JP4581706B2 - Positive photosensitive resin composition, semiconductor device and display element using the positive photosensitive resin composition, and method for manufacturing semiconductor device and display element - Google Patents

Positive photosensitive resin composition, semiconductor device and display element using the positive photosensitive resin composition, and method for manufacturing semiconductor device and display element Download PDF

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JP4581706B2
JP4581706B2 JP2005019292A JP2005019292A JP4581706B2 JP 4581706 B2 JP4581706 B2 JP 4581706B2 JP 2005019292 A JP2005019292 A JP 2005019292A JP 2005019292 A JP2005019292 A JP 2005019292A JP 4581706 B2 JP4581706 B2 JP 4581706B2
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resin composition
positive photosensitive
photosensitive resin
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周作 岡明
誠 堀井
孝 平野
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Sumitomo Bakelite Co Ltd
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Description

本発明は、ポジ型感光性樹脂組成物、該ポジ型感光性樹脂組成物を用いた半導体装置及び表示素子、並びに半導体装置及び表示素子の製造方法に関するものである。   The present invention relates to a positive photosensitive resin composition, a semiconductor device and a display element using the positive photosensitive resin composition, and a method for manufacturing the semiconductor device and the display element.

従来、半導体素子の表面保護膜、層間絶縁膜には、耐熱性に優れ又卓越した電気特性、機械特性等を有するポリベンゾオキサゾール樹脂やポリイミド樹脂が用いられている。一方、プロセスの簡略化するため、それらポリベンゾオキサゾール樹脂やポリイミド樹脂に感光性ジアゾキノン化合物と組み合わせたポジ型感光性樹脂も使用されている(例えば、特許文献1参照)。近年、半導体素子の小型化、高集積化による多層配線化、チップサイズパッケージ(CSP)、ウエハーレベルパッケージ(WLP)への移行等により、低誘電率化や、また、金、銅、アルミニウム、チタニウム等の配線または配線金属との密着性向上の要求があり、更に高性能のポリベンゾオキサゾール樹脂やポリイミド樹脂が必要とされている。
これらポジ型感光性樹脂を実際のプロセスに用いる場合、問題となるのは加工特性であり、その中でも特に重要なのは露光時間である。つまり、スループット向上のため、短時間で露光できるポジ型感光性樹脂が望まれている。
ポジ型感光性樹脂に、有機ケイ素化合物を用いることにより、シリコンやチッ化膜等の基盤との密着性の向上が図られることが知られている(例えば、特許文献2参照)。しかしながら、金等に代表される再配線を構成する材料に対しては、劣る傾向がある。
Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and 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 obtained by combining the polybenzoxazole resin or polyimide resin with a photosensitive diazoquinone compound is also used (for example, see Patent Document 1). In recent years, due to miniaturization of semiconductor elements, multilayer wiring due to high integration, shift to chip size package (CSP), wafer level package (WLP), etc., low dielectric constant, gold, copper, aluminum, titanium There is a demand for improving adhesion to wirings or wiring metals such as high performance polybenzoxazole resins and polyimide resins.
When these positive photosensitive resins are used in an actual process, the problem is processing characteristics, and among them, the exposure time is particularly important. That is, in order to improve throughput, a positive photosensitive resin that can be exposed in a short time is desired.
It is known that by using an organosilicon compound for the positive photosensitive resin, the adhesion with a substrate such as silicon or a nitride film can be improved (for example, see Patent Document 2). However, it tends to be inferior to materials constituting rewiring represented by gold or the like.

特公平1−46862号公報Japanese Examined Patent Publication No. 1-46862 特開2000−281969号公報JP 2000-281969 A

本発明は、基盤との密着性に優れたポリベンゾオキサゾール樹脂、ポリイミド樹脂又はその共重合樹脂を提供することを目的とするポリアミド樹脂とそれらを用いた露光特性に優れるポジ型感光性樹脂組成物、該ポジ型感光性樹脂組成物を用いた半導体装置及び表示素子を提供するものである。   The present invention relates to a polyamide resin intended to provide a polybenzoxazole resin, a polyimide resin or a copolymer resin thereof excellent in adhesion to a substrate, and a positive photosensitive resin composition excellent in exposure characteristics using them. A semiconductor device and a display element using the positive photosensitive resin composition are provided.

このような目的は、下記[1]〜[11]に記載の本発明により達成される。
[1] ポリアミド樹脂(A)、感光性ジアゾキノン化合物(B)及びSを含有した有機ケイ素化合物(C)を含んでなるポジ型感光性樹脂組成物、
[2] 有機ケイ素化合物(C)が一般式(1)及び/または(2)で表される群より選ばれた1種類以上の有機ケイ素化合物(C)を含んでなる第[1]項記載のポジ型感光性樹脂組成物、
Such an object is achieved by the present invention described in the following [1] to [11].
[1] A positive photosensitive resin composition comprising a polyamide resin (A), a photosensitive diazoquinone compound (B), and an organosilicon compound (C) containing S,
[2] Item [1], wherein the organosilicon compound (C) comprises one or more organosilicon compounds (C) selected from the group represented by the general formula (1) and / or (2) A positive photosensitive resin composition,

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

[3] ポリアミド樹脂(A)が一般式(3)で示される構造を有するポリアミド樹脂(A)である第[1]又は[2]項記載のポジ型感光性樹脂組成物、 [3] The positive photosensitive resin composition according to [1] or [2], wherein the polyamide resin (A) is a polyamide resin (A) having a structure represented by the general formula (3),

Figure 0004581706
Figure 0004581706

[4] 第[1]、[2]又は[3]項記載の有機ケイ素化合物(C)が0.1〜20重量部を含んでなるポジ型感光性樹脂組成物、
[5] ポジ型感光性樹脂組成物が、更にフェノール性水酸基を有する化合物(D)を含んでなる第[1]、[2]、[3]又は[4]項記載のポジ型感光性樹脂組成物、
[6]フェノール性水酸基を有する化合物(D)が下記構造である第[5]項に記載のポ
ジ型感光性樹脂組成物、
[4] A positive photosensitive resin composition comprising 0.1 to 20 parts by weight of the organosilicon compound (C) according to item [1], [2] or [3],
[5] The positive photosensitive resin according to item [1], [2], [3] or [4], wherein the positive photosensitive resin composition further comprises a compound (D) having a phenolic hydroxyl group. Composition,
[6] The positive photosensitive resin composition according to item [5], wherein the compound (D) having a phenolic hydroxyl group has the following structure:

