JPH06148895A - Photosensitive resin composition and pattern forming method using that - Google Patents
Photosensitive resin composition and pattern forming method using thatInfo
- Publication number
- JPH06148895A JPH06148895A JP4296954A JP29695492A JPH06148895A JP H06148895 A JPH06148895 A JP H06148895A JP 4296954 A JP4296954 A JP 4296954A JP 29695492 A JP29695492 A JP 29695492A JP H06148895 A JPH06148895 A JP H06148895A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- resin composition
- siloxane polymer
- alkali
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルカリ可溶性シロキ
サンポリマーを含有した感光性樹脂組成物およびこれを
用いたパターン形成方法に関するものであり、さらに詳
しくは塗布性および保存安定性の優れた感光性樹脂組成
物およびこれを用いたパターン形成方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition containing an alkali-soluble siloxane polymer and a pattern forming method using the same, and more specifically to a photosensitive resin composition having excellent coating properties and storage stability. The present invention relates to a resin composition and a pattern forming method using the same.
【０００２】[0002]
【従来の技術】シロキサンポリマーを得る方法として
は、クロロシランを加水分解縮合させる方法が古くから
知られている。しかし、この方法では原料が塩素化合物
であるために、得られるシロキサンポリマーにクロルイ
オンが混入し、電子材料用途には適さないものであっ
た。2. Description of the Related Art As a method for obtaining a siloxane polymer, a method of hydrolyzing and condensing chlorosilane has been known for a long time. However, in this method, since the raw material is a chlorine compound, chlorine ions are mixed in the obtained siloxane polymer, which is not suitable for electronic material applications.
【０００３】このクロルイオンの混入を防ぐ方法として
アルコキシシランを原料とする方法が開示されている。
すなわち、親水性溶媒中でアルコキシシランを水および
触媒を加えて加水分解縮合させ、その溶液を大量の水に
投入し、ポリマーを再沈させるというものである。As a method for preventing the mixing of chlorine ions, a method using an alkoxysilane as a raw material has been disclosed.
That is, the alkoxysilane is hydrolyzed and condensed in a hydrophilic solvent by adding water and a catalyst, and the solution is poured into a large amount of water to reprecipitate the polymer.
【０００４】しかし、この方法では、得られる感光性樹
脂組成物の塗布性は悪く、保存安定性にも劣るものであ
った。さらに、本組成物を使用したパターン形成のプロ
セスにおいても、プリベーク状態で膜が硬化しやすく、
現像残膜が残るという問題を有していた。However, in this method, the coatability of the resulting photosensitive resin composition was poor and the storage stability was also poor. Furthermore, even in the process of pattern formation using the present composition, the film easily hardens in the pre-baked state,
There was a problem that the residual film after development remained.
【０００５】すなわち、塗布性不良の原因について本発
明者らが詳細な検討を行なったところ、シロキサンポリ
マーが疎水性であるにもかかわらず、加水分解のために
加えた水の過剰分や縮合反応によって生成した水の除去
が不十分であるため、溶剤成分に水が含まれていること
が主原因であることが判った。That is, the inventors of the present invention have conducted a detailed study on the cause of poor coating properties. As a result, even though the siloxane polymer is hydrophobic, excess water added for hydrolysis and condensation reaction are added. It was found that the main cause is that the solvent component contains water because the water generated by the method is insufficiently removed.
【０００６】また、保存安定性不良およびパターン形成
不良については、加水分解促進用に加えた触媒の除去に
ついても不十分であるために、保存中に徐々に加水分解
縮合が進行していることが主原因であることが判った。With respect to poor storage stability and poor pattern formation, the removal of the catalyst added to accelerate hydrolysis is insufficient, so that hydrolysis condensation gradually progresses during storage. It turned out to be the main cause.
【０００７】つまり、水の除去のみ、あるいは触媒の除
去のみでは塗布性の向上、保存安定性の向上のいずれを
も達成不可能なことが判明した。すなわち、水の除去の
みを行なって塗布性の向上を図っても、触媒が存在する
限りは脱水縮合反応の進行によって水が生成するため、
経時的に塗布性が劣化してしまうのである。また、触媒
の除去のみを行なって保存安定性の向上を図っても、水
の存在は加水分解を十分に進行させてしまうのである。That is, it has been found that neither the improvement of the coating property nor the improvement of the storage stability can be achieved only by removing the water or only by removing the catalyst. That is, even if only water is removed to improve the coatability, water is produced by the progress of the dehydration condensation reaction as long as the catalyst is present.
The coating property deteriorates with time. Even if only the removal of the catalyst is carried out to improve the storage stability, the presence of water will cause the hydrolysis to proceed sufficiently.
【０００８】すなわち、水および触媒の双方を除去した
場合のみ、塗布性および保存安定性が共に優れた感光性
樹脂組成物が得られることを見出だし、本発明に到達し
たものである。That is, it was found that a photosensitive resin composition excellent in both coating property and storage stability can be obtained only when both water and catalyst are removed, and the present invention has been achieved.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、塗布
性および保存安定性が共に優れた感光性樹脂組成物、お
よびこれを用いた、現像残膜がなくプロセスラティチュ
ードの広いパターン形成方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition which is excellent in both coating property and storage stability, and a method for forming a pattern having a wide process latitude without developing residual film using the same. To provide.
【００１０】[0010]
【課題を解決するための手段】かかる本発明の目的は、
（１）アルカリ可溶性シロキサンポリマー、（２）光に
よって反応促進剤を発生する化合物、および（３）溶剤
を主成分とする感光性樹脂組成物において、アルカリ可
溶性シロキサンポリマーが、アルコキシシランに水およ
び触媒を加えて加水分解縮合させた反応溶液から、水お
よび触媒を除去して得られるアルカリ可溶性シロキサン
ポリマーであることを特徴とする感光性樹脂組成物によ
り達成される。The object of the present invention is as follows.
