JPH06161110A - Heat resistant positive type photoresist composition, photosensitive base material using it and pattern forming method - Google Patents
Heat resistant positive type photoresist composition, photosensitive base material using it and pattern forming methodInfo
- Publication number
- JPH06161110A JPH06161110A JP4310147A JP31014792A JPH06161110A JP H06161110 A JPH06161110 A JP H06161110A JP 4310147 A JP4310147 A JP 4310147A JP 31014792 A JP31014792 A JP 31014792A JP H06161110 A JPH06161110 A JP H06161110A
- Authority
- JP
- Japan
- Prior art keywords
- photoresist composition
- polyimide precursor
- heat
- resistant positive
- compound
- 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.)
- Pending
Links
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は感光性を有する樹脂成分
からなる耐熱性ポジ型フォトレジスト組成物および感光
性基材ならびに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 heat-resistant positive photoresist composition comprising a photosensitive resin component, a photosensitive substrate and a pattern forming method.
【０００２】[0002]
【従来の技術】従来から感光性ポリイミドまたはその前
駆体などを用いてなる耐熱性フォトレジストや、その用
途については良く知られており、例えばネガ型フォトレ
ジストとしては、ポリイミド前駆体にエステル結合ま
たはイオン結合を介してメタクリロイル基を導入する方
法（特開昭４９−１１５４１号公報、特開昭５０−４０
９２２号公報、特開昭５４−１４５７９４号公報、特開
昭５６−３８０３８号公報）、光重合性オレフィンを
有する可溶性ポリイミド（特開昭５９−１０８０３１号
公報、特開昭５９−２２０７３０号公報、特開昭５９−
２３２１２２号公報、特開昭６０−６７２９号公報、特
開昭６０−７２９２５号公報、特開昭６１−５７６２０
号公報）、ベンゾフェノン骨格を有し、かつ窒素原子
が結合する芳香環のオルソ位にアルキル基を有する自己
増感型ポリイミド（特開昭５９−２１９３３０号公報、
特開昭５９−２３１５３３号公報）、ポリイミドと同
程度の耐熱性を有するポリベンゾオキサゾール前駆体
（高分子学会年会予稿集，ｐ６６４，１９８８）などが
提案されている。2. Description of the Related Art Conventionally, heat-resistant photoresists made of photosensitive polyimide or its precursors and their uses are well known. For example, as negative photoresists, polyimide precursors have ester bonds or Method of introducing a methacryloyl group through an ionic bond (JP-A-49-11541, JP-A-50-40)
922, JP-A-54-145794, JP-A-56-38038), soluble polyimides having a photopolymerizable olefin (JP-A-59-108031, JP-A-59-220730). JP-A-59-
No. 232122, JP-A-60-6729, JP-A-60-72925, and JP-A-61-57620.
JP-A-59-219330, which has a benzophenone skeleton and has an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (Japanese Patent Laid-Open No. 59-219330).
JP-A-59-231533), a polybenzoxazole precursor having a heat resistance comparable to that of polyimide (Proceedings of the Annual Meeting of the Polymer Society of Japan, p664, 1988) and the like have been proposed.
【０００３】一方、ポジ型フォトレジストとしては、
ポリイミド前駆体にエステル結合を介してｏ−ニトロベ
ンジル基を導入する方法（J.Macromol.Sci.Chem.,A24,
10,1407,1987）、可溶性ヒドロキシルイミドまたはポ
リオキサゾール前駆体にナフトキノンジアジド化合物を
混合する方法（特公昭６４−６０６３０号公報、米国特
許明細書４３９５４８２号）、可溶性ポリイミドにエ
ステル結合を介してナフトキノンジアジドを導入する方
法（Macromolecules,23,1990）、化学増幅型のポリイ
ミド（特開平３−７６３号公報）、ポリイミド前駆体
にナフトキノンジアジドを混合するもの（特開昭５２−
１３３１５号公報）などが提案されている。On the other hand, as a positive photoresist,
Method for introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (J. Macromol. Sci. Chem., A24,
10 , 1407, 1987), a method of mixing a naphthoquinonediazide compound with a soluble hydroxylimide or polyoxazole precursor (Japanese Patent Publication No. 64-60630, US Pat. No. 4,395,482), and naphthoquinonediazide to a soluble polyimide via an ester bond. (Macromolecules, 23, 1990), a chemically amplified polyimide (JP-A-3-763), and a method in which a naphthoquinonediazide is mixed with a polyimide precursor (JP-A-52-
13315).
