JPH022564A - Positive type electron beam resist - Google Patents
Positive type electron beam resistInfo
- Publication number
- JPH022564A JPH022564A JP14582988A JP14582988A JPH022564A JP H022564 A JPH022564 A JP H022564A JP 14582988 A JP14582988 A JP 14582988A JP 14582988 A JP14582988 A JP 14582988A JP H022564 A JPH022564 A JP H022564A
- Authority
- JP
- Japan
- Prior art keywords
- electron beam
- polymer
- cyanoacrylate
- cyclohexyl
- beam resist
- 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
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- ILRMPAUJTPZAIQ-UHFFFAOYSA-N cyclohexyl 2-cyanoprop-2-enoate Chemical compound N#CC(=C)C(=O)OC1CCCCC1 ILRMPAUJTPZAIQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 3
- NOCUHXPGWAPFGO-UHFFFAOYSA-N butan-2-one;propan-2-ol Chemical compound CC(C)O.CCC(C)=O NOCUHXPGWAPFGO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IUGNCEABJSRDPG-UHFFFAOYSA-N 2,2,2-trichloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(Cl)(Cl)Cl IUGNCEABJSRDPG-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-M 2-chloroacrylate Chemical compound [O-]C(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-M 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IQDPHMACOQAPBQ-UHFFFAOYSA-N 2-ethoxyethyl 2-cyanoprop-2-enoate Chemical compound CCOCCOC(=O)C(=C)C#N IQDPHMACOQAPBQ-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QRWOVIRDHQJFDB-UHFFFAOYSA-N isobutyl cyanoacrylate Chemical compound CC(C)COC(=O)C(=C)C#N QRWOVIRDHQJFDB-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
「産業上の利用分野」
本発明はＬＳ Ｌ 超Ｌｓ Ｉなとの高密度集積回路の
製造に用いられるフォトマスクを製造する際に使用され
る高感度で解像度の高いポジ型電子線レジストに関する
ものであり、また、直接描画による個別半導体等の製造
にも用いられるものでもあって電子機器産業において広
く利用されるものである。[Detailed description of the invention] (a) Object of the invention ``Field of industrial application'' The present invention is used in manufacturing photomasks used in manufacturing high-density integrated circuits such as LSL, ultra-LSI, etc. It relates to a positive electron beam resist with high sensitivity and high resolution, and is also used in the manufacture of individual semiconductors by direct writing, and is widely used in the electronic equipment industry.
「従来の技術」
ＬＳ Ｉ、超ＬＳＩの製造に用いられるフォトマスクは
複雑なパターンを要求される上に精度も高いものである
ことが必要である。そのため、フォトマスク製造のリソ
グラフィー工程で用いられるものは主として解像度の高
い電子線レジストとなっている。電子線レジストには、
電子線照射部が分解して可溶化するポジ型と、電子線照
射部が架橋して不溶化するネガ型とがあるが、一般に、
解像度の点ではポジ型の方が優れており、ポジ型の電子
“線レジストとしては、現在主としてポリブテンスルホ
ンが使用されている。ポリブテンスルホンの感度は１〜
２μＣ／ｃＡとされている。"Prior Art" Photomasks used in the manufacture of LSI and VLSI are required to have complex patterns and also to be highly accurate. Therefore, electron beam resists with high resolution are mainly used in the lithography process for manufacturing photomasks. For electron beam resist,
There is a positive type in which the electron beam irradiated part decomposes and becomes solubilized, and a negative type in which the electron beam irradiated part crosslinks and becomes insolubilized, but generally,
Positive type resists are superior in terms of resolution, and polybutene sulfone is currently mainly used as a positive type electron beam resist.Polybutene sulfone has a sensitivity of 1 to 1.
It is said to be 2μC/cA.
