JPH01273039A - Positive type electron beam resist - Google Patents
Positive type electron beam resistInfo
- Publication number
- JPH01273039A JPH01273039A JP10311988A JP10311988A JPH01273039A JP H01273039 A JPH01273039 A JP H01273039A JP 10311988 A JP10311988 A JP 10311988A JP 10311988 A JP10311988 A JP 10311988A JP H01273039 A JPH01273039 A JP H01273039A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- electron beam
- formula
- ammonium salt
- polymer
- 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.)
- Granted
Links
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 11
- -1 cyclohexyl alpha-cyanoacrylate Chemical compound 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical class CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229920001651 Cyanoacrylate Polymers 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 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
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000609 electron-beam lithography Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000010650 Hyssopus officinalis Nutrition 0.000 description 1
- 240000001812 Hyssopus officinalis Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- PJXSVQGVZNZMTJ-UHFFFAOYSA-O butylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCC[NH3+] PJXSVQGVZNZMTJ-UHFFFAOYSA-O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZTYMNUBYYQNBFP-UHFFFAOYSA-N propyl 2-cyanoprop-2-enoate Chemical compound CCCOC(=O)C(=C)C#N ZTYMNUBYYQNBFP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- AMCYFOSVYJWEBU-UHFFFAOYSA-N tetrabutylazanium borate Chemical compound [O-]B([O-])[O-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AMCYFOSVYJWEBU-UHFFFAOYSA-N 0.000 description 1
- QHOKENWFMZXSEU-UHFFFAOYSA-N tetrabutylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC QHOKENWFMZXSEU-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高感度かつ高解像度のポジ型電子線レジストに
関するものであり、フォトマスクの製造およびシリコン
ウェハーへの直接描画による半導体の製造時における選
択的エツチングや選択的拡散のためのレジストの提供を
目的とする。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a high-sensitivity and high-resolution positive electron beam resist, which is used in the production of photomasks and the production of semiconductors by direct writing on silicon wafers. The purpose is to provide resists for selective etching and selective diffusion.
ネガ型レジストは高感度であるが、解像性が低い。これ
に対して、ポジ型レジストは解像度が高いため大規模集
積回路の高集積化に伴い、ネガ型からポジ型に移行しつ
つある。ポジ型電子線レジストの代表例としてポリメタ
クリル酸メチル（ＰＭＭＡ）が知られているが、解像度
は０．１ μｍと非常に高いが、感度が１００ μＣ
／ｃＪと低いために電子線描画装置のスループントが問
題となり、感度を高めるために数多くの研究がなされて
きた。その一つとしてＰＭＭＡのαメチル基をシアノ基
に置換したα−シアリアクリル酸エステル重合体がある
が、感度が４μＣ／ｃｆｌであり、ＰＭＭＡより２５倍
以上高感度化されているが、電子線描画装置のスループ
ント上、２μＣ／ｃＪの感度が必要であり、まだ感度が
十分とは言えない。Negative resists have high sensitivity but low resolution. On the other hand, positive resists have high resolution, and as large-scale integrated circuits become more highly integrated, there is a shift from negative resists to positive resists. Polymethyl methacrylate (PMMA) is known as a typical example of a positive electron beam resist, but it has a very high resolution of 0.1 μm, but a sensitivity of 100 μC.
/cJ, the throughput of electron beam lithography equipment becomes a problem, and many studies have been conducted to increase the sensitivity. One of these is an α-sialyacrylic acid ester polymer in which the α-methyl group of PMMA is replaced with a cyano group, but it has a sensitivity of 4 μC/cfl, which is more than 25 times more sensitive than PMMA. Due to the throughput of the drawing device, a sensitivity of 2 μC/cJ is required, and the sensitivity cannot be said to be sufficient yet.
本発明は１６メガビツ）ＤＲＡＭ以降の大規模集積回路
用としての高感度かつ高解像度を同時に有するポジ型レ
ジストを提供することを目的としている。An object of the present invention is to provide a positive resist having both high sensitivity and high resolution for use in large-scale integrated circuits such as 16 megabit (DRAM) and later.