Figure 0004581706
Figure 0004581706

[7] 第[1]〜[6]項のいずれか1項に記載のポジ型感光性樹脂組成物を基板上に塗布して組成物層を形成する工程と、概組成物層に活性エネルギー線を照射して現像液と接触させてパターンを形成する工程と、概組成物を加熱する工程を有することを特徴とするパターン状樹脂膜の製造方法、 [7] A step of applying the positive photosensitive resin composition according to any one of items [1] to [6] onto a substrate to form a composition layer, and an active energy in the composition layer. A method for producing a patterned resin film, comprising: a step of forming a pattern by irradiating a line and contacting with a developer; and a step of heating the approximate composition;

[8] 第[1]〜[6]項のいずれか1項に記載のポジ型感光性樹脂組成物を用いて製作されてなることを特徴とする半導体装置。 [8] A semiconductor device manufactured using the positive photosensitive resin composition according to any one of items [1] to [6].

[9] 第[1]〜[6]項のいずれか1項に記載のポジ型感光性樹脂組成物を用いて製作されてなることを特徴とする表示素子、 [9] A display element produced by using the positive photosensitive resin composition according to any one of items [1] to [6],

[10] 第[1]〜[6]項のいずれか1項に記載のポジ型感光性樹脂組成物を加熱後の膜厚が、0.1〜30μmになるように半導体素子上でパターン加工して得られることを特徴とする半導体装置の製造方法、 [10] Pattern processing on the semiconductor element so that the film thickness after heating the positive photosensitive resin composition according to any one of the items [1] to [6] is 0.1 to 30 μm. A method of manufacturing a semiconductor device, characterized in that

[11] 第[1]〜[6]項のいずれか1項に記載のポジ型感光性樹脂組成物を加熱後の膜厚が、0.1〜30μmになるように表示素子用基板上にパターン加工して得られることを特徴とする表示素子の製造方法。 [11] The positive photosensitive resin composition according to any one of items [1] to [6] is heated on the display element substrate so that the film thickness after heating is 0.1 to 30 μm. A display element manufacturing method obtained by patterning.

本発明に従うと、基盤との密着性に優れたポリベンゾオキサゾール樹脂、ポリイミド樹脂、その共重合である樹脂を提供することを目的とするポリアミド樹脂とそれらを用いた露光特性に優れるポジ型感光性樹脂組成物及びそれを用いた半導体装置及び表示素子を得ることができる。   According to the present invention, a polybenzoxazole resin excellent in adhesion to the substrate, a polyimide resin, a polyamide resin for the purpose of providing a resin that is a copolymer thereof, and a positive photosensitive property excellent in exposure characteristics using them. A resin composition and a semiconductor device and a display element using the resin composition can be obtained.

本発明で用いるポリアミド樹脂としては、ポリベンゾオキサゾール前駆体構造、ポリアミド酸構造又はポリアミド酸エステル構造であって、主鎖又は側鎖に水酸基、カルボキシル基、又はスルホン酸基を有する樹脂である。これらの中で好ましくは、一般式(3)で示される構造を有するポリアミド樹脂が挙げられる。
一般式(3)中のXは、2〜4価の有機基を表し、またR7は、水酸基又はO−R9であり、mは0〜2の整数である。各々のR7は同一でも異なっていても良い。一般式(3)中のYは、2〜6価の有機基を表し、R8は水酸基、カルボキシル基、O−R9又はCOO−R9であり、nは0〜4の整数である。各々のR8は同一でも異なっていても良い。ここでR9は炭素数1〜15の有機基である。但し、R7として水酸基がない場合は、R8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。又R8としてカルボキシル基がない場合は、R7は少なくとも1つは水酸基でなければならない。
一般式(3)で示される構造を含むポリアミド樹脂は、例えば、Xの構造を有するジアミン或いはビス(アミノフェノール)、2,4−ジアミノフェノール等から選ばれる化合物とYの構造を有する、テトラカルボン酸無水物、トリメリット酸無水物、ジカルボン酸或いはジカルボン酸ジクロライド、ジカルボン酸誘導体、ヒドロキシジカルボン酸、ヒドロキシジカルボン酸誘導体等から選ばれる化合物とを反応して得られるものである。なお、ジカルボン酸の場合には反応収率等を高めるため、1−ヒドロキシ−1,2,3−ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。
一般式(3)で示される構造を含むポリアミド樹脂において、Xの置換基としてのO−R9、Yの置換基としてのO−R9、COO−R9は、水酸基、カルボキシル基のアルカリ水溶液に対する溶解性を調節する目的で、炭素数1〜15の有機基であるR9で保護された基であり、必要により水酸基、カルボキシル基を保護しても良い。R9の例としては、ホルミル基、メチル基、エチル基、プロピル基、イソプロピル基、ターシャリーブチル基、ターシャリーブトキシカルボニル基、フェニル基、ベンジル基、テトラヒドロフラニル基、テトラヒドロピラニル基等が挙げられる。
このポリアミド樹脂を約250〜400℃で加熱すると脱水閉環し、ポリイミド樹脂、又はポリベンゾオキサゾール樹脂、或いは両者の共重合という形で耐熱性樹脂が得られる。
一般式(3)のXとしては、例えば、
The polyamide resin used in the present invention is a resin having a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure and having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain. Among these, a polyamide resin having a structure represented by the general formula (3) is preferable.
X in the general formula (3) represents a divalent to tetravalent organic group, R 7 is a hydroxyl group or O—R 9 , and m is an integer of 0 to 2. Each R 7 may be the same or different. Y in the general formula (3) represents a divalent to hexavalent organic group, R 8 is a hydroxyl group, a carboxyl group, O—R 9 or COO—R 9 , and n is an integer of 0 to 4. Each R 8 may be the same or different. Here, R 9 is an organic group having 1 to 15 carbon atoms. However, when R 7 has no hydroxyl group, at least one R 8 must be a carboxyl group. When R 8 has no carboxyl group, at least one R 7 must be a hydroxyl group.
The polyamide resin having the structure represented by the general formula (3) is, for example, a tetracarboxylic acid having a Y structure and a compound selected from a diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol or the like. It is obtained by reacting with a compound selected from acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like. In the case of a dicarboxylic acid, an active ester 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.
In the polyamide resin having the structure represented by the general formula (3), O—R 9 as a substituent of X, O—R 9 and COO—R 9 as a substituent of Y are hydroxyl aqueous solutions of hydroxyl groups and carboxyl groups Is a group protected by R 9 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 9 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.
When this polyamide resin 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.
As X in the general formula (3), for example,