In the photosensitive resin composition containing (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent as a main component, the alkali-soluble siloxane polymer is an alkoxysilane containing water and a catalyst. It is achieved by a photosensitive resin composition, which is an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by adding and hydrolyzing and condensing.
【００１１】以下、本発明の構成を順に説明する。The structure of the present invention will be described below in order.
【００１２】本発明において用いられるアルカリ可溶性
シロキサンポリマーは、アルコキシシランに水および触
媒を加えて加水分解縮合させた反応溶液から、水および
触媒を除去して得られるものである。The alkali-soluble siloxane polymer used in the present invention is obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing an alkoxysilane with water and a catalyst.
【００１３】アルカリ可溶性シロキサンポリマーの原料
となるアルコキシシランは、そのアルコキシ基が加水分
解性を有しているものであれば、特に限定されないが、
好ましくは、次の一般式（１）で表されるものである。The alkoxysilane used as a raw material for the alkali-soluble siloxane polymer is not particularly limited as long as the alkoxy group has hydrolyzability.
Preferably, it is represented by the following general formula (1).
【００１４】 Ｒx Ｓｉ（ＯＲ´）4-x （１） （ただし、Ｒ、Ｒ´は同一もしくは異なっていてもよ
く、それぞれ水素、アルキル基、アリール基、アリル
基、フルオロアルキル基を表す。また、ｘは０〜３の整
数である。）一般式（１）で表されるアルコキシシラン
の具体例としては、テトラヒドロキシシラン、テトラメ
トキシシラン、テトラエトキシシラン、メチルトリメト
キシシラン、メチルトリエトキシシラン、ビニルトリメ
トキシシラン、ビニルトリエトキシシランフェニルトリ
メトキシシラン、フェニルトリエトキシシラン、ジメチ
ルジメトキシシラン、ジメチルジエトキシシラン、ジフ
ェニルジメトキシシラン、ジフェニルジエトキシシラ
ン、トリフルオロメチルメトキシシラン、トリフルオロ
エチルトリメトキシシランなどを挙げることができる。
好ましくは、メチルトリメトキシシラン４０〜１００モ
ル％、フェニルトリメトキシシラン０〜４０モル％、お
よびジメチルジメトキシシラン０〜４０モル％から成る
組成物であり、さらに好ましくはメチルトリメトキシシ
ラン５０〜８０モル％、フェニルトリメトキシシラン１
０〜３０モル％、およびジメチルジメトキシシラン１０
〜４０モル％から成る組成物である。R x Si (OR ′) 4-x (1) (However, R and R ′ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an allyl group or a fluoroalkyl group. Further, x is an integer of 0 to 3.) Specific examples of the alkoxysilane represented by the general formula (1) include tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxy. Silane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trifluoromethylmethoxysilane, trifluoroethyltrimethoxy Silane, etc. Rukoto can.
The composition is preferably composed of 40 to 100 mol% of methyltrimethoxysilane, 0 to 40 mol% of phenyltrimethoxysilane, and 0 to 40 mol% of dimethyldimethoxysilane, and more preferably 50 to 80 mol of methyltrimethoxysilane. %, Phenyltrimethoxysilane 1
0 to 30 mol% and dimethyldimethoxysilane 10
The composition consists of ˜40 mol%.
【００１５】アルコキシシランの加水分解縮合反応は無
溶媒で行っても良いが、通常は溶媒中で行なわれる。溶
媒としては、有機溶媒が好ましく、メチルイソブチルケ
トン、ジイソブチルケトン、ジエチルエーテル、酢酸エ
チル、ヘキサン、シクロヘキサン、ノルマルブタノール
などの疎水性有機溶媒がさらに好ましい。溶媒の量とし
ては、任意に選択可能であるが、アルコキシシラン１重
量に対して、０．１〜３．０倍重量の範囲で用いるのが
好ましい。The hydrolysis-condensation reaction of the alkoxysilane may be carried out without a solvent, but it is usually carried out in a solvent. As the solvent, an organic solvent is preferable, and a hydrophobic organic solvent such as methyl isobutyl ketone, diisobutyl ketone, diethyl ether, ethyl acetate, hexane, cyclohexane, and normal butanol is more preferable. Although the amount of the solvent can be arbitrarily selected, it is preferably used in the range of 0.1 to 3.0 times the weight of 1 weight of the alkoxysilane.
【００１６】加水分解縮合反応をさせるために用いられ
る水としては、イオン交換水が好ましく、その量として
は、アルコキシシラン１モルに対して、１〜４倍モルの
範囲で用いるのが好ましい。また、加水分解縮合反応さ
せるために用いる触媒は酸触媒が好ましく、塩酸、硫
酸、酢酸、トリフルオロ酢酸、リン酸、ほう酸などが好
ましい例としてあげられる。The water used for the hydrolysis-condensation reaction is preferably ion-exchanged water, and the amount thereof is preferably 1 to 4 times mol per mol of the alkoxysilane. The catalyst used for the hydrolysis condensation reaction is preferably an acid catalyst, and hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, boric acid and the like can be mentioned as preferable examples.
【００１７】加水分解縮合反応の温度および時間として
は、反応系の凝固点から沸点の範囲で適宜選択される
が、高分子量のシロキサンポリマーを得るには、還流下
で数時間行なうのが好ましい。The temperature and time of the hydrolysis-condensation reaction are appropriately selected within the range from the freezing point of the reaction system to the boiling point, but in order to obtain a high molecular weight siloxane polymer, it is preferable to carry out under reflux for several hours.