本発明は、一般式（１）：
（式中Ｒは炭素数１〜６のアルキル基もしくはシクロヘ
キシル基を示す）で表わされるα−シアノアクリル酸エ
ステル重合体を主成分とするレジストに一般式（２）：
（式中、Ｒ＋、 Ｒ’ｚ、 Ｒ：１． Ｒ４，は炭素数
１〜２ｏのアルキル基であり、Ｘ−はＨＳ Ｏ４−、Ｈ
４Ｆ ０４−、ＢＯ２−、ＢＦ、−、Ｎｏ３−を示す）
で表わされる第４級アンモニウム塩を添加することによ
り高感度と高解像度を同時に満たすポジ型電子線レジス
トを提供する。The present invention provides a resist with the general formula (1): (wherein R represents an alkyl group having 1 to 6 carbon atoms or a cyclohexyl group) as a main component. 2): (In the formula, R+, R'z, R: 1. R4, is an alkyl group having 1 to 2 o carbon atoms, and X- is HSO4-, H
4F 04-, BO2-, BF,-, No3-)
A positive electron beam resist that satisfies high sensitivity and high resolution at the same time is provided by adding a quaternary ammonium salt represented by:
本発明で用いるα−シアノアクリル酸エステル重合体は
通常の合成法で得られたα−シアンアクリル酸エステル
モノマーをアニオン重合またはラジカル重合することに
よって得られ、分子量は１万〜３００万であるが、塗布
性および感度から１０万〜１００万程度のものが好まし
い。なお、α−シアノアクリル酸エステルモノマーは、
一般式（３）で表わされ、具体的にはα−シアノアクリ
ル酸メチル、α−シアノアクリル酸エチル、α−シアノ
アクリル酸プロピル、α−シアノアクリル酸ブチル、α
−シアノアクリル酸シクロヘキシル等である。また、添
加する第４級アンモニウム塩は前記（２）弐におイア
Ｒ＋、 Ｒ２，Ｒ３，Ｒａ は炭素数１〜２゜のアルキ
ル基でメチル基、エチル基、ブチル基、オクチル基、デ
シル基、ドデシル基等であり、Ｘ−はＨ３Ｏ，−、Ｈ２
ＰＯ４−、ＢＯ２−、ＢＦ４− 、 Ｎ Ｏ：ｌ−等
であり、具体的には硫酸水素テトラブチルアンモニウム
、リン酸テトラブチルアンモニアム、ホウ酸テトラブチ
ルアンモニウム、ホウフッ化テトラブチルアンモニウム
、硝酸ブチルテトラブチルアンモニウム等である。The α-cyanoacrylic acid ester polymer used in the present invention is obtained by anionic or radical polymerization of α-cyanoacrylic acid ester monomer obtained by a conventional synthesis method, and has a molecular weight of 10,000 to 3,000,000. , from about 100,000 to 1,000,000 is preferable from the viewpoint of coating properties and sensitivity. In addition, the α-cyanoacrylic acid ester monomer is
It is represented by the general formula (3), and specifically, α-methyl cyanoacrylate, α-ethyl cyanoacrylate, α-propyl cyanoacrylate, α-butyl cyanoacrylate, α
-cyclohexyl cyanoacrylate, etc. In addition, the quaternary ammonium salt to be added is
R+, R2, R3, Ra are alkyl groups having 1 to 2 degrees of carbon atoms, such as methyl group, ethyl group, butyl group, octyl group, decyl group, dodecyl group, and X- is H3O, -, H2
PO4-, BO2-, BF4-, NO:l-, etc., and specifically, tetrabutylammonium hydrogen sulfate, tetrabutylammonium phosphate, tetrabutylammonium borate, tetrabutylammonium borofluoride, butyltetra nitrate. Butylammonium, etc.
なお、第４級アンモニウム塩の添加量は前記α−シアノ
アクリル酸エステル重合体に対して１〜３０重量％で、
感度および解像度を考慮すると５〜１５重景％が好まし
い。The amount of the quaternary ammonium salt added is 1 to 30% by weight based on the α-cyanoacrylic acid ester polymer,
In consideration of sensitivity and resolution, 5 to 15% double focus is preferable.