「発明が解決しようとする問題点」
しかし、目的とする半導体集積回路の高集積化にともな
いフォトマスクの微細化が進み既存の電子線レジストで
は感度、解像度、特に寸法安定性が不十分となりつつあ
る。また、現在主として用いられているポリブテンスル
ホンには現像液組成および温度による感度の変動や、水
分、湿度に対する不安定さといった問題点もある。その
ため、ポリブテンスルホンに代わるポジ型電子線レジス
トとして種々のレジストが提案されており、例えば、ポ
リ（２，２，３，４，４，４，−へキサフルオロブチル
メタクリレート） 、２，２，２．− トリクロロエチ
ルメタクリレートの共重合体、ポリ（α−クロロアクリ
ル酸２，２，２．−１−リフルオロエチル）などが挙げ
られている。しかし、これらハロゲン含有レジストは高
感度が得られるものの、密着性の問題やプロセス安定性
の問題がありほとんど実用化されていない。"Problems to be Solved by the Invention" However, as the target semiconductor integrated circuits become more highly integrated, photomasks are becoming finer and the sensitivity, resolution, and especially dimensional stability of existing electron beam resists are becoming insufficient. be. In addition, polybutene sulfone, which is currently mainly used, has problems such as sensitivity fluctuations depending on developer composition and temperature, and instability with respect to moisture and humidity. Therefore, various resists have been proposed as positive electron beam resists to replace polybutenesulfone, such as poly(2,2,3,4,4,4,-hexafluorobutyl methacrylate), 2,2,2 ．． - Copolymers of trichloroethyl methacrylate, poly(2,2,2.-1-lifluoroethyl α-chloroacrylate), etc. are mentioned. However, although these halogen-containing resists can provide high sensitivity, they have problems with adhesion and process stability, and are hardly ever put into practical use.
本発明者等は、上記の問題点を解決したポジ型電子線レ
ジストを得るべく鋭意検討した。The present inventors have made extensive studies to obtain a positive electron beam resist that solves the above problems.
（ロ）発明の構成
「問題点を解決するための手段」
検討の結果、本発明者らは、上記の問題点のない、すな
わち感度、解像度及び特に寸法安定性に優れ、かつ密着
性にも優れたポジ型電子線レジストを見いだし本発明を
完成した。(b) Structure of the invention "Means for solving the problems" As a result of the study, the present inventors have found that the invention does not have the above problems, that is, it has excellent sensitivity, resolution, and especially dimensional stability, and also has good adhesion. An excellent positive electron beam resist was discovered and the present invention was completed.
すなわち、本発明は構成単量体の一部又は全部がシクロ
ヘキシル２−シアノアクリレートである重合体を含有す
ることを特徴とするポジ型電子線レジストに関するもの
である。That is, the present invention relates to a positive electron beam resist characterized by containing a polymer in which part or all of the constituent monomers are cyclohexyl 2-cyanoacrylate.
本発明におけるポジ型電子線レジストに含有される構成
単量体の一部又は全部がシクロヘキシル２−シアノアク
リレートである重合体としては、例えば、まずシクロヘ
キシル２−シアノアクリレートを単独重合して得られる
重合体、即ちシクロヘキシル２−シアノアクリレートの
みからなる重合体を挙げることができる。また、シクロ
ヘキシル２−シアノアクリレートにこれと共重合可能な
モノマーを共重合させて得られる重合体を、ポジ型電子
線レジストとして使用すると、その性能がさらに向上し
たものとなる。Examples of polymers in which part or all of the constituent monomers contained in the positive electron beam resist of the present invention are cyclohexyl 2-cyanoacrylate include, for example, polymers obtained by first homopolymerizing cyclohexyl 2-cyanoacrylate. Mention may be made of polymers consisting solely of cyclohexyl 2-cyanoacrylate. Furthermore, when a polymer obtained by copolymerizing cyclohexyl 2-cyanoacrylate with a monomer copolymerizable therewith is used as a positive electron beam resist, its performance is further improved.
性能を向上させる共重合モノマーとしては、メチル２−
シアノアクリレート、エチル２−シアノアクリレート、
イソブチル２−シアノアクリレート、２−エトキシエチ
ル２−シアノアクリレートなどのシアノアクリレート類
が好ましく、より好ましくはメチル２−シアノアクリレ
ートである。As a copolymerizable monomer that improves performance, methyl 2-
cyanoacrylate, ethyl 2-cyanoacrylate,
Cyanoacrylates such as isobutyl 2-cyanoacrylate and 2-ethoxyethyl 2-cyanoacrylate are preferred, and methyl 2-cyanoacrylate is more preferred.
