3-benzotriazole
(5) E4: a carboxylic acid derivative obtained by reacting 1,3-bis (carbonylbutyl) -1,1 ′, 3,3′-tetramethyldisiloxane and 1-hydroxy-1,2,3-benzotriazole
(6) E5; a carboxylic acid derivative obtained by reacting 4,4′-dicarbonylphenyl ether with 1-hydroxy-1,2,3-benzotriazole
(7) Nadic acid; 5-norbornene-2,3-dicarboxylic anhydride (Acros)
(8) KK-1; 4-Ethynylphthalic anhydride (Fuji Film)
(9) TekOC-4HBPA; 2,2′-bis [4,4′-bis (4-hydroxy-3-methylphenyl) cyclohexyl] propane and 3-diazo-3,4-dihydro-4-oxo-naphthalene Derivatives consisting of 1-sulfonic acid
(10) o, o'-BPF;2,2'-dihydroxydiphenylmethane (Tokyo Kasei)

  The compounds used in the examples of the present invention are synthesized according to the following scheme.

  The present invention is a positive photosensitive resin composition and a semiconductor device that are excellent in reflow resistance and hydrofluoric acid aqueous solution resistance, and can be suitably used for a surface protective film and an interlayer insulating film of a semiconductor element.

FIG. 1 is a cross-sectional view of a resin-encapsulated semiconductor device having a bump structure of the present invention. FIG. 2 is an NMR spectrum of the polyamide resin (A-1) of the present invention. FIG. 3 is an IR spectrum of the polyamide resin (A-1) of the present invention.

Explanation of symbols

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

Claims (14)

A polyamide resin containing structural units (I) and (II) represented by the following formula.

(In the formula, Y ₁ is an organic group having a siloxane bond, Y ₂ is an organic group having a triple bond. X is a divalent to tetravalent organic group, Y ₁ and Y ₂ are divalent to hexavalent organic groups. X, Y ₁ and Y ₂ in the resin may be the same or different, a is an integer of 0 to 2, b is an integer of 0 to 4. R ¹ is a hydroxyl group, or —O—R ^3. R ² represents one of a hydroxyl group, a carboxyl group, —O—R ³ , and —COO—R ^3. R ³ represents an organic group having 1 to 15 carbon atoms, and R ¹ and R ² are repeated. Each may be the same or different.) A polyamide resin represented by the structure represented by formula (1).

Wherein Y ₁ is an organic group having a siloxane bond, Y ₂ is an organic group having a triple bond, and Y ₃ is an organic group having neither a siloxane bond nor an unsaturated bond. X is 2 to 4. A valent organic group, Y ₁ , Y ₂ , and Y ₃ represent a divalent to hexavalent organic group, and X, Y ₁ , Y ₂ , and Y ₃ in the resin may be the same or different. m and n are molar ratios of structural units, and l + m + n = 100, l, m> 0, and n ≧ 0, a is an integer of 0 to 2, b is an integer of 0 to 4. R ¹ is Represents a hydroxyl group or —O—R ^3. R ² represents a hydroxyl group, a carboxyl group, —O—R ³ or —COO—R ^3. R ³ represents an organic group having 1 to 15 carbon atoms. R ¹ and R ² may be the same or different in the repetition.) The polyamide resin according to claim 1 or 2, wherein the siloxane bond has a structure represented by the following formula.

(In the formula, R ⁴ and R ⁵ each represent a divalent organic group, R ⁶ and R ⁷ each represent a monovalent organic group, and n represents 0 to 20.) The polyamide resin according to any one of claims 1 to 3 , wherein both ends of the resin are sealed with an acid anhydride having an unsaturated bond. The polyamide resin according to any one of claims 1 to 3 , wherein both ends of the resin are
An acid anhydride having a double bond in the molecule; and
An acid anhydride having a triple bond in the molecule;
A polyamide resin characterized by being sealed by. (A) the polyamide resin according to any one of claims 1 to 5 ,
(B) a photosensitive diazoquinone compound,
A positive photosensitive resin composition comprising: The positive photosensitive resin composition according to claim 6 , further comprising (C) a compound having a phenolic hydroxyl group. The positive photosensitive resin composition according to claim 7, wherein the compound (C) having a phenolic hydroxyl group has a structure represented by the following formula.

(Wherein R ⁸ and R ⁹ represent one selected from a halogen atom, an alkyl group, an alkoxy group, an alkyl ester group, a cycloalkyl group and a cycloalkoxy group. M = 0 to 5, n = R ⁸ and R ⁹ may be the same or different, and p = 0 to 3, an integer of q = 0 to 3, and p + q ≧ 2.R ¹⁰ is a single bond, methylene Represents one selected from a group, an alkylene group, an oxygen atom, a carbonyl group, a carbonyl ether group, a sulfur atom, a sulfonyl group, and an azo group.) Applying the positive photosensitive resin composition according to any one of claims 6 to 8 on a substrate to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
A step of bringing a developer into contact with the resin layer after irradiation with the active energy ray and then heating the resin layer;
The pattern formation method characterized by including. A semiconductor device comprising a semiconductor chip and a protective film laminated on the circuit surface side,
The semiconductor device wherein the protective layer is constituted by a positive-type photosensitive resin composition according to any one of claims 6 to 8. A display element comprising a display element substrate and a planarizing film covering the surface thereof,
Display element and the planarization layer are those comprising a positive photosensitive resin composition according to any one of claims 6 to 8. Wherein the display device is further be one comprising an insulating film, a display device according to claim 11, wherein the insulating film is one that includes a positive photosensitive resin composition according to any one of claims 6 to 8. A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film laminated on the circuit surface side,
Applying the positive photosensitive resin composition according to any one of claims 6 to 8 on the semiconductor chip to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
Forming a protective film by bringing a developer into contact with the resin layer after irradiation with the active energy ray and then heating the resin layer;
A method for manufacturing a semiconductor device, comprising: A display element manufacturing method comprising a display element substrate and a planarizing film covering the surface thereof,
Forming a resin layer by applying the positive photosensitive resin composition according to any one of claims 6 to 8 on a substrate for the display device,
Irradiating active energy rays to a desired portion of the resin layer;
A step of bringing the developer into contact with the resin layer after irradiation with active energy rays and then heating the resin layer to form the planarizing film;
A method for manufacturing a display element, comprising:

Images