図面の第１図は、分子量５１万のα−シアノアクリル酸
シクロキシル重合体に硝酸テトラブチルアンモニウム塩
を添加した本発明のポジ型電子線レジストと、無添加の
場合の比較を示す残膜感度曲線である。電子ビーム描画
の照射量（μＣ／ｃｆｆｌ）に対する規格化膜厚により
示されている。なお、照射電子ヒームの加速電圧は２０
ＫＶであり、照射後の現像条件は、
［現像液組成・・・メチルイソブチルケトン° イソプ
である。Figure 1 of the drawings shows a residual film sensitivity curve showing a comparison between the positive electron beam resist of the present invention in which tetrabutylammonium nitrate is added to α-cycloxyl cyanoacrylate polymer with a molecular weight of 510,000, and the case without the addition. It is. It is shown by the normalized film thickness with respect to the irradiation dose (μC/cffl) of electron beam lithography. The acceleration voltage of the irradiation electron beam is 20
KV, and the development conditions after irradiation were as follows: [Developer composition: methyl isobutyl ketone] isop.
また、第２図は、α−シアノアクリル酸シクロキシル重
合体に硝酸テトラブチルアンモニウム塩を添加した本発
明のポジ型電子線レジストと、無添加の場合の比較を示
す。現像液の組成がメチルイソブチルケトン・イソプメ
ロピルアルコールー２：１である以外は、上述と同し現
像条件である。Moreover, FIG. 2 shows a comparison between the positive electron beam resist of the present invention in which tetrabutylammonium nitrate salt is added to the cycloxyl cyanoacrylate polymer and the case in which no additive is added. The developing conditions were the same as above, except that the composition of the developer was methyl isobutyl ketone/isopropyl alcohol-2:1.
これを見てもわかるように、本発明のポジ型電子線レジ
ストは、感度の向上が顕著に見られ、解像度も改善され
ている。As can be seen from this figure, the positive electron beam resist of the present invention shows a remarkable improvement in sensitivity and resolution.
本発明によれば、第４級アンモニウム塩を無添加のα−
シアンアクリル酸シクロキシル重合体に比べて、添加し
たものは、３倍以上の感度が得られ、且つ線幅０．５
μｍ以下の高解像度が得られ、半導体の製造において高
生産性とコスト低減に大きな効果をもたらすことができ
る。According to the present invention, the quaternary ammonium salt is added to α-
Compared to cycloxyl cyanacrylate polymer, the added one provides more than three times the sensitivity and a line width of 0.5
High resolution of micrometers or less can be obtained, and it can have a significant effect on high productivity and cost reduction in semiconductor manufacturing.
以下、本発明の実施例を示すが、この本発明はこれらの
実施例に限定されるものではないことは言うまでもない
。Examples of the present invention will be shown below, but it goes without saying that the present invention is not limited to these Examples.
〔実施例１〕
分子量５１０，０００のα−シアノアクリル酸シクロキ
シル重合体の３重量％のシクロヘキサノン溶液を作り、
さらに硝酸ｎ−ブチルアンモニウム塩を重合体に対して
１０重量％加え、１０００人の厚さでクロム蒸着された
ガラスに回転塗布法により１３００ｒｐｍで４７００人
の厚さの被膜を形成し、１２０度で３０分間熱処理後、
照射量１μ／ Ｃａ、加速電圧２０ＫＶで電子線照射し
た。電子線照射後、メチルイソブチルケトンとイソプロ
ピルアルコールの５：４の混合溶媒に２０°Ｃにおいて
５分間浸漬し、その後イソプロピルアルコール中にてリ
ンスして乾燥することによってレジストパターンが得ら
れた。さらに、１２０°Ｃ１３０分間加熱処理し、硝酸
第２セルウムアンモニウムと過塩素酸のクロムエツチン
グ液に３０秒間、浸漬すると１０００人のクロム層がエ
ツチングされ、レジスト被膜はアセトンで容易に除かれ
、ガラス基板上に０５８ｍ線幅のクロムパターンが得ら
れた。[Example 1] A 3% by weight cyclohexanone solution of α-cyanoacrylic acid cycloxyl polymer having a molecular weight of 510,000 was prepared,
Furthermore, 10% by weight of n-butylammonium nitrate salt was added to the polymer, and a coating with a thickness of 4,700 nm was formed at 1,300 rpm using a spin coating method on chromium-deposited glass to a thickness of 1,000 nm. After heat treatment for 30 minutes,
Electron beam irradiation was performed at an irradiation dose of 1 μ/Ca and an acceleration voltage of 20 KV. After electron beam irradiation, a resist pattern was obtained by immersing it in a 5:4 mixed solvent of methyl isobutyl ketone and isopropyl alcohol at 20°C for 5 minutes, and then rinsing in isopropyl alcohol and drying. Further, heat treatment at 120°C for 130 minutes and immersion in a chromium etching solution of ceric ammonium nitrate and perchloric acid for 30 seconds etched the 1,000 chromium layer, and the resist film was easily removed with acetone. A chrome pattern with a line width of 0.058 m was obtained on the substrate.