共重合モノマーは一種類に限らず二種類以上用いてもよ
いが、シクロヘキシル２−シアノアクリレートに対する
割合は８０ｍｏ１％以下であることが好ましい。共重合
上ツマ−の割合が８０ｍｏ１％を超えると感度、解像度
及び寸法安定性等が低下する様になる。The number of copolymerizable monomers is not limited to one type, but two or more types may be used, but the proportion to cyclohexyl 2-cyanoacrylate is preferably 80 mo1% or less. If the proportion of copolymerized polymer exceeds 80 mo1%, sensitivity, resolution, dimensional stability, etc. will decrease.
上記重合体としては、重量平均分子量が１万〜４００万
ものが好ましく、より好ましくは５万〜２００万、特に
好ましくは１０万〜１００万のものが用いられる。分子
量があまり大きいと薄膜塗布する際に溶解性のよい溶剤
がながったり、また溶液中でゲルを生成し均一な薄膜を
得ることができなくなったりする。また分子量があまり
小さくても適当な厚さの均一な薄膜を得ることが難しく
なる。The above polymer preferably has a weight average molecular weight of 10,000 to 4,000,000, more preferably 50,000 to 2,000,000, particularly preferably 100,000 to 1,000,000. If the molecular weight is too large, a solvent with good solubility will run out when applying a thin film, or a gel will form in the solution, making it impossible to obtain a uniform thin film. Furthermore, if the molecular weight is too small, it becomes difficult to obtain a uniform thin film with an appropriate thickness.
本発明で重合体をポジ型電子線レジストとして用いる際
に使用される溶剤としては、例えば、メチルエチルケト
ン、メチルイソブチルケトン、シクロヘキサノン、酢酸
エチル、酢酸イソブチル、メチルセロソルブアセテート
、エチルセロソルブアセテート、トルエン、キシレン、
１．２−ジクロロエタンなどが用いられる。Examples of the solvent used when the polymer is used as a positive electron beam resist in the present invention include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, isobutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene,
1,2-dichloroethane and the like are used.
使用する溶剤の種類と量は、−船釣に使用されるポジ型
電子線レジストとしての粘度（約５０ｃｐｓ程度）にな
る様に、使用する重合体の組成、重合度に応じて、定め
ればよい。The type and amount of the solvent to be used should be determined according to the composition and degree of polymerization of the polymer used, so that the viscosity (approximately 50 cps) is achieved as a positive electron beam resist used for boat fishing. good.
こうして得られるポジ型電子線レジスト液は、通常の回
転塗布機を用いてクロムマスクのようなマスク基板に薄
膜塗布することができる。レジスト液の薄膜塗布後適当
な温度でプリベークしたのち、所定のパターンに従って
電子線照射が行われる。本発明の重合体は電子線照射に
より主鎖の分解を受は分子量が低下するため、電子線照
射部と未照射部では溶解性の差が生じる。従って、電子
線を照射した基板を適当な現像液で処理することによっ
て、電子線照射部が選択的に溶解除去され、上記パター
ンに応じた凹凸の画像が得られる。The positive electron beam resist solution thus obtained can be coated as a thin film onto a mask substrate such as a chrome mask using an ordinary spin coater. After applying a thin film of resist solution and prebaking at an appropriate temperature, electron beam irradiation is performed according to a predetermined pattern. When the polymer of the present invention undergoes decomposition of the main chain by electron beam irradiation, the molecular weight decreases, so a difference in solubility occurs between the electron beam irradiated area and the non-irradiated area. Therefore, by treating the substrate irradiated with the electron beam with an appropriate developer, the electron beam irradiated portions are selectively dissolved and removed, and an image with irregularities corresponding to the above-mentioned pattern can be obtained.
この際使用される適当な現像液は、電子線照射部と未照
射部とを区別し照射部を選択的に溶解するものであれば
なんでもよいが、一般には該重合体の良溶剤と貧溶剤と
の組合せの中から選ばれる。The appropriate developing solution used at this time may be any developer as long as it can distinguish between the electron beam irradiated area and the non-irradiated area and selectively dissolve the irradiated area, but generally it is a developer that is a good solvent and a poor solvent for the polymer. selected from among the combinations.