【００１８】反応溶液から水および触媒を除去する方法
としては特に限定されない。例えば、イオン交換樹脂、
イオン交換繊維、モレキュラーシーブなどの吸着剤およ
び乾燥剤などを用いて行うことができるが、好ましく
は、メチルイソブチルケトン、ジイソブチルケトン、ジ
エチルエーテル、酢酸エチル、酢酸ブチルなどの疎水性
有機溶剤を用いて該反応溶液からシロキサンポリマーを
抽出し、その有機層を水洗する方法である。上記疎水性
有機溶剤の中で特に好ましいものは、メチルイソブチル
ケトン、ジイソブチルケトン、酢酸エチルである。有機
層を水洗後、さらに完全に水分を除去するために、無水
硫酸ナトリウム、無水硫酸マグネシウムなどの乾燥剤を
用いることも可能である。The method for removing water and the catalyst from the reaction solution is not particularly limited. For example, ion exchange resin,
It can be carried out using an ion exchange fiber, an adsorbent such as a molecular sieve and a desiccant, but preferably, a hydrophobic organic solvent such as methyl isobutyl ketone, diisobutyl ketone, diethyl ether, ethyl acetate or butyl acetate is used. In this method, a siloxane polymer is extracted from the reaction solution and the organic layer is washed with water. Of the above hydrophobic organic solvents, particularly preferred are methyl isobutyl ketone, diisobutyl ketone, and ethyl acetate. After the organic layer is washed with water, it is possible to use a desiccant such as anhydrous sodium sulfate and anhydrous magnesium sulfate in order to completely remove water.
【００１９】水洗後、あるいは水洗乾燥後の溶液に、光
によって反応促進剤を発生する化合物を加え感光性樹脂
組成物とすることも可能であるが、必要に応じて、溶剤
を追加あるいは除去して粘度を調製すること、あるいは
溶剤を除去してシロキサンポリマーを単離し、再び所望
の溶剤に溶解してから、光によって反応促進剤を発生す
る化合物を加え、感光性樹脂組成物とすることも好まし
く行われる。感光性樹脂組成物中のアルカリ可溶性シロ
キサンポリマーの好ましい配合割合としては、１０〜６
０重量％である。It is possible to add a compound which generates a reaction accelerator by light to the solution after washing with water or after drying with water to obtain a photosensitive resin composition, but a solvent may be added or removed as necessary. It is also possible to prepare a photosensitive resin composition by adjusting the viscosity with a solvent, or by removing the solvent to isolate the siloxane polymer, dissolving it again in a desired solvent, and then adding a compound that generates a reaction accelerator by light. It is preferably carried out. The preferable blending ratio of the alkali-soluble siloxane polymer in the photosensitive resin composition is 10 to 6
It is 0% by weight.
【００２０】ここで用いられる溶剤としては、イソプロ
パノール、ノルマルブタノール、メチルセロソルブ、ブ
チルセロソルブ、プロピレングリコールモノメチルエー
テル、エチルセロソルブアセテート、トルエン、キシレ
ン、メチルイソブチルケトン、ジイソブチルケトンなど
を挙げることができる。Examples of the solvent used here include isopropanol, normal butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethyl cellosolve acetate, toluene, xylene, methyl isobutyl ketone and diisobutyl ketone.
【００２１】光によって反応促進剤を発生する化合物と
しては、特に限定されないが、光酸発生剤、あるいは光
塩基発生剤が好ましい。具体的には、光酸発生剤として
は、ベンゾイントシレート、トリ（ニトロベンジル）フ
ォスフェート、トリアニソインフォスフェート、ジアリ
ールヨードニウム塩、トリアリールスルホニウム塩な
ど、光塩基発生剤としては、ニトロベンジルシクロヘキ
シルカルバメート、ジ（メトキシベンジル）ヘキサメチ
レンジカルバメートなどを挙げることができる。これら
の化合物の使用量としては、シロキサンポリマーに対し
て、０．１〜５．０重量％の範囲にあることが好まし
く、より好ましくは、０．２〜２．０重量％である。The compound which generates the reaction accelerator by light is not particularly limited, but a photoacid generator or a photobase generator is preferable. Specifically, as the photo-acid generator, benzointosylate, tri (nitrobenzyl) phosphate, trianisoinfosphate, diaryliodonium salt, triarylsulfonium salt, and the like, and as the photobase generator, nitrobenzylcyclohexyl Carbamate, di (methoxybenzyl) hexamethylene dicarbamate and the like can be mentioned. The amount of these compounds used is preferably in the range of 0.1 to 5.0% by weight, more preferably 0.2 to 2.0% by weight, based on the siloxane polymer.
【００２２】次に、本発明の感光性樹脂組成物を用いた
パターン形成方法を順に説明する。本発明の感光性樹脂
組成物をスピンナー、ディッピングなどの公知の方法に
よってシリコンウェハー、セラミックス板などの基板上
に塗布し、乾燥する。乾燥後の膜厚としては、０．５〜
５．０μｍ、乾燥温度としては、５０〜１５０℃の範囲
にあることが好ましい。Next, a pattern forming method using the photosensitive resin composition of the present invention will be described in order. The photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer or a ceramic plate by a known method such as spinner or dipping and dried. The film thickness after drying is from 0.5 to
The drying temperature is preferably 5.0 μm and is preferably in the range of 50 to 150 ° C.
【００２３】乾燥後、マスクを介して露光する。露光に
際しては、“ＰＬＡ”（キヤノン製紫外線露光機）など
の露光機を用い、２００〜２０００ｍＪ／ｃｍ2 程度
（３６５ｎｍ）を露光すればよい。After drying, exposure is performed through a mask. At the time of exposure, an exposure device such as "PLA" (UV exposure device manufactured by Canon Inc.) may be used to expose about 200 to 2000 mJ / cm 2 (365 nm).