Figure 0004581706
Figure 0004581706

等であるが、これらに限定されるものではない。
これらの中で特に好ましいものとしては、

Figure 0004581706
However, it is not limited to these.
Among these, particularly preferred are:
Figure 0004581706

より選ばれるものであり、又2種類以上用いても良い。
又一般式(3)で示される構造を含むポリアミド樹脂で使用できるYは、例えば、

Figure 0004581706
Two or more types may be used.
Y that can be used in the polyamide resin having the structure represented by the general formula (3) is, for example,
Figure 0004581706

等であるが、これらに限定されるものではない。
これらの中で特に好ましいものとしては、

Figure 0004581706
However, it is not limited to these.
Among these, particularly preferred are:
Figure 0004581706

より選ばれるものであり、又2種類以上用いても良い。
又本発明においては、保存性という観点から、末端を封止する事が望ましい。封止にはアルケニル基又はアルキニル基を少なくとも1個有する脂肪族基又は環式化合物基を有する誘導体を一般式(3)で示されるポリアミドの末端に酸誘導体やアミン誘導体として導入することができる。具体的には、例えば、Xの構造を有するジアミン或いはビス(アミノフェノール)、2,4−ジアミノフェノール等から選ばれる化合物とYの構造を有するテトラカルボン酸無水物、トリメリット酸無水物、ジカルボン酸或いはジカルボン酸ジクロライド、ジカルボン酸誘導体、ヒドロキシジカルボン酸、ヒドロキシジカルボン酸誘導体等から選ばれる化合物とを反応させて得られた一般式(3)で示される構造を含むポリアミド樹脂を合成した後、該ポリアミド樹脂中に含まれる末端のアミノ基をアルケニル基又はアルキニル基を少なくとも1個有する脂肪族基又は環式化合物基を含む酸無水物又は酸誘導体を用いてアミドとしてキャップすることが好ましい。アミノ基と反応した後のアルケニル基又はアルキニル基を少なくとも1個有する脂肪族基又は環式化合物基を含む酸無水物又は酸誘導体に起因する基としては、例えば、
Two or more types may be used.
In the present invention, it is desirable to seal the end from the viewpoint of storage stability. For sealing, a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polyamide represented by the general formula (3). Specifically, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, and the like, and a tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid having a structure of Y After synthesizing a polyamide resin having a structure represented by the general formula (3) obtained by reacting with a compound selected from acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. It is preferable to cap the terminal amino group contained in the polyamide resin as an amide using an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include:

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

等が挙げられるが、これらに限定されるものではない。
これらの中で特に好ましいものとしては、

Figure 0004581706
However, it is not limited to these.
Among these, particularly preferred are:
Figure 0004581706

より選ばれるものであり、又2種類以上用いても良い。
更に、必要によって用いる一般式(3)で示される構造を含むポリアミド樹脂のZは、例えば、

Figure 0004581706
Two or more types may be used.
Furthermore, Z of the polyamide resin including the structure represented by the general formula (3) used as necessary is, for example,
Figure 0004581706

等が挙げられるが、これらに限定されるものではない。
これらの中で特に好ましいものとしては、

Figure 0004581706
However, it is not limited to these.
Among these, particularly preferred are:
Figure 0004581706

より選ばれるものであり、又2種類以上用いても良い。
一般式(3)で示される構造を含むポリアミド樹脂のZは、例えば、シリコンウエハーのような基盤に対して、特に優れた密着性が必要な場合に用いるが、その使用割合bは最大40モル%までである。40モル%を超えると露光部の樹脂の溶解性が極めて低下し、現像残り(スカム)が発生し、パターン加工ができなくなる。
Two or more types may be used.
Z of the polyamide resin having the structure represented by the general formula (3) is used when particularly excellent adhesion is required for a substrate such as a silicon wafer, for example. Up to%. When it exceeds 40 mol%, the solubility of the resin in the exposed area is extremely lowered, developing residue (scum) is generated, and pattern processing becomes impossible.

本発明で用いる感光性ジアゾキノン化合物(B)は、1,2−ベンゾキノンジアジド或いは1,2−ナフトキノンジアジド構造を有する化合物であり、米国特許明細書第2772975号、第2797213号、第3669658号により公知の物質である。例えば、下記のものが挙げられる。   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. Nos. 2,729,975, 2,797,213 and 3,669,658. It is a substance. For example, the following are mentioned.

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

これらの内で、特に好ましいのは、フェノール化合物と1,2−ナフトキノン−2−ジアジド−5−スルホン酸又は1,2−ナフトキノン−2−ジアジド−4−スルホン酸とのエステルである。それらについては例えば、下記のものが挙げられるが、これらに限定されるものではない。これらは2種以上用いても良い。   Among these, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is particularly preferable. Examples of these include, but are not limited to, the following. Two or more of these may be used.