良溶剤、貧溶剤の例を挙げれば、アセトン、メチルエチ
ルケトン、メチルイソブチルケトン、シクロヘキサノン
、テトラヒドロフラン、酢酸エチル、酢酸イソブチル、
メチルセロソルブアセテート、エチルセロソルブアセテ
ート、アセトニトリル、ニトロメタン、Ｎ−メチルピロ
リドン、γ−ブチロラクトン、トルエン、キシレン、１
，２−ジクロロエタンなどが良溶剤であり、メタノール
、エタノール、イソプロピルアルコール、エチルセロソ
ルブ、水、ヘキサン、シクロヘキサンなどが貧溶剤であ
る。Examples of good and poor solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, ethyl acetate, isobutyl acetate,
Methyl cellosolve acetate, ethyl cellosolve acetate, acetonitrile, nitromethane, N-methylpyrrolidone, γ-butyrolactone, toluene, xylene, 1
, 2-dichloroethane, etc. are good solvents, and methanol, ethanol, isopropyl alcohol, ethyl cellosolve, water, hexane, cyclohexane, etc. are poor solvents.
現像後すみやかにリンスを行い、続いてポストベークを
行うことにより電子線照射を行った上記のパターンどお
りの凹凸画像が完成される。Immediately after development, rinsing is performed, followed by post-bake to complete a concavo-convex image in accordance with the above-mentioned pattern after electron beam irradiation.
「作用」
膜厚０．５μｍの本発明レジスト膜に対して電子線照射
を行い残膜感度曲線を求めたところ、０．５〜２μＣ／
ｃｆｆｌの感度が得られた。また、１ｕｍ、２μｍ、４
μｍのラインアンドスペースのパターンでテストしたと
ころ電子線照射部と未照射部との境界は急峻でコントラ
ストが良好であり、寸法安定性のよいラインアンドスペ
ースが得られた。"Operation" When the resist film of the present invention with a film thickness of 0.5 μm was irradiated with an electron beam and the remaining film sensitivity curve was determined, it was found that the resist film of the present invention with a film thickness of 0.5 μm
A sensitivity of cffl was obtained. Also, 1um, 2μm, 4
When a line and space pattern of μm was tested, the boundary between the electron beam irradiated area and the non-irradiated area was steep and the contrast was good, and a line and space pattern with good dimensional stability was obtained.
このような効果が如何なる理由により発現するかは定か
でないが、本発明の繰り返し単位の主鎖構造と側鎖のシ
クロヘキシル基による特異的な効果であると考えられる
。Although it is not clear why such an effect occurs, it is thought to be a specific effect due to the main chain structure of the repeating unit of the present invention and the cyclohexyl group in the side chain.
以下に実施例を挙げて本発明を説明するが、本発明はこ
れに限定されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
撹拌棒、温度計、乾燥管をつけた三ロフラスコにアセト
ン２００成とシクロヘキシル２−シアノアクリレート５
０ｇを入れ、攪拌しなからＯ″Ｃに冷却した。ここにＮ
、Ｎ−ジメチル−ｐ−ｔ−ルイジン０．１ｇをアセトン
２０ｍ１に溶解した液をすばやく添加した。３時間攪拌
した後、酢酸５ｇを加え、この混合液を石油エーテル１
１００ｄに注ぎ重合物を析出させた。石油エーテルでよ
くすすいだ後約６０°Ｃで減圧乾燥した。重合体はアセ
トン／石油エーテル系で再析出することにより精製し、
再び約６０°ＣＴ：減圧乾燥した。収率は９０％、液体
クロマトグラフィーによる重量平均分子量は３８万であ
った。Example 1 200 g of acetone and 5 g of cyclohexyl 2-cyanoacrylate were placed in a three-ring flask equipped with a stirring bar, a thermometer, and a drying tube.
0g was added and cooled to O''C without stirring.