【００２４】露光後、加熱（ポストエクスポージャーベ
ーク）を行うことが好ましい。ポストエクスポージャー
ベークを行うことによって、露光によって発生した反応
促進剤の作用により露光部の重合化が進行し、未露光部
との現像液溶解度差が広がり、解像コントラストが向上
するという効果が得られる。ポストエクスポージャーベ
ークの温度範囲としては、５０〜１５０℃、時間として
は、３０秒〜５分間が好ましい。After the exposure, it is preferable to perform heating (post exposure bake). By performing the post-exposure bake, the polymerization of the exposed area proceeds due to the action of the reaction accelerator generated by the exposure, and the difference in the solubility of the developer with the unexposed area is widened, and the effect of improving the resolution contrast can be obtained. . The temperature range of post-exposure bake is preferably 50 to 150 ° C., and the time is preferably 30 seconds to 5 minutes.
【００２５】つづいて、現像を行う。現像方法として
は、現像液に１０秒〜１０分間浸漬することが好まし
い。現像液としては、“ＮＭＤ−３”（東京応化工業製
フォトレジスト用現像液）などのアルカリ水溶液を用い
ることが好ましい。現像後、水洗し、乾燥することによ
り、パターンが形成される。Subsequently, development is performed. As a developing method, it is preferable to immerse the film in a developing solution for 10 seconds to 10 minutes. As the developing solution, it is preferable to use an alkaline aqueous solution such as "NMD-3" (a photoresist developing solution manufactured by Tokyo Ohka Kogyo Co., Ltd.). After development, a pattern is formed by washing with water and drying.
【００２６】さらに、必要に応じて、再露光を行うこと
により、その後のキュアを完全に行なうことができる。Further, if necessary, re-exposure can be performed, so that the subsequent curing can be performed completely.
【００２７】さらに、パターン形成された膜を通常のキ
ュア温度である２５０〜５００℃程度まで加熱し、キュ
アすることによって、所望のパターニングされた膜を得
ることができる。Further, a desired patterned film can be obtained by heating the patterned film to a usual curing temperature of about 250 to 500 ° C. and curing it.
【００２８】本発明の感光性樹脂組成物は、半導体素子
の保護膜、層間絶縁膜、導波路形成用材料、位相シフタ
ー用材料、さらには各種電子部品の保護膜として用いる
ことができるが、これらに限定されない。The photosensitive resin composition of the present invention can be used as a protective film for semiconductor elements, an interlayer insulating film, a material for forming a waveguide, a material for phase shifters, and a protective film for various electronic parts. Not limited to.
【００２９】[0029]
【実施例】次に、実施例により本発明をさらに詳細に説
明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００３０】実施例１ メチルトリメトキシシラン１３６ｇ（１．０ｍｏｌ）を
ジイソブチルケトン５０ｇに溶解し、イオン交換水６０
ｇ、酢酸３ｇを攪拌しながら加えた。得られた溶液を加
熱し、還流させながら、２４時間反応させた。その後、
酢酸ブチル５００ｇを用いてシロキサンポリマーを抽出
し、有機層にイオン交換水２００ｇを加えて振とうし、
静置後、水層を分離除去した。得られた有機層を濃縮
し、ニトロベンジルシクロヘキシルカルバメート０．２
ｇを加え、感光性樹脂組成物を得た。Example 1 136 g (1.0 mol) of methyltrimethoxysilane was dissolved in 50 g of diisobutyl ketone, and ion-exchanged water 60 was added.
g and acetic acid 3 g were added with stirring. The resulting solution was heated and refluxed for 24 hours. afterwards,
The siloxane polymer was extracted with 500 g of butyl acetate, 200 g of ion-exchanged water was added to the organic layer, and the mixture was shaken.
After standing, the aqueous layer was separated and removed. The obtained organic layer was concentrated and nitrobenzylcyclohexylcarbamate 0.2
g was added to obtain a photosensitive resin composition.
【００３１】この感光性樹脂組成物をシリコンウェハ上
にスピンコーターを用いてコートしたところ、ムラのな
い良好な膜が得られ、良好な塗布性を示した。また、こ
の感光性樹脂組成物は室温で３ケ月保存後も、粘度上昇
は見られず、塗布性の劣化も見られず、良好な保存安定
性を有していた。When this photosensitive resin composition was coated on a silicon wafer by using a spin coater, a good film without unevenness was obtained and good coatability was exhibited. The photosensitive resin composition had good storage stability even after storage at room temperature for 3 months without any increase in viscosity or deterioration in coating property.
【００３２】塗布膜をホットプレートを用いて、１００
℃で５分乾燥後、所望のマスクを介して、１５００ｍＪ
／ｃｍ2 （３６５ｎｍ）露光した。ホットプレートを用
いて１００℃で１分間、ポストエクスポージャーベーク
を行なった後、２．３８％のテトラメチルアンモニウム
ハイドロオキサイド水溶液で１分間浸漬現像した。つづ
いて水洗し、乾燥したところ、最小０．５μｍの良好な
Ｌ＆Ｓパターンが得られた。The coating film was coated with a hot plate to 100
After drying for 5 minutes at ℃, 1500mJ through the desired mask
/ Cm 2 (365 nm) exposure. Post-exposure bake was performed at 100 ° C. for 1 minute using a hot plate, and then immersion development was performed for 1 minute with a 2.38% tetramethylammonium hydroxide aqueous solution. Subsequently, when washed with water and dried, a good L & S pattern with a minimum of 0.5 μm was obtained.