〈比較例１〉
分子量５１０．０００のα−シアノアクリル酸シクロキ
シル重合体の３重量％のシクロヘキサノン溶液を作り、
第４級アンモニウム塩は添加せず、実施例１と同様に処
理したが、電子線照射量ｌμＣ／ｃＪでは、電子線照射
部のレジストはすべて溶解せず膜残りが生した。なお、
電子線照射部をすべて溶解させるには４μＣ／ａａの電
子線照射量を必要とした。<Comparative Example 1> A 3% by weight cyclohexanone solution of α-cyanoacrylic acid cycloxyl polymer having a molecular weight of 510.000 was prepared,
The process was carried out in the same manner as in Example 1 without adding a quaternary ammonium salt, but at an electron beam irradiation dose of 1 μC/cJ, the resist in the electron beam irradiated area was not completely dissolved and a film remained. In addition,
An electron beam irradiation amount of 4 μC/aa was required to dissolve all the electron beam irradiated parts.
〈実施例２〉
実施例１と同様に硫酸水素テトラ−ｎ−ブチルアンモニ
ウムをα−シアノアクリル酸シクロキシル重合体に対し
て１０重量％添加した溶液を作り、被膜形成後２μＣ／
ｃｆｆｌの電子線を照射し、メチルイソアミルケトンと
イソプロピルアルコールの２：１の現像液において、５
分間浸漬し、イソプロピルアルコールでリンスし乾燥し
た。得られたレジストパターンを電子顕微鏡で観察した
ところ、非常にシャープなパターンが観認、された。<Example 2> In the same manner as in Example 1, a solution was prepared in which 10% by weight of tetra-n-butylammonium hydrogen sulfate was added to the cycloxyl α-cyanoacrylate polymer.
cffl electron beam, and in a developer solution of 2:1 methyl isoamyl ketone and isopropyl alcohol.
It was soaked for a minute, rinsed with isopropyl alcohol, and dried. When the obtained resist pattern was observed under an electron microscope, a very sharp pattern was observed.
第１図はα−シアノアクリル酸シクロヘキシルに硝酸テ
トラブチルアンモニウム塩を添加した場合と無添加の場
合の残膜感度曲線を示すグラフ図であり、第２図は硫酸
水素テトラブチルアンモニウム塩を添加した場合と無添
加の場合の残膜感度曲線の比較を示すグラフ図である。
特 許 出 願 人
凸版印刷株式会社
代表者 鈴木和夫Figure 1 is a graph showing residual film sensitivity curves when tetrabutylammonium nitrate is added to cyclohexyl α-cyanoacrylate and when it is not added, and Figure 2 is a graph showing residual film sensitivity curves when tetrabutylammonium hydrogen sulfate is added. FIG. 3 is a graph showing a comparison of residual film sensitivity curves in the case of the case where the additive was added and the case where no additive was added. Patent application: Kazuo Suzuki, Representative of Toppan Printing Co., Ltd.