【０００４】しかしながら、ネガ型フォトレジストでは
その機能上、解像度に問題があったり用途によっては製
造時の歩留まり低下を招くなどの問題がある。また、上
記、、のものでは用いるポリマーの構造が限定さ
れるために、最終的に得られる被膜の物性が限定されて
しまい多目的用途には不向きなものである。一方、ポジ
型フォトレジストにおいても上記のように感光剤の吸
収波長に伴う問題から感度や解像度が低かったり、上記
、、も構造が限定されるので、上記、、と
同様な問題を有する。さらに、上記では画像形成後の
高温処理に伴う膜減りの問題があり、未だ実用化に至る
ものはないのが実状である。However, the negative type photoresist has a problem in resolution due to its function and may cause a decrease in yield at the time of manufacturing depending on its use. Further, in the above-mentioned ones, since the structure of the polymer used is limited, the physical properties of the coating film finally obtained are limited, which is not suitable for multipurpose use. On the other hand, the positive type photoresist also has the same problems as those described above because the sensitivity and resolution are low due to the problems associated with the absorption wavelength of the photosensitizer as described above and the structures of the above are limited. Further, in the above, there is a problem of film loss due to high temperature processing after image formation, and it is the actual situation that it has not yet been put to practical use.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、従来
からのフォトレジストが有する課題を解決し、レジスト
形成物質としてのポリイミド前駆体がいかなる構造であ
っても充分に対応でき、しかも感度や解像度も良好な耐
熱性ポジ型フォトレジスト組成物を提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of conventional photoresists, to sufficiently cope with any structure of a polyimide precursor as a resist forming substance, and to improve sensitivity and sensitivity. It is to provide a heat-resistant positive photoresist composition having good resolution.
【０００６】また、他の目的は上記耐熱性ポジ型フォト
レジスト組成物を用いてなる感光性基材ならびにパター
ン形成方法を提供することにある。Another object of the present invention is to provide a photosensitive substrate and a pattern forming method using the above heat-resistant positive photoresist composition.
【０００７】[0007]
【課題を解決するための手段】本発明者らは鋭意検討を
重ねた結果、下記（化４）にて示されるポリイミド前駆
体に、特定のビニルエーテル化合物および活性光線の照
射によって酸性を呈する化合物を配合することによっ
て、上記本発明の目的を達成できる組成物が得られるこ
とを見い出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive investigations by the present inventors, as a result, a polyimide precursor represented by the following (Chemical Formula 4) was treated with a specific vinyl ether compound and a compound exhibiting acidity upon irradiation with actinic rays. It has been found that a composition that can achieve the above-mentioned object of the present invention can be obtained by blending, and the present invention has been completed.
【０００８】即ち、本発明の耐熱性ポジ型フォトレジス
ト組成物は、下記（化４）にて示される構造単位を有す
るポリイミド前駆体と、That is, the heat-resistant positive photoresist composition of the present invention comprises a polyimide precursor having a structural unit represented by the following (Chemical Formula 4):
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】下記（化５）または（化６）にて示される
ビニルエーテル化合物と、A vinyl ether compound represented by the following (formula 5) or (formula 6),
【００１１】[0011]
【化５】 [Chemical 5]
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】活性光線の照射によって酸性を呈する化合
物、とを含有してなるものである。A compound which exhibits acidity upon irradiation with actinic rays.
【００１４】さらに、本発明は支持体の表面に上記耐熱
性ポジ型フォトレジスト組成物を塗設することによって
得られる感光性基材、および上記耐熱性ポジ型フォトレ
ジスト組成物から得られたフィルムに、フォトマスクを
介して活性光線の照射、および加熱処理を行なったの
ち、アルカリ性現像液にて露光部分を除去することを特
徴とするパターン形成方法、ならびに上記耐熱性ポジ型
フォトレジスト組成物から得られたフィルムに、加熱処
理を行い、さらにフォトマスクを介して活性光線の照射
を行ったのち、アルカリ性現像液にて露光部分を除去す
ることを特徴とするパターン形成方法を提供するもので
ある。The present invention further provides a photosensitive substrate obtained by coating the heat-resistant positive photoresist composition on the surface of a support, and a film obtained from the heat-resistant positive photoresist composition. In addition, after irradiating with actinic rays through a photomask, and heat treatment, the pattern forming method characterized by removing the exposed portion with an alkaline developing solution, and from the heat-resistant positive photoresist composition A pattern forming method is provided, which comprises subjecting the obtained film to a heat treatment, further irradiating an actinic ray through a photomask, and then removing an exposed portion with an alkaline developing solution. .