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

本発明で用いる感光性ジアゾキノン化合物(B)の好ましい添加量は、ポリアミド樹脂100重量部に対して1〜50重量部である。1重量部未満の場合では良好なパターンが得られず、50重量部を越えると感度が大幅に低下する。   The preferable addition amount of the photosensitive diazoquinone compound (B) used in the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin. If the amount is less than 1 part by weight, a good pattern cannot be obtained, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

本発明で用いるSを含有する有機ケイ素化合物は、感光性樹脂と基盤(金、アルミニウム、銅、チタニウムなどの金属単体膜あるいは合金膜などで、特に金)との密着性を向上させ、更に良好な加工性を維持するために用いられるものである。好ましくは、一般式(1)、(2)で示される有機ケイ素化合物であり、これらを1種又は、2種以上混合して用いても良い。添加量はポリアミド樹脂100重量部に対して、0.1〜20重量部であ
ることが望ましい。0.1重量部未満では接着性向上効果が得られないので好ましくなく、20重量部を超えると、半導体素子上に形成されるポリベンゾオキサゾール皮膜の機械的強度が低下して応力緩和効果が薄れるので好ましくない。一般式(1)、(2)の有機ケイ素化合物は、例えば、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、ビス(3−トリエトキシシリルプロピル)ジスルファン、ビス(3−トリエトキシシリルプロピル)テトラスルファン、ビス(3−トリエトキシシリルプロピル)ヘキサスルファン、ビス(3−トリエトキシシリルプロピル)オクタスルファン等であるが、これらに限定されない。
更に本発明では、高感度で現像時に現像残り(スカム)無く高解像度でパターニングできるようにフェノール性水酸基を有する化合物(D)を併用することが好ましい。フェノール性水酸基を有する化合物の配合量は、ポリアミド樹脂100重量部に対して1〜30重量部が好ましい。好ましいフェノール化合物としては一般式(4)で示されるものである。一般式(4)の具体的な構造としては下記のもの等を挙げることができるがこれらに限定されない。

The organosilicon compound containing S used in the present invention improves the adhesion between the photosensitive resin and the substrate (single metal film or alloy film of gold, aluminum, copper, titanium, etc., particularly gold), and is even better. It is used for maintaining good workability. The organic silicon compounds represented by the general formulas (1) and (2) are preferable, and these may be used alone or in combination. The addition amount is desirably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin. If the amount is less than 0.1 parts by weight, it is not preferable because the effect of improving the adhesiveness cannot be obtained. Therefore, it is not preferable. Examples of the organosilicon compounds represented by the general formulas (1) and (2) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, bis (3-triethoxysilylpropyl) disulfane, and bis (3-triethoxy). Silylpropyl) tetrasulfane, bis (3-triethoxysilylpropyl) hexasulfane, bis (3-triethoxysilylpropyl) octasulfane, and the like, but are not limited thereto.
Further, in the present invention, it is preferable to use a compound (D) having a phenolic hydroxyl group in combination so that high-sensitivity development and no development residue (scum) can be performed at a high resolution. As for the compounding quantity of the compound which has a phenolic hydroxyl group, 1-30 weight part is preferable with respect to 100 weight part of polyamide resins. Preferred phenol compounds are those represented by the general formula (4). Specific examples of the general formula (4) include the following, but are not limited thereto.

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
これらの中で好ましくは
Figure 0004581706
Of these, preferably

Figure 0004581706
から選ばれるものである。
Figure 0004581706
It is chosen from.

本発明におけるポジ型感光性樹脂組成物には、必要によりレベリング剤、シランカップリング剤、チタネート系カップリング剤およびそれらの各反応物等の添加剤を添加することができる。
本発明のポリアミド樹脂は溶剤に溶解し、ワニス状にして使用する。溶剤としては、N−メチル−2−ピロリドン、γ−ブチロラクトン、N,N−ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル−1,3−ブチレングリコールアセテート、1,3−ブチレングリコール−3−モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、メチル−3−メトキシプロピオネート等が挙げられ、単独でも混合して用いても良い。
本発明のポジ型感光性樹脂組成物の使用方法は、まず該組成物を適当な支持体、例えば、シリコンウエハー、セラミック基板、アルミ基板等に塗布する。塗布量は、半導体装置の場合、硬化後の最終膜厚が0.1〜50μmになるよう塗布する。膜厚が下限値未満の場合、半導体素子の表面保護膜としての機能を十分に発揮することが困難となり、上限値を越えると、微細な加工パターンを得ることが困難となるばかりでなく、加工に時間がかかりスループットが低下する。塗布方法としては、スピンナーを用いた回転塗布、スプレーコーターを用いた噴霧塗布、浸漬、印刷、ロールコーティング等がある。次に、60〜130℃でプリベークして塗膜を乾燥後、所望のパターン形状に化学線を照射する。化学線としては、X線、電子線、紫外線、可視光線等が使用できるが、200〜500nmの波長のものが好ましい。
If necessary, additives such as a leveling agent, a silane coupling agent, a titanate coupling agent, and their respective reactants can be added to the positive photosensitive resin composition in the present invention.
The polyamide resin of the present invention is 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.
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 surface protection film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine 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 prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the 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.

次に照射部を現像液で溶解除去することによりレリーフパターンを得る。現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、n−プロピルアミン等の第1アミン類、ジエチルアミン、ジ−n−プロピルアミン等の第2アミン類、トリエチルアミン、メチルジエチルアミン等の第3アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の第4級アンモニウム塩等のアルカリ類の水溶液及びこれにメタノール、エタノールのごときアルコール類等の水溶性有機溶媒や界面活性剤を適当量添加した水溶液を好適に使用することができる。現像方法としては、スプレー、パドル、浸漬、超音波等の方式が可能である。
次に、現像によって形成したレリーフパターンをリンスする。リンス液としては、蒸留水を使用する。次に加熱処理を行い、オキサゾール環及び/又はイミド環を形成し、耐熱性に富む最終パターンを得る。
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, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a 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, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.
Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance.