Claims (1)
ヘキシル基を示す）で表わされるα−シアノアクリル酸
エステル重合体および共重合体を主成分とするレジスト
に、一般式（２）： ▲数式、化学式、表等があります▼・・・・・（２） （式中Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４、は炭素数１〜
２０のアルキル基であり、Ｘ＾−はＨＳＯ＿４＾−、Ｈ
＿２ＰＯ＿４＾−、ＢＯ＿２＾−、ＢＦ＿４＾−、ＮＯ
＿３＾−を示す）で表わされる第４級アンモニウム塩を
添加することより成るポジ型電子線レジスト。[Claims] 1) General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) (In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a cyclohexyl group) General formula (2): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) (in the formula R_1, R_2, R_3, R_4 have 1 or more carbon atoms
20 alkyl group, X^- is HSO_4^-, H
_2PO_4^-, BO_2^-, BF_4^-, NO
A positive electron beam resist comprising the addition of a quaternary ammonium salt represented by _3^-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63103119A JP2550655B2 (en) | 1988-04-26 | 1988-04-26 | Positive electron beam resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63103119A JP2550655B2 (en) | 1988-04-26 | 1988-04-26 | Positive electron beam resist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01273039A true JPH01273039A (en) | 1989-10-31 |
| JP2550655B2 JP2550655B2 (en) | 1996-11-06 |
Family
ID=14345697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63103119A Expired - Fee Related JP2550655B2 (en) | 1988-04-26 | 1988-04-26 | Positive electron beam resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2550655B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH022564A (en) * | 1988-06-15 | 1990-01-08 | Toagosei Chem Ind Co Ltd | Positive type electron beam resist |
| JPH02264955A (en) * | 1989-04-06 | 1990-10-29 | Toppan Printing Co Ltd | Positive type resist using electron beams |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5226217A (en) * | 1975-08-22 | 1977-02-26 | Toyobo Co Ltd | Photosensitive composition having high sensitivity |
| JPS5453966A (en) * | 1977-10-07 | 1979-04-27 | Fuji Yakuhin Kogyo Kk | Development method of electron beam resist |
| JPS58108213A (en) * | 1981-12-22 | 1983-06-28 | Toagosei Chem Ind Co Ltd | Preparation of polymer of 2-cyanoacrylic acid ester |
| JPS58202442A (en) * | 1982-04-02 | 1983-11-25 | ノ−ス・アメリカン・フイリツプス・コ−ポレ−シヨン | Positive type photoresist composition |
| JPS61264339A (en) * | 1985-05-20 | 1986-11-22 | Toray Ind Inc | Photosensitive resin composition |
| JPS62160441A (en) * | 1986-01-09 | 1987-07-16 | Hitachi Chem Co Ltd | Photosensitive composition for photoresist |
| JPS62240956A (en) * | 1985-12-25 | 1987-10-21 | Tosoh Corp | Positive type resist pattern forming 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 |
-
1988
- 1988-04-26 JP JP63103119A patent/JP2550655B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5226217A (en) * | 1975-08-22 | 1977-02-26 | Toyobo Co Ltd | Photosensitive composition having high sensitivity |
| JPS5453966A (en) * | 1977-10-07 | 1979-04-27 | Fuji Yakuhin Kogyo Kk | Development method of electron beam resist |
| JPS58108213A (en) * | 1981-12-22 | 1983-06-28 | Toagosei Chem Ind Co Ltd | Preparation of polymer of 2-cyanoacrylic acid ester |
| JPS58202442A (en) * | 1982-04-02 | 1983-11-25 | ノ−ス・アメリカン・フイリツプス・コ−ポレ−シヨン | Positive type photoresist composition |
| JPS61264339A (en) * | 1985-05-20 | 1986-11-22 | Toray Ind Inc | Photosensitive resin composition |
| JPS62240956A (en) * | 1985-12-25 | 1987-10-21 | Tosoh Corp | Positive type resist pattern forming method |
| JPS62160441A (en) * | 1986-01-09 | 1987-07-16 | Hitachi Chem Co Ltd | Photosensitive composition for photoresist |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH022564A (en) * | 1988-06-15 | 1990-01-08 | Toagosei Chem Ind Co Ltd | Positive type electron beam resist |
| JPH02264955A (en) * | 1989-04-06 | 1990-10-29 | Toppan Printing Co Ltd | Positive type resist using electron beams |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2550655B2 (en) | 1996-11-06 |
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