【００１５】上記（化４）で示されるポリイミド前駆体
の構造単位中のＲ1 は、具体的にはベンゼン、ナフタレ
ン、ペリレン、ビフェニル、ジフェニルエーテル、ジフ
ェニルスルホン、ジフェニルプロパン、ジフェニルヘキ
サフルオロプロパン、ベンゾフェノン、ブタン、シクロ
ブタンなどの骨格を有する４価の芳香族または脂肪族炭
化水素残基が典型的な例として例示されるが、これらに
限定されるものではない。好ましい基としてはフェニ
ル、ビフェニル、ジフェニルエーテル、およびベンゾフ
ェノンである。なお、必要に応じてＲ1 として上記にて
例示した基の二種類以上を含有させることもできる。R 1 in the structural unit of the polyimide precursor represented by the above (Chemical Formula 4) is specifically benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl propane, diphenyl hexafluoropropane, benzophenone, A tetravalent aromatic or aliphatic hydrocarbon residue having a skeleton such as butane or cyclobutane is exemplified as a typical example, but is not limited thereto. Preferred groups are phenyl, biphenyl, diphenyl ether, and benzophenone. In addition, two or more kinds of the groups exemplified above may be contained as R 1 if necessary.
【００１６】また、Ｒ2 としては、具体的にはジフェニ
ルエーテル、ジフェニルチオエーテル、ベンゾフェノ
ン、ジフェニルメタン、ジフェニルプロパン、ジフェニ
ルヘキサフルオロプロパン、ジフェニルスルホキシド、
ジフェニルスルホン、ビフェニル、ピリジン、ベンゼン
などの骨格を有する２価の芳香族または脂肪族炭化水素
残基が典型的な例として例示されるが、これらに限定さ
れるものではない。好ましい基としてはジフェニルエー
テル、ジフェニルスルホン、およびベンゼンである。な
お、必要に応じてＲ2 として上記にて例示した基の二種
類以上を含有させることもできる。Specific examples of R 2 include diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfoxide,
A divalent aromatic or aliphatic hydrocarbon residue having a skeleton such as diphenyl sulfone, biphenyl, pyridine or benzene is exemplified as a typical example, but the present invention is not limited thereto. Preferred groups are diphenyl ether, diphenyl sulfone, and benzene. If necessary, R 2 may contain two or more types of the groups exemplified above.
【００１７】上記構造単位を有するポリイミド前駆体
は、例えば上記Ｒ1 を分子内に有する芳香族もしくは脂
肪族テトラカルボン酸二無水物と、上記Ｒ2 を分子内に
有する芳香族もしくは脂肪族ジアミンの略等モル量を、
Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセト
アミド、ジメチルホルムアミド、ジメチルスルホキシ
ド、ヘキサメチルホスホルアミドなどの有機溶媒中にて
反応させることによって得ることができる。The polyimide precursor having the structural unit, for example an aromatic or aliphatic tetracarboxylic acid dianhydride having the R 1 in the molecule, an aromatic or aliphatic diamine having in the R 2 molecule Substantially equimolar amount,
It can be obtained by reacting in an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide.
【００１８】本発明の耐熱性ポジ型フォトレジスト組成
物に含有させるビニルエーテル化合物としては、上記
（化５）および（化６）にて表される化合物を用いる。
（化５）および（化６）におけるＲ5 およびＲ6 はビニ
ルエーテル基を１つ以上結合する有機基であって、具体
的にはベンゼン、ジフェニルプロパン、ジフェニルヘキ
サフルオロプロパン、ジフェニルエーテル、シクロヘキ
サン、エタンなどを基本骨格とする１価もしくは多価の
芳香族もしくは脂肪族炭化水素基が例示される。好まし
い基としてはベンゼン、ジフェニルプロパン、シクロヘ
キサンであり、２〜４価の有機基が好ましい。As the vinyl ether compound contained in the heat-resistant positive photoresist composition of the present invention, the compounds represented by the above (formula 5) and (formula 6) are used.