本発明による感光性樹脂組成物は、半導体用途のみならず、多層回路の層間絶縁やフレキシブル銅張板のカバーコート、ソルダーレジスト膜や液晶配向膜、表示装置用途としても有用である。
半導体用としての具体的用途の例としては、半導体素子上に上述の感光性樹脂組成物膜を形成することによるパッシベーション膜、また半導体素子上に形成されたパッシベーション膜上に上述の感光性樹脂組成物膜を形成することによるバッファコート膜、半導体素子上に形成された回路上に上述の感光性樹脂組成物膜を形成することによる層間絶縁膜などを挙げることができる。
その中で、本発明の感光性樹脂組成物を半導体装置に用いた応用例の1つとして、バンプを有する半導体装置への応用について図面を用いて説明する。図1は、本発明のバンプを有する半導体装置のパット部分の拡大断面図である。図1に示すように、シリコンウェハー1には入出力用のAlパッド2上にパッシベーション膜3が形成され、そのパッシベーション膜3にビアホールが形成されている。更に、この上にポジ型感光性樹脂(バッファコート膜)4が形成され、更に、金属(Cr、Ti等)膜5がAlパッド2と接続されるように形成され、その金属膜5はハンダバンプ9の周辺をエッチングして、各パッド間を絶縁する。絶縁されたパッドにはバリアメタル8とハンダバンプ9が形成されている。
表示体装置用途としての例は、TFT用層間絶縁膜、TFT素子平坦化膜、カラーフィルター平坦化膜、MVA型液晶表示装置用突起、有機EL素子用陰極隔壁がある。その使用方法は、半導体用途に順じ、表示体素子やカラーフィルターを形成した基板上にパターン化された感光性樹脂組成物層を、上記の方法で形成することによる。表示体装置用途、特に層間絶縁膜や平坦化膜には、高い透明性が要求されるが、この感光性樹脂組成物層の硬化前に、後露光工程を導入することにより、透明性に優れた樹脂層が得られることもでき、実用上更に好ましい。
The photosensitive resin composition according to the present invention is useful not only for semiconductor applications, but also for interlayer insulation of multilayer circuits, flexible copper-clad cover coats, solder resist films, liquid crystal alignment films, and display devices.
Examples of specific uses for semiconductors include a passivation film obtained by forming the above-described photosensitive resin composition film on a semiconductor element, and a photosensitive resin composition described above on a passivation film formed on a semiconductor element. Examples thereof include a buffer coat film formed by forming a physical film, and an interlayer insulating film formed by forming the above-described photosensitive resin composition film on a circuit formed on a semiconductor element.
Among them, as one application example in which the 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 a silicon wafer 1, and a via hole is formed in the passivation film 3. Further, a positive photosensitive resin (buffer coating 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 formed of solder bumps. 9 is etched to insulate between the pads. Barrier metal 8 and solder bumps 9 are formed on the insulated pads.
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 device, and a cathode partition for an organic EL element. The usage method is based on forming the photosensitive resin composition layer patterned on the board | substrate which formed the display body element and the color filter by said method according to a semiconductor use. High transparency is required for display device applications, especially interlayer insulation films and planarization films, but excellent transparency is achieved by introducing a post-exposure step before curing of the photosensitive resin composition layer. A resin layer can be obtained, which is more preferable in practical use.

参考例1
[ポリアミド樹脂の合成]
4,4’−オキシジフタル酸無水物17.1g(0.055モル)と2−メチル−2−プロパノール12.4g(0.167モル)とピリジン10.9g(0.138モル)とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた4つ口のセパラブルフラスコに入れ、N−メチル−2−ピロリドン150gを加えて溶解させた。この反応溶液に1−ヒドロキシ−1,2,3−ベンゾトリアゾール14.9g(0.110モル)をN−メチル−2−ピロリドン30gと共に滴下した後、ジシクロヘキシルカルボジイミド22.7 g(0.110モル)をN−メチル−2−ピロリドン50gと共に滴下し、室温で一
晩反応させた。その後、この反応溶液にジフェニルエーテル−4,4’−ジカルボン酸1モルと1−ヒドロキシ−1,2,3−ベンゾトリアゾール2 モルとを反応させて得られ
たジカルボン酸誘導体(活性エステル)27.1g(0.055モル)とヘキサフルオロ−2,2−ビス(3−アミノ−4−ヒドロキシフェニル)プロパン44.8g(0.122モル)をN−メチル−2−ピロリドン70gと共に添加し、室温で2時間攪拌した。その後オイルバスを用いて75℃にて12時間攪拌して反応を終了した。反応混合物を濾過した後、反応混合物を水/メタノール=3/1(体積比)の溶液に投入、沈殿物を濾集し水で十分洗浄した後、真空下で乾燥し、一般式(3)で示され、Xが下記式X−1、Yが下記式Y−1及びY−2で、a=100、b=0からなるポリアミド樹脂(A−1)を合成した。

<< Reference Example 1 >>
[Synthesis of polyamide resin]
A thermometer containing 17.1 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 12.4 g (0.167 mol) of 2-methyl-2-propanol and 10.9 g (0.138 mol) of pyridine. Into a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved. To this reaction solution, 14.9 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole was added dropwise together with 30 g of N-methyl-2-pyrrolidone, and then 22.7 g (0.110 mol) of dicyclohexylcarbodiimide. ) Was added dropwise together with 50 g of N-methyl-2-pyrrolidone and allowed to react overnight at room temperature. Thereafter, 27.1 g of a dicarboxylic acid derivative (active ester) obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole with this reaction solution. (0.055 mol) and 44.8 g (0.122 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane with 70 g of N-methyl-2-pyrrolidone are added at room temperature. Stir for 2 hours. Thereafter, the reaction was terminated by stirring for 12 hours at 75 ° C. using an oil bath. 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, and then dried under vacuum to obtain the general formula (3) And X is the following formula X-1, Y is the following formulas Y-1 and Y-2, and a polyamide resin (A-1) having a = 100 and b = 0 was synthesized.

[樹脂組成物の作製]
合成したポリアミド樹脂(A−1)10g、下記構造を有する感光性ジアゾキノン(B−1)2g、下記構造を有する有機ケイ素化合物(C−1)1g、γ―ブチロラクトン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。
[Preparation of resin composition]
After dissolving in 10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the following structure, 1 g of organosilicon compound (C-1) having the following structure, and 70 g of γ-butyrolactone, fluororesin The mixture was filtered with a filter made to obtain a positive photosensitive resin composition.