A solution of 0.1 g of N-dimethyl-pt-luidine dissolved in 20 ml of acetone was quickly added. After stirring for 3 hours, 5 g of acetic acid was added, and the mixture was diluted with petroleum ether 1
100d to precipitate a polymer. After rinsing thoroughly with petroleum ether, it was dried under reduced pressure at about 60°C. The polymer was purified by reprecipitation in an acetone/petroleum ether system,
It was dried again at about 60°C under reduced pressure. The yield was 90%, and the weight average molecular weight determined by liquid chromatography was 380,000.
この重合体４０ｇをシクロへキサノン７６０ｇに溶解し
、０．２μｍのテフロンメンブランフィルタ−で加圧ろ
過してレジスト液とした。40 g of this polymer was dissolved in 760 g of cyclohexanone, and filtered under pressure through a 0.2 μm Teflon membrane filter to obtain a resist solution.
この液をクロムマスクに２００Ｏｒｐｍで回転塗布した
後、１３０°Ｃで１５分間プリベークすることにより、
０．４μｍの均一な薄膜が得られた。After spin-coating this solution on a chrome mask at 200 rpm, prebaking at 130°C for 15 minutes,
A uniform thin film of 0.4 μm was obtained.
次に、この薄膜に加速電圧２０ｋＶの電子線を照射し、
メチルエチルケトン−イソプロパノール系の現像液を用
いて残膜感度曲線を求めた。２０°Ｃにて容量比３／２
の液に１分間浸漬した後、イソプロパツールで１５秒間
リンスを行い、１４０°Ｃで１０分間ポストベークを行
う条件によって、残膜感度１．６μＣ／ｃｒｄおよびγ
値２．０が得られた。Next, this thin film was irradiated with an electron beam at an accelerating voltage of 20 kV,
A residual film sensitivity curve was determined using a methyl ethyl ketone-isopropanol developer. Capacity ratio 3/2 at 20°C
The residual film sensitivity was 1.6 μC/crd and γ by immersing the solution in the solution for 1 minute, rinsing with isopropanol for 15 seconds, and post-baking at 140°C for 10 minutes.
A value of 2.0 was obtained.
また、同じように作成した薄膜に、１μｍ、２μｍ、４
μｍのラインアンドスペースのパターンで３μＣ／ｃ＋
ｆｌの電子線を照射した。メチルエチルケトン−イソプ
ロパノール（容量比３／２）に１分間浸漬して現像し、
同様にリンス、ポストベークすることにより寸法のパタ
ーン依存性のないきれいな凹凸画像が得られた。In addition, 1 μm, 2 μm, 4 μm
3μC/c+ with μm line and space pattern
It was irradiated with an electron beam of fl. Developed by immersing in methyl ethyl ketone-isopropanol (volume ratio 3/2) for 1 minute,
Similarly, by rinsing and post-baking, a clean uneven image with no dependence on pattern dimensions was obtained.
さらに、硝酸第２セリウムアンモンと過塩素酸の水溶液
で湿式エツチングを行ったところ、レジストの密着性は
良好でサイドエッチはなく、電子線照射した設計寸法ど
おりのクロムマスクパターンが得られた。Furthermore, when wet etching was performed using an aqueous solution of ceric ammonium nitrate and perchloric acid, the adhesion of the resist was good, there was no side etching, and a chrome mask pattern with the designed dimensions by electron beam irradiation was obtained.
実施例２
実施例１において、シクロヘキシル２−シアノアクリレ
ートの代わりにシクロヘキシル２−シアノアクリレート
とメチル２−シアノアクリレートとを５ ｍｏｌ／ １
ｍｏｌの割合で混合して用いて、同様に重合を行った
。収率は９２％、重量平均分子量は４３万であった。ま
た、ＮＭＲより共重合比を求めたところ５．５ ｍｏｌ
／ １ ｍｏｌであった。Example 2 In Example 1, 5 mol/1 of cyclohexyl 2-cyanoacrylate and methyl 2-cyanoacrylate were used instead of cyclohexyl 2-cyanoacrylate.
Polymerization was carried out in the same manner by mixing them in molar proportions. The yield was 92%, and the weight average molecular weight was 430,000. In addition, the copolymerization ratio was determined from NMR and was 5.5 mol.
/1 mol.
この重合体４０ｇをメチルセロソルブアセテート９６０
ｇに？容解し、０，２μｍのテフロンメンブランフィル
ターで加圧ろ過してレジスト液とした。40g of this polymer was converted into 960g of methyl cellosolve acetate.