R 5 and R 6 in (Chemical Formula 5) and (Chemical Formula 6) are organic groups that bond one or more vinyl ether groups, and specifically include benzene, diphenylpropane, diphenylhexafluoropropane, diphenylether, cyclohexane, ethane and the like. A monovalent or polyvalent aromatic or aliphatic hydrocarbon group having a basic skeleton is exemplified. Preferred groups are benzene, diphenylpropane, and cyclohexane, and divalent to tetravalent organic groups are preferred.
【００１９】上記ビニルエーテル化合物は前記のポリイ
ミド前駆体１００重量部に対して１０〜８０重量部、好
ましくは４０〜６０重量部の範囲で含有させる。含有量
が１０重量部に満たない場合には、現像時における未露
光部分の膜減りが大きくなり、また、含有量が８０重量
部を超えると、高温加熱時に膜減りが大きくなったり、
最終低に得られる被膜の物性に悪影響を及ぼしたりして
好ましくない。The vinyl ether compound is contained in an amount of 10 to 80 parts by weight, preferably 40 to 60 parts by weight, based on 100 parts by weight of the polyimide precursor. When the content is less than 10 parts by weight, the film loss of the unexposed portion during development becomes large, and when the content exceeds 80 parts by weight, the film loss at high temperature heating becomes large,
It is not preferable because it has a bad influence on the physical properties of the coating film obtained at the final low.
【００２０】一方、上記ビニルエーテル化合物と共に含
有させ、活性光線の照射によって酸性を呈する化合物と
しては、所謂光分解性プロトン発生剤と呼ばれる物質で
あって、例えばジアリルスルホニウム塩、トリアリルス
ルホニウム塩、ジアニキルフェナシルスルホニウム塩、
アリルジアゾニウム塩などのオニウム塩や、芳香族テト
ラカルボン酸エステル、芳香族スルホン酸エステル、ニ
トロベンジルエステル、芳香族スルファミド、ナフトキ
ノンジアジド−４−スルホン酸エステルなどが挙げられ
る。On the other hand, a compound which is contained together with the above vinyl ether compound and exhibits acidity upon irradiation with actinic rays is a substance called a so-called photodegradable proton generator, and examples thereof include diallyl sulfonium salts, triallyl sulfonium salts and dianil phemes. Nacilsulfonium salt,
Examples thereof include onium salts such as allyldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic sulfamides, and naphthoquinonediazide-4-sulfonic acid esters.
【００２１】これらの化合物は前記ポリイミド前駆体１
００重量部に対して５〜５０重量部、好ましくは１０〜
２０重量部の範囲で含有させる。含有量が５重量部に満
たない場合には紫外線や可視光線などの活性光線を照射
した際に、光感度が充分ではなく溶解性コントラストが
不鮮明となりやすく、また、含有量が５０重量部を超え
ると、フォトレジスト組成物として溶液状態で保存した
場合に保存安定性が悪くなる傾向を示し、さらに、光照
射後に得られる画像に対しても悪影響を及ぼし、解像度
が低下する傾向を示す。These compounds are the above-mentioned polyimide precursors 1.
5 to 50 parts by weight, preferably 10 to 100 parts by weight
It is contained in the range of 20 parts by weight. When the content is less than 5 parts by weight, the photosensitivity is not sufficient and the solubility contrast is liable to be unclear when irradiated with active rays such as ultraviolet rays and visible rays, and the content exceeds 50 parts by weight. When the composition is stored as a photoresist composition in a solution state, the storage stability tends to be poor, and the image obtained after light irradiation is also adversely affected, and the resolution tends to be lowered.