[現像性評価]
このポジ型感光性樹脂組成物をシリコンウエハー上にスピンコーターを用いて塗布した後、ホットプレートにて120℃で4分乾燥し、膜厚約10μmの塗膜を得た。この塗膜に凸版印刷(株)製マスク(テストチャートNo.1:幅0.88〜50μmの残しパターン及び抜きパターンが描かれている)を通して、(株)ニコン製i線ステッパNSR―4425iを用いて、露光量を200mJ/cm2から10mJ/cm2ステップで増やして露光を行った。次に2.38%のテトラメチルアンモニウムヒドロキシド水溶液に80秒浸漬することによって露光部を溶解除去した後、純水で30秒間リンスした。パターンを観察したところ、露光量560mJ/cm2で、5μmのパターンまで良好に開口していることが確認できた。
[Developability evaluation]
This positive photosensitive resin composition was applied on 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: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn), Nikon Corporation i-line stepper NSR-4425i The exposure amount was increased by 200 mJ / cm 2 to 10 mJ / cm 2 steps. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 80 seconds, and then rinsed with pure water for 30 seconds. When the pattern was observed, it was confirmed that the pattern was well opened up to a pattern of 5 μm with an exposure amount of 560 mJ / cm 2 .

[物性評価]
このポジ型感光性樹脂組成物を硬化後5μmになるように金メッキ処理された6インチシリコンウエハー上にスピンコーターを用いて塗布した後、ホットプレートにて120℃で4分乾燥し、次にクリーンオーブンを用いて酸素濃度1000ppm以下で、150℃/30分+320℃/30分で加熱硬化を行った。得られた塗膜のパターン開口を行っていない未露光部分の塗膜を1cm角に100個の碁盤目にカットした。これにセロテープ(登録商標)を貼り付け、引き剥がそうとしたが、剥がれた塗膜の数は0であり、硬化膜の金属への密着性も優れていることが確認できた。
[Evaluation of the physical properties]
This positive photosensitive resin composition was applied onto a 6-inch silicon wafer that had been gold-plated to a thickness of 5 μm after curing using a spin coater, dried on a hot plate at 120 ° C. for 4 minutes, and then cleaned. Heat curing was performed at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using an oven. The coating film of the unexposed part which did not perform pattern opening of the obtained coating film was cut into 100 square grids at 1 cm square. Cellotape (registered trademark) was affixed and peeled off, but the number of peeled coating films was 0, and it was confirmed that the adhesion of the cured film to the metal was excellent.

《実施例2》
[ポリアミド樹脂の合成]
ヘキサフルオロ−2,2−ビス(3−アミノ−4−ヒドロキシフェニル)プロパン44.0g(0.12モル)をN−メチル−2−ピロリドン200gに溶解させた後、N−メチル−2−ピロリドン160gに溶解させた無水トリメリット酸クロライド50.6g(0.24モル)を5℃以下に冷却しながら加えた。更にピリジン22.8g(0.29モル)を加えて、20℃ 以下で3 時間攪拌した。次に、4,4’−ジアミノジフェニルエーテル24.0g(0.12モル)を加えた後、室温で5時間反応させた。次に内温を85℃に上げ、3時間攪拌した。反応終了後、濾過した反応混合物を、水/メタノール=5/1(体積比)に投入し、沈殿物を濾集して水で充分洗浄した後、真空下で乾燥し、一般式(3)で示され、Xが下記式X−1、X―2で、Yが下記式Y−3からなる混合物で、a=100、b=0からなる目的のポリアミド樹脂(A−2)を合成した。
[樹脂組成物の作製、現像性及び物性評価]
合成したポリアミド樹脂(A−2)10g、下記構造を有する感光性ジアゾキノン(B−1)2g、下記構造を有する有機ケイ素化合物(C−2)0.2g、γ−ブチロラクト
ン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。
参考例1と同様にして評価を行ったところ、現像時間80秒で露光量550mJ/cm、4μmのパターンまで良好に開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥がれ塗膜の数は0であり、密着性が優れていることが確認された。

Example 2
[Synthesis of polyamide resin]
After dissolving 44.0 g (0.12 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in 200 g of N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone 50.6 g (0.24 mol) of trimellitic anhydride chloride dissolved in 160 g was added while cooling to 5 ° C. or lower. Further, 22.8 g (0.29 mol) of pyridine was added and stirred at 20 ° C. or lower for 3 hours. Next, after adding 44.0 '(diaminodiphenyl ether) 24.0g (0.12mol), it was made to react at room temperature for 5 hours. Next, the internal temperature was raised to 85 ° C. and stirred for 3 hours. After completion of the reaction, the filtered reaction mixture was poured into water / methanol = 5/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the general formula (3) A target polyamide resin (A-2) having a = 100 and b = 0 was synthesized in which X is a mixture of the following formulas X-1 and X-2 and Y is the following formula Y-3. .
[Production of resin composition, developability and evaluation of physical properties]
After dissolving in 10 g of synthesized polyamide resin (A-2), 2 g of photosensitive diazoquinone (B-1) having the following structure, 0.2 g of organosilicon compound (C-2) having the following structure, and 70 g of γ-butyrolactone, It filtered with the filter made from a fluororesin, and the positive photosensitive resin composition was obtained.
When evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that a pattern with an exposure amount of 550 mJ / cm 2 and 4 μm was satisfactorily opened with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 0, and it was confirmed that the adhesion was excellent.

参考例2
参考例1のポリアミド樹脂(A−1)10gを用いて、下記構造を有する感光性ジアゾキノン(B−2)2g、下記構造を有する有機ケイ素化合物(C−1)1g、γ−ブチロ
ラクトン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量540mJ/cm、5μmのパターンまで良好に開口していることが確認できた。物性評価は、実施例1と同様に作製して、剥がれ塗膜の数は0であり、密着性が優れていることが確認された。

<< Reference Example 2 >>
Using 10 g of polyamide resin (A-1) of Reference Example 1 , dissolved in 2 g of photosensitive diazoquinone (B-2) having the following structure, 1 g of organosilicon compound (C-1) having the following structure, and 70 g of γ-butyrolactone. Then, the mixture was filtered with a fluororesin filter to obtain a positive photosensitive resin composition. When the evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that a pattern with an exposure amount of 540 mJ / cm 2 and 5 μm was satisfactorily opened in a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 0, and it was confirmed that the adhesion was excellent.