【００３３】比較例１ 実施例１と同様に、メチルトリメトキシシラン１３６ｇ
（１．０ｍｏｌ）をジイソブチルケトン５０ｇに溶解
し、イオン交換水６０ｇ、酢酸３ｇを攪拌しながら加え
た。得られた溶液を加熱し、還流させながら、２４時間
反応させた。得られた溶液を濃縮して、ニトロベンジル
シクロヘキシルカルバメート０．２ｇを加え、感光性樹
脂組成物を得た。Comparative Example 1 As in Example 1, 136 g of methyltrimethoxysilane
(1.0 mol) was dissolved in 50 g of diisobutyl ketone, and 60 g of ion-exchanged water and 3 g of acetic acid were added with stirring. The resulting solution was heated and refluxed for 24 hours. The resulting solution was concentrated and 0.2 g of nitrobenzylcyclohexyl carbamate was added to obtain a photosensitive resin composition.
【００３４】この感光性樹脂組成物をシリコンウェハ上
にスピンコーターを用いて塗布したところ、多数のクレ
ーター状のムラが見られ、塗布性に劣るものであった。
さらに、この感光性樹脂組成物は室温保存により、粘度
上昇が見られ、保存安定性にも劣るものであった。When this photosensitive resin composition was applied onto a silicon wafer using a spin coater, many crater-like unevenness was observed and the coatability was poor.
Furthermore, this photosensitive resin composition showed an increase in viscosity upon storage at room temperature and was inferior in storage stability.
【００３５】また、この塗布膜を、実施例１と同様にパ
ターン形成したところ、プリベークが強いと未露光部に
現像残膜が残りやすく、プロセスラティチュードが狭か
った。When this coating film was patterned in the same manner as in Example 1, when the pre-baking was strong, the undeveloped film was likely to have an undeveloped residual film, resulting in a narrow process latitude.
【００３６】実施例２ メチルトリメトキシシラン１９０ｇ（１．４ｍｏｌ）、
ジメチルジメトキシシラン７２ｇ（０．６ｍｏｌ）、フ
ェニルトルメトキシシラン７．９ｇ（０．４ｍｏｌ）を
メチルイソブチルケトン９０ｇに溶解し、これに、イオ
ン交換水１２０ｇ、リン酸１０ｇを攪拌しながら加え
た。得られた溶液を加熱し、還流させながら、３時間反
応させた。その後、メチルイソブチルケトン１０００ｇ
を用いてシロキサンポリマーを抽出し、有機層をイオン
交換水１０００ｇを加えて振とうし、静置後、水層を分
離除去した。得られた有機層を濃縮して、シロキサンポ
リマーを得た。このポリマー２０ｇをプロピレングリコ
ールモノメチルエーテル３０ｇに溶解し、さらにベンゾ
イントシレート０．１ｇを加え、感光性樹脂組成物を得
た。Example 2 190 g (1.4 mol) of methyltrimethoxysilane,
72 g (0.6 mol) of dimethyldimethoxysilane and 7.9 g (0.4 mol) of phenyltolumethoxysilane were dissolved in 90 g of methyl isobutyl ketone, to which 120 g of ion-exchanged water and 10 g of phosphoric acid were added with stirring. The obtained solution was heated and reacted under reflux for 3 hours. After that, 1000 g of methyl isobutyl ketone
The siloxane polymer was extracted by using, and the organic layer was added with 1000 g of ion-exchanged water and shaken. After standing, the aqueous layer was separated and removed. The obtained organic layer was concentrated to obtain a siloxane polymer. 20 g of this polymer was dissolved in 30 g of propylene glycol monomethyl ether, and 0.1 g of benzoin tosylate was further added to obtain a photosensitive resin composition.
【００３７】この感光性樹脂組成物をシリコンウェハ上
にスピンコーターを用いてコートしたところ、ムラのな
い良好な膜が得られ、良好な塗布性を示した。また、こ
の感光性樹脂組成物は室温で３ケ月保存後も、粘度上昇
は見られず、塗布性の劣化も見られず、良好な保存安定
性を有していた。When this photosensitive resin composition was coated on a silicon wafer using a spin coater, a good film without unevenness was obtained, and good coatability was exhibited. The photosensitive resin composition had good storage stability even after storage at room temperature for 3 months without any increase in viscosity or deterioration in coating property.
【００３８】塗布膜をホットプレートを用いて、１００
℃で５分乾燥後、所望のマスクを介して、６００ｍＪ／
ｃｍ2 （３６５ｎｍ）露光した。ホットプレートを用い
て１００℃で１分間、ポストエクスポージャーベークを
行なった後、２．３８％のテトラメチルアンモニウムハ
イドロオキサイド水溶液で１分間浸漬現像した。つづい
て水洗し、乾燥したところ、最小０．５μｍの良好なＬ
＆Ｓパターンが得られた。The coating film was coated with a hot plate to 100
After drying at 5 ℃ for 5 minutes, 600mJ /
It was exposed to cm 2 (365 nm). Post-exposure bake was performed at 100 ° C. for 1 minute using a hot plate, and then immersion development was performed for 1 minute with a 2.38% tetramethylammonium hydroxide aqueous solution. Then, after washing with water and drying, a good L of 0.5 μm minimum
The & S pattern was obtained.
【００３９】比較例２ 実施例２と同様に、メチルトリメトキシシラン１９０ｇ
（１．４ｍｏｌ）、ジメチルジメトキシシラン７２ｇ
（０．６ｍｏｌ）、フェニルトルメトキシシラン７．９
ｇ（０．４ｍｏｌ）をメチルイソブチルケトン９０ｇに
溶解し、これに、イオン交換水１２０ｇ、リン酸１０ｇ
を攪拌しながら加えた。得られた溶液を加熱し、還流さ
せながら、３時間反応させた。得られた溶液をイオン交
換水１０００ｇに加えて攪拌し、静置した後、白色の沈
殿したシロキサンポリマーを瀘別し、５０℃で８時間真
空乾燥した。得られたポリマー２０ｇをプロピレングリ
コールモノメチルエーテル３０ｇに溶解し、さらにベン
ゾイントシレート０．１ｇを加え、感光性樹脂組成物を
得た。Comparative Example 2 As in Example 2, 190 g of methyltrimethoxysilane
(1.4 mol), 72 g of dimethyldimethoxysilane
(0.6 mol), phenyltolumethoxysilane 7.9
g (0.4 mol) was dissolved in 90 g of methyl isobutyl ketone, and 120 g of ion-exchanged water and 10 g of phosphoric acid were added to the solution.