【００２２】本発明の耐熱性ポジ型フォトレジスト組成
物からは次のようにして所望のパターンが形成されると
推測される。つまり、露光前、もしくは露光後の加熱処
理によってポリイミド前駆体におけるカルボキシル基が
ビニルエーテル化合物によって付加、保護される。特
に、ビニルエーテル化合物が多官能性の場合にはポリイ
ミド前駆体が架橋構造となる。未露光部分は上記のよう
にカルボキシル基が保護された状態のためにアルカリ現
像液に対して非溶解状態であるが、露光部分は前記活性
光線によって酸性を呈する物質がプロトンを発生するた
めに、ポリイミド前駆体の保護されたカルボキシル基が
脱保護され、架橋構造体の場合には架橋が切断されてア
ルカリ現像液に対して可溶状態となる。このようにして
露光部と非露光部との溶解コントラストが生じて所望の
ポジ型パターンを得ることができるのである。It is presumed that a desired pattern is formed from the heat-resistant positive photoresist composition of the present invention as follows. That is, the carboxyl group in the polyimide precursor is added and protected by the vinyl ether compound by the heat treatment before or after the exposure. In particular, when the vinyl ether compound is polyfunctional, the polyimide precursor has a crosslinked structure. The unexposed portion is in a non-dissolved state in an alkali developing solution due to the state in which the carboxyl group is protected as described above, but the exposed portion is a substance that is acidic due to the actinic rays, so that a proton is generated, The protected carboxyl group of the polyimide precursor is deprotected, and in the case of a cross-linked structure, the cross-linking is cleaved so that the polyimide precursor becomes soluble in an alkaline developer. In this way, a dissolution contrast between the exposed portion and the non-exposed portion occurs, and a desired positive pattern can be obtained.
【００２３】次に、本発明の耐熱性ポジ型フォトレジス
ト組成物を用いて画像を形成する方法の一例を示す。Next, an example of a method for forming an image using the heat resistant positive photoresist composition of the present invention will be shown.
【００２４】まず、前記（化４）にて示したポリイミド
前駆体と、（化５）または（化６）によって示される特
定のビニルエーテル化合物と、活性光線の照射によって
酸性を呈する化合物とをを、前記した有機溶剤に溶解し
て感光液を調製する。次いで、この感光液をシリコンウ
エハのような基材上に乾燥後の膜厚が１〜４０μｍ、好
ましくは１０〜２０μｍとなるように塗布する。First, the polyimide precursor represented by the above (Chemical formula 4), the specific vinyl ether compound represented by the (Chemical formula 5) or (Chemical formula 6), and the compound exhibiting acidity upon irradiation with actinic rays are prepared. A photosensitive solution is prepared by dissolving it in the above-mentioned organic solvent. Next, this photosensitive solution is applied onto a substrate such as a silicon wafer so that the film thickness after drying is 1 to 40 μm, preferably 10 to 20 μm.
【００２５】塗布した塗膜を乾燥して有機溶剤を除去し
た後に、通常のフォトマスクを通して露光を行ない、露
光後、後加熱（約８０〜１５０℃、１０分程度）を行な
う。そののち、照射部を除去すべくパドル法や浸漬法、
スプレー法などによって現像処理を行う。また、本発明
においては上記露光と後加熱との工程を逆に行なっても
良いものである。After the applied coating film is dried to remove the organic solvent, it is exposed through a normal photomask, and after the exposure, post-heating (about 80 to 150 ° C., about 10 minutes) is performed. After that, paddle method and dipping method to remove the irradiated part,
Development is performed by a spray method or the like. Further, in the present invention, the steps of exposure and post-heating may be performed in reverse.
【００２６】現像処理に用いる現像液としては、露光膜
を適当な時間内で完全に溶解除去できるものが好まし
く、水酸化ナトリウム、水酸化カリウムなどの無機アル
カリ性水溶液、またはプロピルアミン、ブチルアミン、
モノエタノールアミン、テトラメチルアンモニウムハイ
ドロオキサイド、コリンなどの有機アルカリ性水溶液な
どを単独もしくは二種以上混合して用いる。また、この
アルカリ性水溶液には必要に応じてアルコール類などの
有機溶剤や、各種界面活性剤を含有させることもでき
る。The developer used for the developing treatment is preferably one which can completely dissolve and remove the exposed film within a proper time, and an inorganic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or propylamine, butylamine,
An organic alkaline aqueous solution of monoethanolamine, tetramethylammonium hydroxide, choline or the like is used alone or in combination of two or more. Further, the alkaline aqueous solution may contain organic solvents such as alcohols and various surfactants, if necessary.
【００２７】現像したのち、リンス液で洗浄することに
より所望のパターンを有するポリイミド前駆体からなる
画像が形成される。After development, an image composed of a polyimide precursor having a desired pattern is formed by washing with a rinse liquid.