《実施例4》
参考例1のポリアミド樹脂(A−1)10gを用いて、下記構造を有する感光性ジアゾキノン(B−2)2g、下記構造を有する有機ケイ素化合物(C−2)1g、フェノール性水酸基を有する化合物(D−1)1.5g、γ−ブチロラクトン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量370mJ/cm2、3μmのパターン
まで良好に開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥
がれ塗膜の数は0であり、密着性が優れていることが確認された。

Example 4
10 g of polyamide resin (A-1) of Reference Example 1 , 2 g of photosensitive diazoquinone (B-2) having the following structure, 1 g of organosilicon compound (C-2) having the following structure, compound having a phenolic hydroxyl group (D-1) After dissolving in 1.5 g and γ-butyrolactone 70 g, the mixture was filtered with a fluororesin filter to obtain a positive photosensitive resin composition. When evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that a pattern with an exposure amount of 370 mJ / cm 2 and 3 μm was satisfactorily opened with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 0, and it was confirmed that the adhesion was excellent.

参考例3
実施例2のポリアミド樹脂(A−2)10gを用いて、下記構造を有する感光性ジアゾキノン(B−2)2g、下記構造を有する有機ケイ素化合物(C−1)0.5g、フェノール性水酸基を有する化合物(D−2)1.5g、γ−ブチロラクトン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量390mJ/cm、3μmのパターンまで良好に開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥がれ塗膜の数は0であり、密着性が優れていることが確認された。

<< Reference Example 3 >>
Using 10 g of the polyamide resin (A-2) of Example 2, 2 g of photosensitive diazoquinone (B-2) having the following structure, 0.5 g of an organosilicon compound (C-1) having the following structure, and a phenolic hydroxyl group After dissolving in 1.5 g of the compound (D-2) having and 70 g of γ-butyrolactone, the mixture was filtered with a fluororesin filter to obtain a positive photosensitive resin composition. When evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that a pattern with an exposure amount of 390 mJ / cm 2 and 3 μm was satisfactorily opened in a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 0, and it was confirmed that the adhesion was excellent.

《比較例1》
参考例1のポリアミド樹脂(A−1)10gを用いて、下記構造を有する感光性ジアゾキノン(B−1)2g、γ−ブチロラクトン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量540mJ/cm、5μmのパターンまで開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥がれ塗膜の数は80個であり、密着性が劣ることが確認された。

<< Comparative Example 1 >>
Using 10 g of the polyamide resin (A-1) of Reference Example 1 and dissolving in 2 g of photosensitive diazoquinone (B-1) having the following structure and 70 g of γ-butyrolactone, the mixture was filtered through a fluororesin filter, and positive photosensitive A functional resin composition was obtained. When the evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that the pattern had an exposure amount of 540 mJ / cm 2 and a pattern of 5 μm with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 80, and it was confirmed that the adhesion was inferior.

《比較例2》
参考例1のポリアミド樹脂(A−1)10gを用いて、下記構造を有する感光性ジアゾキノン(B−2)2g、γ−ブチロラクトン70gに溶解した後、フッ素樹脂製フィルターで濾過し、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量530mJ/cm、6μmのパターンまで開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥がれ塗膜の数は90個であり、密着性が劣ることが確認された。

<< Comparative Example 2 >>
10 g of the polyamide resin (A-1) of Reference Example 1 was dissolved in 2 g of photosensitive diazoquinone (B-2) having the following structure and 70 g of γ-butyrolactone, and then filtered through a fluororesin filter, and positive photosensitive A functional resin composition was obtained. When the evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that the pattern had an exposure amount of 530 mJ / cm 2 and a pattern of 6 μm with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 90, and it was confirmed that the adhesion was inferior.

《比較例3》
比較例2のワニスに、該有機ケイ素化合物以外の有機ケイ素化合物(C−3)を0.5g添加して、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量550mJ/cm、6μmのパターンまで開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥がれ塗膜の数は90個であり、密着性が劣ることが確認された。

<< Comparative Example 3 >>
0.5 g of organosilicon compound (C-3) other than the organosilicon compound was added to the varnish of Comparative Example 2 to obtain a positive photosensitive resin composition. When the evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that the pattern was opened to an exposure amount of 550 mJ / cm 2 and 6 μm in a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 90, and it was confirmed that the adhesion was inferior.

《比較例4》
比較例2のワニスに、該有機ケイ素化合物以外の有機ケイ素化合物(C−4)を1g、添加して、ポジ型感光性樹脂組成物を得た。参考例1と同様にして評価を行ったところ、現像時間80秒で露光量540mJ/cm、6μmのパターンまで開口していることが確認できた。物性評価は、参考例1と同様に作製して、剥がれ塗膜の数は60個であり、密着性が劣ることが確認された。

<< Comparative Example 4 >>
1 g of an organosilicon compound (C-4) other than the organosilicon compound was added to the varnish of Comparative Example 2 to obtain a positive photosensitive resin composition. When evaluation was performed in the same manner as in Reference Example 1 , it was confirmed that the pattern had an exposure amount of 540 mJ / cm 2 and an opening of 6 μm in a development time of 80 seconds. The physical property evaluation was made in the same manner as in Reference Example 1. The number of peeled coating films was 60, and it was confirmed that the adhesion was inferior.

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

Figure 0004581706
Figure 0004581706

本発明は、基盤との密着性に優れたポリベンゾオキサゾール樹脂、ポリイミド樹脂又はその共重合樹脂を提供することを目的とするポリアミド樹脂とそれらを用いた露光特性に優れるポジ型感光性樹脂組成物及び半導体装置であって、半導体用途のみならず、多層回路の層間絶縁やフレキシブル銅張板のカバーコート、ソルダーレジスト膜や液晶配向膜、表示素子における素子の平坦化膜や絶縁膜等に好適に用いることができる。   The present invention relates to a polyamide resin intended to provide a polybenzoxazole resin, a polyimide resin or a copolymer resin thereof excellent in adhesion to a substrate, and a positive photosensitive resin composition excellent in exposure characteristics using them. In addition to semiconductor applications, it is suitable not only for semiconductor applications but also for interlayer insulation of multilayer circuits, flexible copper-clad plate cover coats, solder resist films and liquid crystal alignment films, flattening films and insulating films of elements in display elements, etc. Can be used.

本発明のバンプを有する半導体装置の一例のパット部分の拡大断面図を示す。The expanded sectional view of the pad part of an example of the semiconductor device which has a bump of the present invention is shown.