Was added with stirring. The obtained solution was heated and reacted under reflux for 3 hours. The obtained solution was added to 1000 g of ion-exchanged water, stirred, and allowed to stand, then, a white precipitated siloxane polymer was filtered and vacuum dried at 50 ° C. for 8 hours. 20 g of the obtained polymer was dissolved in 30 g of propylene glycol monomethyl ether, and 0.1 g of benzoin tosylate was further added to obtain a photosensitive resin composition.
【００４０】この感光性樹脂組成物をシリコンウェハ上
にスピンコーターを用いてコートしたところ、ムラのな
い良好な膜が得られ、良好な塗布性を示した。しかし、
室温保存で急激な粘度上昇が見られ、１ケ月保存後には
ゲル化し、保存安定性に劣るものであった。When this photosensitive resin composition was coated on a silicon wafer by using a spin coater, a good film without unevenness was obtained and good coatability was exhibited. But,
A sharp increase in viscosity was observed upon storage at room temperature, and gelation occurred after storage for 1 month, resulting in poor storage stability.
【００４１】また、この塗布膜を、実施例２と同様にパ
ターン形成したところ、プリベークが強いと未露光部に
現像残膜が残りやすく、プロセスラティチュードが狭か
った。When this coating film was patterned in the same manner as in Example 2, when the pre-baking was strong, the undeveloped film was likely to have an undeveloped residual film, resulting in a narrow process latitude.
【００４２】実施例３ テトラメトキシシラン３０４ｇ（２．０ｍｏｌ）、メチ
ルトリメトキシシラン１３６ｇ（１．０ｍｏｌ）、ジメ
チルジメトキシシラン６０ｇ（０．５ｍｏｌ）をメタノ
ール１００ｇに溶解し、これに、イオン交換水２００
ｇ、塩酸１５ｇを攪拌しながら加えた。得られた溶液を
加熱し、還流させながら、８時間反応させた。その後、
この溶液をイオン交換樹脂１ｋｇを充填したカラムに通
し、水および触媒を除去し、得られた有機層を濃縮し
て、シロキサンポリマーを得た。このポリマー２０ｇを
プロピレングリコールモノメチルエーテル３０ｇに溶解
し、さらにトリ（ニトロベンジル）フォスフェート０．
１ｇを加え、感光性樹脂組成物を得た。Example 3 304 g (2.0 mol) of tetramethoxysilane, 136 g (1.0 mol) of methyltrimethoxysilane and 60 g (0.5 mol) of dimethyldimethoxysilane were dissolved in 100 g of methanol, and 200 g of ion-exchanged water was added thereto.
g and hydrochloric acid 15 g were added with stirring. The obtained solution was heated and reacted under reflux for 8 hours. afterwards,
This solution was passed through a column packed with 1 kg of an ion exchange resin to remove water and a catalyst, and the obtained organic layer was concentrated to obtain a siloxane polymer. This polymer (20 g) was dissolved in propylene glycol monomethyl ether (30 g), and tri (nitrobenzyl) phosphate was added.
1 g was added to obtain a photosensitive resin composition.
【００４３】この感光性樹脂組成物をシリコンウェハ上
にスピンコーターを用いてコートしたところ、ムラのな
い良好な膜が得られ、良好な塗布性を示した。また、さ
らに、この感光性樹脂組成物は室温で３ケ月保存後も、
粘度上昇は見られず、塗布性の劣化も見られず、良好な
保存安定性を有していた。When this photosensitive resin composition was coated on a silicon wafer using a spin coater, a good film with no unevenness was obtained and good coatability was exhibited. Furthermore, even after this photosensitive resin composition was stored at room temperature for 3 months,
No increase in viscosity was observed, no deterioration in coating property was observed, and good storage stability was obtained.
【００４４】塗布膜をホットプレートを用いて、１００
℃で５分乾燥後、所望のマスクを介して、６００ｍＪ／
ｃｍ2 （３６５ｎｍ）露光した。ホットプレートを用い
て１００℃で１分間、ポストエクスポージャーベークを
行なった後、２．３８％のテトラメチルアンモニウムハ
イドロオキサイド水溶液で１分間浸漬現像した。つづい
て水洗し、乾燥したところ、最小０．５μｍの良好なＬ
＆Ｓパターンが得られた。The coating film was coated with a hot plate to 100
After drying at 5 ℃ for 5 minutes, 600mJ /
It was exposed to cm 2 (365 nm). Post-exposure bake was performed at 100 ° C. for 1 minute using a hot plate, and then immersion development was performed for 1 minute with a 2.38% tetramethylammonium hydroxide aqueous solution. Then, after washing with water and drying, a good L of 0.5 μm minimum
The & S pattern was obtained.