【００２８】以上のようにして得られた画像は、最終的
な高温加熱処理（約２００〜４００℃）をすることによ
ってイミド化され、耐熱性を有するポリイミド樹脂から
なる画像となるのである。The image obtained as described above is imidized by the final high-temperature heat treatment (about 200 to 400 ° C.) and becomes an image made of a heat-resistant polyimide resin.
【００２９】[0029]
【実施例】以下に本発明の実施例を示し、本発明をさら
に具体的に説明する。EXAMPLES The present invention will be described in more detail below by showing Examples of the present invention.
【００３０】実施例１ ３，３’，４，４’−ビフェニルテトラカルボン酸二無
水物と、４，４’−ジアミノジフェニルスルホンとの略
等モル量を、ジメチルアセトアミド中、室温下で２４時
間反応させ、前記（化４）にて示される構造単位を有す
るポリイミド前駆体溶液を得た。Example 1 About equimolar amounts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfone were added in dimethylacetamide at room temperature for 24 hours. The reaction was performed to obtain a polyimide precursor solution having the structural unit represented by the above (Chemical formula 4).
【００３１】得られたポリイミド前駆体溶液の固形分１
００重量部に対して、下記（化７）にて表されるビニル
エーテル化合物を４０重量部を添加、混合し、さらに、
光分解性プロトン発生剤としてのジフェニルイオドニウ
ム−８−アニリノナフタレン−１−スルホネートを１０
重量部添加、混合した。Solid content 1 of the obtained polyimide precursor solution
40 parts by weight of a vinyl ether compound represented by the following (Chemical formula 7) was added to and mixed with 00 parts by weight.
Diphenyliodonium-8-anilinonanaphthalene-1-sulfonate as a photodegradable proton generating agent was added to
Parts by weight were added and mixed.
【００３２】[0032]
【化７】 [Chemical 7]
【００３３】これらの溶液をシリコンウエハ上にスピン
コートして、１０〜１５μｍの乾燥塗膜を形成し、その
のちガラスマスクを通して２５０Ｗ超高圧水銀灯を用い
て光源から３０ｃｍのところで３分間、真空密着露光を
行った。These solutions were spin-coated on a silicon wafer to form a dry coating film of 10 to 15 μm, and then vacuum contact exposure was performed through a glass mask using a 250 W ultra-high pressure mercury lamp at a distance of 30 cm from the light source for 3 minutes. I went.
【００３４】露光後、１３０℃で１０分間加熱したの
ち、テトラメチルアンモニウムハイドロオキサイド１．
５重量％水溶液にて３分間現像、水でリンスしたとこ
ろ、表１に示す解像性ならびに高温加熱（３５０℃／１
時間）後の残膜厚率を得た。なお、上記実施例品の特性
値は実用レベルに達する値であった。After exposure, after heating at 130 ° C. for 10 minutes, tetramethylammonium hydroxide 1.
After development with a 5% by weight aqueous solution for 3 minutes and rinsing with water, the resolution and high temperature heating shown in Table 1 (350 ° C / 1
The remaining film thickness ratio after (time) was obtained. In addition, the characteristic values of the above-mentioned example products were values that reached a practical level.
【００３５】実施例２ 実施例１において３，３’，４，４’−ジフェニルエー
テルテトラカルボン酸二無水物と、４，４’−ジアミノ
ジフェニルスルホンとの略等モル量を、ジメチルアセト
アミド中、室温下で２４時間反応させて得られたポリイ
ミド前駆体溶液を用いた以外は、実施例１と同様にして
感光液を調製し、パターン形成を行った。結果を表１に
示す。なお、上記実施例品の特性値は実用レベルに達す
る値であった。Example 2 In Example 1, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl sulfone were mixed in an approximately equimolar amount in dimethylacetamide at room temperature. A photosensitive solution was prepared in the same manner as in Example 1 except that the polyimide precursor solution obtained by reacting under the conditions of 24 hours was used to form a pattern. The results are shown in Table 1. In addition, the characteristic values of the above-mentioned example products were values that reached a practical level.