符号の説明Explanation of symbols

1 シリコンウエハ
2 Alパッド
3 パッシベーション膜
4 バッファコート膜
5 金属(Cr、Ti等)膜
6 配線(Al、Cu等)
7 絶縁膜
8 バリアメタル
9 ハンダバンプ
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 (10)

ポリアミド樹脂(A)、感光性ジアゾキノン化合物(B)及びSを含有した有機ケイ素化合物(C)を含んでなるポジ型感光性樹脂組成物であって、前記有機ケイ素化合物(C)が一般式(2)で表される群より選ばれた1種類以上の有機ケイ素化合物(C)を含んでなるポジ型感光性樹脂組成物
Figure 0004581706
A positive photosensitive resin composition comprising a polyamide resin (A), a photosensitive diazoquinone compound (B) and an organosilicon compound (C) containing S , wherein the organosilicon compound (C) is represented by the general formula ( A positive photosensitive resin composition comprising at least one organosilicon compound (C) selected from the group represented by 2) .
Figure 0004581706
ポリアミド樹脂(A)が一般式(3)で示される構造を有するポリアミド樹脂(A)である請求項1記載のポジ型感光性樹脂組成物。
Figure 0004581706
Polyamide resin (A) is the general formula (3) The positive photosensitive resin composition according to claim 1 Symbol mounting a polyamide resin (A) having a structure represented by.
Figure 0004581706
請求項1、又は2記載の有機ケイ素化合物(C)が、ポリアミド樹脂(A)100重量部に対して0.1〜20重量部を含んでなるポジ型感光性樹脂組成物。 Claim 1 or 2 Symbol placement organosilicon compound (C) is a polyamide resin (A) The positive photosensitive resin composition comprising 0.1 to 20 parts by weight per 100 parts by weight. ポジ型感光性樹脂組成物が、更にフェノール性水酸基を有する化合物(D)を含んでなる請求項1、2、又は3記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition further compound having a phenolic hydroxyl group (D) comprising Claim 1, 2 or 3 Symbol placement of positive photosensitive resin composition. フェノール性水酸基を有する化合物(D)が下記構造である請求項に記載のポジ型感光性樹脂組成物。
Figure 0004581706
The positive photosensitive resin composition according to claim 4 , wherein the compound (D) having a phenolic hydroxyl group has the following structure.
Figure 0004581706
請求項1〜のいずれか1項に記載のポジ型感光性樹脂組成物を基板上に塗布して組成物層を形成する工程と、概組成物層に活性エネルギー線を照射して現像液と接触させてパターンを形成する工程と、概組成物を加熱する工程を有することを特徴とするパターン状樹脂膜の製造方法。 A step of applying the positive photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form a composition layer, and irradiating active energy rays to the approximate composition layer to develop a developer A method for producing a patterned resin film, comprising: a step of forming a pattern by contacting with a substrate; and a step of heating the approximate composition. 請求項1〜のいずれか1項に記載のポジ型感光性樹脂組成物を用いて製作されてなることを特徴とする半導体装置。 The semiconductor device characterized by comprising been fabricated using the positive photosensitive resin composition according to any one of claims 1-5. 請求項1〜のいずれか1項に記載のポジ型感光性樹脂組成物を用いて製作されてなることを特徴とする表示素子。 Display element characterized by comprising been fabricated using the positive photosensitive resin composition according to any one of claims 1-5. 請求項1〜のいずれか1項に記載のポジ型感光性樹脂組成物を加熱後の膜厚が、0.1〜30μmになるように半導体素子上でパターン加工して得られることを特徴とする半導体装置の製造方法。 It is obtained by patterning on a semiconductor element so that the film thickness after heating the positive photosensitive resin composition according to any one of claims 1 to 5 is 0.1 to 30 µm. A method for manufacturing a semiconductor device. 請求項1〜のいずれか1項に記載のポジ型感光性樹脂組成物を加熱後の膜厚が、0.1〜30μmになるように表示素子用基板上にパターン加工して得られることを特徴とする表示素子の製造方法。 The positive photosensitive resin composition according to any one of claims 1 to 5 is obtained by patterning on a display element substrate so that the film thickness after heating is 0.1 to 30 µm. A method for manufacturing a display element.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02210443A (en) * 1988-09-20 1990-08-21 M & T Chem Inc Ultraviolet hardening composition for forming solder mask film having covering capacity
JPH10307394A (en) * 1997-05-09 1998-11-17 Hitachi Ltd Positive photosensitive resin composition and pattern forming method by using the same and method of manufacture of electronic device
JP2000187321A (en) * 1998-12-24 2000-07-04 Hitachi Chemical Dupont Microsystems Ltd Photosensitive resin composition, production of relief pattern and electronic parts
JP2001242640A (en) * 2000-02-29 2001-09-07 Sumitomo Bakelite Co Ltd Processing method for photosensitive resin composition and semiconductor device using same
JP2003005367A (en) * 2001-06-22 2003-01-08 Sumitomo Bakelite Co Ltd Positive type photosensitive resin composition and semiconductor device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6939659B2 (en) * 2003-03-11 2005-09-06 Arch Specialty Chemicals, Inc. Photosensitive resin compositions
US7195849B2 (en) * 2003-03-11 2007-03-27 Arch Specialty Chemicals, Inc. Photosensitive resin compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02210443A (en) * 1988-09-20 1990-08-21 M & T Chem Inc Ultraviolet hardening composition for forming solder mask film having covering capacity
JPH10307394A (en) * 1997-05-09 1998-11-17 Hitachi Ltd Positive photosensitive resin composition and pattern forming method by using the same and method of manufacture of electronic device
JP2000187321A (en) * 1998-12-24 2000-07-04 Hitachi Chemical Dupont Microsystems Ltd Photosensitive resin composition, production of relief pattern and electronic parts
JP2001242640A (en) * 2000-02-29 2001-09-07 Sumitomo Bakelite Co Ltd Processing method for photosensitive resin composition and semiconductor device using same
JP2003005367A (en) * 2001-06-22 2003-01-08 Sumitomo Bakelite Co Ltd Positive type photosensitive resin composition and semiconductor device

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