In g? The solution was dissolved and filtered under pressure using a 0.2 μm Teflon membrane filter to obtain a resist solution.
この液をクロムマスクに２０００ｒｐｍで回転塗布した
後、１３０°Ｃで１５分間プリベークすることにより０
．５μｍの均一な薄膜が得られた。After spin-coating this solution on a chrome mask at 2000 rpm, prebaking at 130°C for 15 minutes resulted in zero
．． A uniform thin film of 5 μm was obtained.
実施例１と同様に残膜感度曲線を求めたところ、メチル
エチルケトン−イソプロパノール（容量比２／１）に１
分間浸漬した後、イソプロパツールで１５秒間リンスを
行い、１４０°Ｃで１０分間ポストベークを行う条件に
よって、残膜感度１．０μＣ／ｃｉおよびＴ値２．５が
得られた。When the residual film sensitivity curve was obtained in the same manner as in Example 1, it was found that methyl ethyl ketone-isopropanol (volume ratio 2/1)
After immersion for 1 minute, rinsing with isopropanol for 15 seconds, and post-baking at 140°C for 10 minutes, a residual film sensitivity of 1.0 μC/ci and a T value of 2.5 were obtained.
また、２μＣ／ｃｆｆｌの電子線照射後、同様に現像、
リンスおよびポストベークを行うことによりパターン依
存性のないきれいな凹凸画像が得られた。In addition, after irradiation with an electron beam of 2 μC/cffl, development was performed in the same manner.
By performing rinsing and post-baking, a clean uneven image without pattern dependence was obtained.
さらに、湿式エツチングにおいても密着性が良好であっ
た。Furthermore, the adhesion was also good in wet etching.
（ハ）発明の効果
本発明によれば、高感度、高解像度で寸法安定性に優れ
、かつ密着性にも優れたポジ型電子線レジストが得られ
、精度のよいフォトマスクを安定して製造することがで
きる。従って、本発明がＬＳＩ、超ＬＳＩの高集積化に
果たす役割は絶大である。(c) Effects of the Invention According to the present invention, a positive electron beam resist with high sensitivity, high resolution, excellent dimensional stability, and excellent adhesion can be obtained, and highly accurate photomasks can be stably manufactured. can do. Therefore, the role played by the present invention in increasing the degree of integration of LSIs and VLSIs is enormous.
Claims (1)
アノアクリレートである重合体を含有することを特徴と
するポジ型電子線レジスト。1. A positive electron beam resist characterized by containing a polymer in which part or all of the constituent monomers are cyclohexyl 2-cyanoacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14582988A JPH022564A (en) | 1988-06-15 | 1988-06-15 | Positive type electron beam resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14582988A JPH022564A (en) | 1988-06-15 | 1988-06-15 | Positive type electron beam resist |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH022564A true JPH022564A (en) | 1990-01-08 |
Family
ID=15394082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14582988A Pending JPH022564A (en) | 1988-06-15 | 1988-06-15 | Positive type electron beam resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH022564A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60160872A (en) * | 1984-01-30 | 1985-08-22 | Ajinomoto Co Inc | Drink composition |
| JPH041764A (en) * | 1990-04-19 | 1992-01-07 | Toppan Printing Co Ltd | Production of photomask |
| JPH05249684A (en) * | 1991-12-26 | 1993-09-28 | Toppan Printing Co Ltd | Positive electron beam resist composition |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54133322A (en) * | 1978-04-07 | 1979-10-17 | Cho Lsi Gijutsu Kenkyu Kumiai | Positive type ionizing radiation sensitive resist |
| JPS5653114A (en) * | 1979-10-08 | 1981-05-12 | Kohjin Co Ltd | Preparation of polymeric material for positive resist sensitive to radiation and far ultraviolet rays |
| JPS5654434A (en) * | 1979-10-11 | 1981-05-14 | Kohjin Co Ltd | Radiation and far ultraviolet ray sensitive positive type resist method |