【００３６】比較例１ 実施例１において用いた光分解性プロトン発生剤の代わ
りに、光ラジカル発生剤であるジメチルアミノベンゾフ
ェノンを用いた以外は、実施例１と同様にして感光液を
調製し、パターン形成を行った。Comparative Example 1 A photosensitive solution was prepared in the same manner as in Example 1, except that dimethylaminobenzophenone, which was a photoradical generator, was used in place of the photodecomposable proton generator used in Example 1. A pattern was formed.
【００３７】その結果、現像後の塗膜に明確なコントラ
ストが得られず、レリーフ画像を得ることができなかっ
た。As a result, no clear contrast was obtained in the coating film after development, and a relief image could not be obtained.
【００３８】比較例２ 実施例１において用いたビニルエーテル化合物の代わり
に、二官能性のメタクリロイル単量体である１，２−ビ
スメタクリロイルエチレンを用いた以外は、実施例１と
同様にして感光液を調製し、パターン形成を行った。Comparative Example 2 A photosensitive solution was prepared in the same manner as in Example 1 except that 1,2-bismethacryloylethylene, which is a bifunctional methacryloyl monomer, was used in place of the vinyl ether compound used in Example 1. Was prepared and pattern formation was performed.
【００３９】その結果、現像後の塗膜に明確なコントラ
ストが得られず、レリーフ画像を得ることができなかっ
た。As a result, a clear contrast was not obtained in the coating film after development, and a relief image could not be obtained.
【００４０】実施例３ 実施例１において、露光工程と後加熱工程を逆にした以
外は、実施例１と同様にして画像形成を行なった。Example 3 Image formation was carried out in the same manner as in Example 1 except that the exposure step and the post-heating step were reversed.
【００４１】その結果、表１に示すように実施例１とほ
ぼ同様の特性値の良好なパターンを得ることができた。As a result, as shown in Table 1, good patterns having substantially the same characteristic values as in Example 1 could be obtained.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【発明の効果】本発明の耐熱性ポジ型フォトレジスト組
成物は以上のような組成からなり、アルカリ可溶性を呈
するポリイミド前駆体が特定のポリビニル化合物によっ
てカルボキシル基が保護されるので溶解性が低下する。
そして、活性光線が照射された露光部分のポリイミド前
駆体のカルボキシル基は脱保護されるので、アルカリ可
溶性となり、露光部分と非露光部分とのアルカリ現像液
に対する溶解性が異なり、高感度で高解像度の実用に耐
えうる所望のパターン形成が可能となる。EFFECT OF THE INVENTION The heat-resistant positive photoresist composition of the present invention has the composition as described above, and the solubility of the polyimide precursor exhibiting alkali solubility is lowered because the carboxyl group is protected by the specific polyvinyl compound. .
Then, the carboxyl group of the polyimide precursor in the exposed portion irradiated with actinic rays is deprotected, so that it becomes alkali-soluble and the exposed portion and the non-exposed portion have different solubilities in an alkali developing solution, and have high sensitivity and high resolution. It is possible to form a desired pattern that can withstand the above practical use.
【００４４】さらに、高温加熱処理して得られる最終物
（ポリイミド樹脂）は耐熱性や電気的特性、機械的特定
に優れるので、半導体工業における固体素子や、回路基
板の保護膜、絶縁膜を形成するための材料としても好適
なものである。Furthermore, since the final product (polyimide resin) obtained by high-temperature heat treatment is excellent in heat resistance, electrical characteristics, and mechanical identification, it forms a solid element in the semiconductor industry, a protective film for a circuit board, and an insulating film. It is also suitable as a material for
Claims (4)
するポリイミド前駆体と、 【化１】 下記（化２）または（化３）にて示されるビニルエーテ
ル化合物と、 【化２】 【化３】 活性光線の照射によって酸性を呈する化合物、とを含有
してなる耐熱性ポジ型フォトレジスト組成物。1. A polyimide precursor having a structural unit represented by the following (Chemical formula 1); A vinyl ether compound represented by the following (Chemical Formula 2) or (Chemical Formula 3), and [Chemical 3] A heat-resistant positive photoresist composition containing a compound that exhibits acidity upon irradiation with actinic rays.
ジ型フォトレジスト組成物を塗設してなる感光性基材。2. A photosensitive substrate obtained by coating the heat-resistant positive photoresist composition according to claim 1 on the surface of a support.