【００４５】比較例３ 実施例３と同様に、テトラメトキシシラン３０４ｇ
（２．０ｍｏｌ）、メチルトリメトキシシラン１３６ｇ
（１．０ｍｏｌ）、ジメチルジメトキシシラン６０ｇ
（０．５ｍｏｌ）をメタノール１００ｇに溶解し、これ
に、イオン交換水２００ｇ、塩酸１５ｇを攪拌しながら
加えた。得られた溶液を加熱し、還流させながら、８時
間反応させた。次に、シロキサンポリマーを得るため、
この反応溶液を濃縮したところ、ゲル化し、保存安定性
の悪いものであった。COMPARATIVE EXAMPLE 3 As in Example 3, 304 g of tetramethoxysilane
(2.0 mol), 136 g of methyltrimethoxysilane
(1.0 mol), 60 g of dimethyldimethoxysilane
(0.5 mol) was dissolved in 100 g of methanol, and 200 g of ion-exchanged water and 15 g of hydrochloric acid were added to this while stirring. The obtained solution was heated and reacted under reflux for 8 hours. Next, to obtain the siloxane polymer,
When this reaction solution was concentrated, it gelled and had poor storage stability.
【００４６】[0046]
【発明の効果】本発明の感光性樹脂組成物は、塗布性に
優れており、塗布後の被膜にムラ、筋などの欠陥が発生
しない。また、保存中も粘度変化、塗布性劣化がなく、
保存安定性が優れている。さらに、プロセスラティチュ
ードが広く、パターン加工容易性を有している。EFFECTS OF THE INVENTION The photosensitive resin composition of the present invention has excellent coatability and does not cause defects such as unevenness and streaks in the coating film after coating. In addition, there is no change in viscosity or deterioration of coating properties during storage,
Excellent storage stability. Further, it has a wide process latitude and is easy to pattern.
Claims (8)
ー、 （２）光によって反応促進剤を発生する化合物、および （３）溶剤を主成分とする感光性樹脂組成物において、
アルカリ可溶性シロキサンポリマーが、アルコキシシラ
ンに水および触媒を加えて加水分解縮合させた反応溶液
から、水および触媒を除去して得られるアルカリ可溶性
シロキサンポリマーであることを特徴とする感光性樹脂
組成物。1. A photosensitive resin composition comprising (1) an alkali-soluble siloxane polymer, (2) a compound which generates a reaction accelerator by light, and (3) a solvent as a main component,
A photosensitive resin composition, wherein the alkali-soluble siloxane polymer is an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing an alkoxysilane with water and a catalyst.
ルコキシシランに水および触媒を加えて加水分解縮合さ
せた反応溶液から疎水性有機溶剤を用いて抽出した有機
層を水洗することによって、水および触媒を除去して得
られるアルカリ可溶性シロキサンポリマーであることを
特徴とする請求項１記載の感光性樹脂組成物。2. An alkali-soluble siloxane polymer is hydrolyzed and condensed by adding water and a catalyst to an alkoxysilane, and the organic layer extracted with a hydrophobic organic solvent is washed with water to remove the water and the catalyst. The photosensitive resin composition according to claim 1, which is an alkali-soluble siloxane polymer obtained by the above.
であるアルコキシシランが、下記一般式（１）で表され
るアルコキシシランであることを特徴とする請求項１ま
たは２記載の感光性樹脂組成物。 Ｒx Ｓｉ（ＯＲ´）4-x （１） （ただし、Ｒ、Ｒ´は同一もしくは異なっていてもよ
く、それぞれ水素、アルキル基、アリール基、アリル
基、フルオロアルキル基を表す。また、ｘは０〜３の整
数である。）3. The photosensitive resin composition according to claim 1 or 2, wherein the alkoxysilane which is a raw material of the alkali-soluble siloxane polymer is an alkoxysilane represented by the following general formula (1). R x Si (OR ′) 4-x (1) (wherein R and R ′ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an allyl group or a fluoroalkyl group. Is an integer of 0 to 3.)
光酸発生剤であることを特徴とする請求項１〜３いずれ
か記載の感光性樹脂組成物。4. The photosensitive resin composition according to claim 1, wherein the compound which generates a reaction accelerator by light is a photoacid generator.
光塩基発生剤であることを特徴とする請求項１〜３いず
れか記載の感光性樹脂組成物。5. The photosensitive resin composition according to claim 1, wherein the compound which generates a reaction accelerator by light is a photobase generator.
成物を基板上に塗布、乾燥後、マスクを介して露光し、
つづいて現像することを特徴とするパターン形成方法。6. A photosensitive resin composition according to any one of claims 1 to 5 is applied onto a substrate, dried, and then exposed through a mask,
A pattern forming method, characterized by the subsequent development.
ることを特徴とする請求項６記載のパターン形成方法。7. The pattern forming method according to claim 6, wherein heating is performed after exposure through a mask and before development.