| JPS62247356A (en) * | 1986-02-10 | 1987-10-28 | ロクタイト．（アイルランド）．リミテツド | Manufacture of evaporation photoresist of anionic polymerizable monomer and product thereof |
| JPS63241251A (en) * | 1987-03-27 | 1988-10-06 | 日立金属株式会社 | Panel for clean room |
| JPS63271254A (en) * | 1986-12-29 | 1988-11-09 | Toppan Printing Co Ltd | Radiation sensitive positive type resist having high resolution |
| JPS63271250A (en) * | 1986-12-29 | 1988-11-09 | Toppan Printing Co Ltd | Positive type resist material having dry etching resistance |
| JPS63271252A (en) * | 1986-12-29 | 1988-11-09 | Toppan Printing Co Ltd | Radiation sensitive resist |
| JPS63277128A (en) * | 1987-03-26 | 1988-11-15 | Sumitomo Metal Ind Ltd | Switchover device for route of capsule conveyance |
| JPS6433109A (en) * | 1986-12-29 | 1989-02-03 | Toppan Printing Co Ltd | Production of alpha-cyanoacrylate polymer |
| JPH01154146A (en) * | 1987-12-11 | 1989-06-16 | Toppan Printing Co Ltd | Radiation sensitive resist having high sensitivity |
| JPH01217341A (en) * | 1988-02-25 | 1989-08-30 | Toppan Printing Co Ltd | Pattern forming method of positive type electron beam resist |
| JPH01273039A (en) * | 1988-04-26 | 1989-10-31 | Toppan Printing Co Ltd | Positive type electron beam resist |
-
1988
- 1988-06-15 JP JP14582988A patent/JPH022564A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54133322A (en) * | 1978-04-07 | 1979-10-17 | Cho Lsi Gijutsu Kenkyu Kumiai | Positive type ionizing radiation sensitive resist |
| JPS5653114A (en) * | 1979-10-08 | 1981-05-12 | Kohjin Co Ltd | Preparation of polymeric material for positive resist sensitive to radiation and far ultraviolet rays |
| JPS5654434A (en) * | 1979-10-11 | 1981-05-14 | Kohjin Co Ltd | Radiation and far ultraviolet ray sensitive positive type resist method |
| JPS62247356A (en) * | 1986-02-10 | 1987-10-28 | ロクタイト．（アイルランド）．リミテツド | Manufacture of evaporation photoresist of anionic polymerizable monomer and product thereof |
| JPS63271250A (en) * | 1986-12-29 | 1988-11-09 | Toppan Printing Co Ltd | Positive type resist material having dry etching resistance |
| JPS63271254A (en) * | 1986-12-29 | 1988-11-09 | Toppan Printing Co Ltd | Radiation sensitive positive type resist having high resolution |
| JPS63271252A (en) * | 1986-12-29 | 1988-11-09 | Toppan Printing Co Ltd | Radiation sensitive resist |
| JPS6433109A (en) * | 1986-12-29 | 1989-02-03 | Toppan Printing Co Ltd | Production of alpha-cyanoacrylate polymer |
| JPS63277128A (en) * | 1987-03-26 | 1988-11-15 | Sumitomo Metal Ind Ltd | Switchover device for route of capsule conveyance |
| JPS63241251A (en) * | 1987-03-27 | 1988-10-06 | 日立金属株式会社 | Panel for clean room |
| JPH01154146A (en) * | 1987-12-11 | 1989-06-16 | Toppan Printing Co Ltd | Radiation sensitive resist having high sensitivity |
| JPH01217341A (en) * | 1988-02-25 | 1989-08-30 | Toppan Printing Co Ltd | Pattern forming method of positive type electron beam resist |
| JPH01273039A (en) * | 1988-04-26 | 1989-10-31 | Toppan Printing Co Ltd | Positive type electron beam resist |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60160872A (en) * | 1984-01-30 | 1985-08-22 | Ajinomoto Co Inc | Drink composition |
| JPH0358265B2 (en) * | 1984-01-30 | 1991-09-04 | Ajinomoto Kk | |
| JPH041764A (en) * | 1990-04-19 | 1992-01-07 | Toppan Printing Co Ltd | Production of photomask |
| JPH05249684A (en) * | 1991-12-26 | 1993-09-28 | Toppan Printing Co Ltd | Positive electron beam resist composition |
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