スト組成物から得られたフィルムに、フォトマスクを介
して活性光線の照射を行い、さらに加熱処理を行ったの
ち、アルカリ性現像液にて露光部分を除去することを特
徴とするパターン形成方法。3. A film obtained from the heat-resistant positive photoresist composition according to claim 1, is irradiated with an actinic ray through a photomask, and is further heat-treated, followed by an alkaline developer. A pattern forming method characterized by removing an exposed portion.
スト組成物から得られたフィルムに、加熱処理を行い、
さらにフォトマスクを介して活性光線の照射を行ったの
ち、アルカリ性現像液にて露光部分を除去することを特
徴とするパターン形成方法。4. A film obtained from the heat-resistant positive photoresist composition according to claim 1, is heat-treated,
Furthermore, after irradiating an actinic ray through a photomask, the exposed portion is removed with an alkaline developing solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4310147A JPH06161110A (en) | 1992-11-19 | 1992-11-19 | Heat resistant positive type photoresist composition, photosensitive base material using it and pattern forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4310147A JPH06161110A (en) | 1992-11-19 | 1992-11-19 | Heat resistant positive type photoresist composition, photosensitive base material using it and pattern forming method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06161110A true JPH06161110A (en) | 1994-06-07 |
Family
ID=18001735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4310147A Pending JPH06161110A (en) | 1992-11-19 | 1992-11-19 | Heat resistant positive type photoresist composition, photosensitive base material using it and pattern forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06161110A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06308733A (en) * | 1993-04-23 | 1994-11-04 | Kansai Paint Co Ltd | Photosensitive composition and formation of pattern |
| JPH07146552A (en) * | 1993-04-16 | 1995-06-06 | Kansai Paint Co Ltd | Photosensitive composition and pattern forming method |
| WO1999054788A1 (en) * | 1998-04-17 | 1999-10-28 | Kansai Paint Co., Ltd. | Photosensitive resin composition |
| EP1099983A1 (en) * | 1999-11-12 | 2001-05-16 | Shin-Etsu Chemical Co., Ltd. | Chemically amplified positive resist composition and patterning method |
| JP2005316117A (en) * | 2004-04-28 | 2005-11-10 | Kansai Paint Co Ltd | Photosensitive resin composition |
| WO2005111724A1 (en) * | 2004-05-14 | 2005-11-24 | Nissan Chemical Industries, Ltd. | Antireflective film-forming composition containing vinyl ether compound |
| US7666573B2 (en) | 2005-07-14 | 2010-02-23 | Mitsui Chemicals, Inc. | Positive photosensitive resin composition and method for forming pattern |
-
1992
- 1992-11-19 JP JP4310147A patent/JPH06161110A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07146552A (en) * | 1993-04-16 | 1995-06-06 | Kansai Paint Co Ltd | Photosensitive composition and pattern forming method |
| JPH06308733A (en) * | 1993-04-23 | 1994-11-04 | Kansai Paint Co Ltd | Photosensitive composition and formation of pattern |
| WO1999054788A1 (en) * | 1998-04-17 | 1999-10-28 | Kansai Paint Co., Ltd. | Photosensitive resin composition |
| US6344307B1 (en) | 1998-04-17 | 2002-02-05 | Kansai Paint Co., Ltd. | Photosensitive resin composition |
| EP1099983A1 (en) * | 1999-11-12 | 2001-05-16 | Shin-Etsu Chemical Co., Ltd. | Chemically amplified positive resist composition and patterning method |
| JP2005316117A (en) * | 2004-04-28 | 2005-11-10 | Kansai Paint Co Ltd | Photosensitive resin composition |
| JP4499471B2 (en) * | 2004-04-28 | 2010-07-07 | 関西ペイント株式会社 | Photosensitive resin composition |
| WO2005111724A1 (en) * | 2004-05-14 | 2005-11-24 | Nissan Chemical Industries, Ltd. | Antireflective film-forming composition containing vinyl ether compound |
| US8501393B2 (en) | 2004-05-14 | 2013-08-06 | Nissan Chemical Industries, Ltd. | Anti-reflective coating forming composition containing vinyl ether compound |
| US7666573B2 (en) | 2005-07-14 | 2010-02-23 | Mitsui Chemicals, Inc. | Positive photosensitive resin composition and method for forming pattern |
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