であることを特徴とする請求項６記載のパターン形成方
法。8. The pattern forming method according to claim 6, wherein the developing solution used for development is an aqueous alkaline solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4296954A JPH06148895A (en) | 1992-11-06 | 1992-11-06 | Photosensitive resin composition and pattern forming method using that |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4296954A JPH06148895A (en) | 1992-11-06 | 1992-11-06 | Photosensitive resin composition and pattern forming method using that |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06148895A true JPH06148895A (en) | 1994-05-27 |
Family
ID=17840338
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4296954A Pending JPH06148895A (en) | 1992-11-06 | 1992-11-06 | Photosensitive resin composition and pattern forming method using that |
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| Country | Link |
|---|---|
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| JP2004184999A (en) * | 2002-12-02 | 2004-07-02 | Rohm & Haas Electronic Materials Llc | Photoimageable waveguide composition and waveguide formed therefrom |
| WO2005010077A1 (en) * | 2003-07-29 | 2005-02-03 | Toagosei Co., Ltd. | Silicon-containing polymer, process for rpoducing the same, heat-resistant resin composition, and heat-resistant film |
| WO2005036269A1 (en) * | 2003-10-07 | 2005-04-21 | Hitachi Chemical Co., Ltd. | Radiation-curing composition, method for storing same, method for forming cured film, method for forming pattern, method for using pattern, electronic component, and optical waveguide |
| WO2005036270A1 (en) * | 2003-10-07 | 2005-04-21 | Hitachi Chemical Co., Ltd. | Radiation-curing composition, method for storing same, method for forming cured film, method for forming pattern, method for using pattern, electronic component, and optical waveguide |
| JP2005325344A (en) * | 2004-04-14 | 2005-11-24 | Rohm & Haas Electronic Materials Llc | Waveguide composition and waveguide produced from the composition |
| KR100617421B1 (en) * | 1998-06-18 | 2006-08-30 | 제이에스알 가부시끼가이샤 | Photo-Curable Compositions and Photo-Cured Products |
| JP2006522861A (en) * | 2003-04-02 | 2006-10-05 | ダウ グローバル テクノロジーズ インコーポレイティド | Organosilicate resin formulations for use in microelectronic devices |
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-
1992
- 1992-11-06 JP JP4296954A patent/JPH06148895A/en active Pending
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| US5861235A (en) * | 1996-06-26 | 1999-01-19 | Dow Corning Asia, Ltd. | Ultraviolet-curable composition and method for patterning the cured product therefrom |
| KR100617421B1 (en) * | 1998-06-18 | 2006-08-30 | 제이에스알 가부시끼가이샤 | Photo-Curable Compositions and Photo-Cured Products |
| JP2004184999A (en) * | 2002-12-02 | 2004-07-02 | Rohm & Haas Electronic Materials Llc | Photoimageable waveguide composition and waveguide formed therefrom |
| JP2006522861A (en) * | 2003-04-02 | 2006-10-05 | ダウ グローバル テクノロジーズ インコーポレイティド | Organosilicate resin formulations for use in microelectronic devices |
| WO2005010077A1 (en) * | 2003-07-29 | 2005-02-03 | Toagosei Co., Ltd. | Silicon-containing polymer, process for rpoducing the same, heat-resistant resin composition, and heat-resistant film |
| US8329815B2 (en) | 2003-07-29 | 2012-12-11 | Toagosei Co., Ltd. | Silicone-containing polymer and a heat-resistant resin composition comprising the silicon-containing polymer |
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| JP2011102399A (en) * | 2003-07-29 | 2011-05-26 | Toagosei Co Ltd | Silicon-containing polymer compound, manufacturing method of the same, heat-resistant resin composition, and heat-resistant coating |
| JPWO2005010077A1 (en) * | 2003-07-29 | 2006-11-30 | 東亞合成株式会社 | SILICON-CONTAINING POLYMER COMPOUND, PROCESS FOR PRODUCING THE SAME, HEAT-RESISTANT RESIN COMPOSITION AND HEAT-RESISTANT FILM |
| US7811637B2 (en) | 2003-07-29 | 2010-10-12 | Toagosei Co., Ltd. | Silicon-containing polymer, process for producing the same, heat-resistant resin composition, and heat-resistant film |
| KR100853054B1 (en) * | 2003-10-07 | 2008-08-19 | 히다치 가세고교 가부시끼가이샤 | Radiation curable composition, storing method thereof, forming method of cured film, patterning method, use of pattern, electronic components and optical waveguide |
| WO2005036270A1 (en) * | 2003-10-07 | 2005-04-21 | Hitachi Chemical Co., Ltd. | Radiation-curing composition, method for storing same, method for forming cured film, method for forming pattern, method for using pattern, electronic component, and optical waveguide |
| US7297464B2 (en) | 2003-10-07 | 2007-11-20 | Hitachi Chemical Co., Ltd. | Radiation curable composition, storing method thereof, forming method of cured film, patterning method, use of pattern, electronic components and optical waveguide |
| KR100869882B1 (en) * | 2003-10-07 | 2008-11-24 | 히다치 가세고교 가부시끼가이샤 | Radiation curable composition, forming method of cured film and patterning method |
| WO2005036269A1 (en) * | 2003-10-07 | 2005-04-21 | Hitachi Chemical Co., Ltd. | Radiation-curing composition, method for storing same, method for forming cured film, method for forming pattern, method for using pattern, electronic component, and optical waveguide |
| US8034545B2 (en) | 2003-10-07 | 2011-10-11 | Hitachi Chemical Co., Ltd. | Radiation curable composition, storing method thereof, forming method of cured film, patterning method, use of pattern, electronic components and optical waveguide |
| JP2005325344A (en) * | 2004-04-14 | 2005-11-24 | Rohm & Haas Electronic Materials Llc | Waveguide composition and waveguide produced from the composition |
| JP2007225802A (en) * | 2006-02-22 | 2007-09-06 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| US8119323B2 (en) | 2006-06-13 | 2012-02-21 | Sekisui Chemical Co., Ltd. | Process for producing patterned film and photosensitive resin composition |
| WO2008047654A1 (en) * | 2006-10-12 | 2008-04-24 | Sekisui Chemical Co., Ltd. | Composition for formation of film, method for production of patterned film, and insulation film for electronic device |
| JP2010282031A (en) * | 2009-05-01 | 2010-12-16 | Jsr Corp | Negative radiation-sensitive composition, cured pattern forming method and cured pattern |
| WO2012157543A1 (en) * | 2011-05-13 | 2012-11-22 | セントラル硝子株式会社 | Condensation product, photosensitive composition, method for producing photosensitive composition, and method for forming negative resist pattern using photosensitive composition |
| KR101286189B1 (en) * | 2011-07-13 | 2013-07-15 | 삼성정밀화학 주식회사 | Heat resistant composition for coating and the manufacturing method of the same |
| US8871425B2 (en) | 2012-02-09 | 2014-10-28 | Az Electronic Materials (Luxembourg) S.A.R.L. | Low dielectric photoimageable compositions and electronic devices made therefrom |
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