JPH0150894B2 - - Google Patents
Info
- Publication number
- JPH0150894B2 JPH0150894B2 JP22761182A JP22761182A JPH0150894B2 JP H0150894 B2 JPH0150894 B2 JP H0150894B2 JP 22761182 A JP22761182 A JP 22761182A JP 22761182 A JP22761182 A JP 22761182A JP H0150894 B2 JPH0150894 B2 JP H0150894B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- phenyl
- benzyl
- methyl
- acetoxy
- 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.)
- Expired
Links
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 9
- 125000006267 biphenyl group Chemical group 0.000 claims description 9
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 9
- 229920002120 photoresistant polymer Polymers 0.000 claims description 9
- 150000003377 silicon compounds Chemical class 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 230000005865 ionizing radiation Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 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 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 7
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009489 vacuum treatment Methods 0.000 description 3
- WQMWHMMJVJNCAL-UHFFFAOYSA-N 2,4-dimethylpenta-1,4-dien-3-one Chemical compound CC(=C)C(=O)C(C)=C WQMWHMMJVJNCAL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- HOMYFVKFSFMSFF-UHFFFAOYSA-N ethenyl-[ethenyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)O[Si](C=C)(C=1C=CC=CC=1)C1=CC=CC=C1 HOMYFVKFSFMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JNZRJYXUMDPPRK-UHFFFAOYSA-N methyl-[methyl(diphenyl)silyl]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si]([Si](C)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNZRJYXUMDPPRK-UHFFFAOYSA-N 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VCYDUTCMKSROID-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VCYDUTCMKSROID-UHFFFAOYSA-N 0.000 description 1
- -1 3-ethoxy-1,1,3,3-tetraphenyldisiloxane Chemical compound 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- UOBPHQJGWSVXFS-UHFFFAOYSA-N [O].[F] Chemical compound [O].[F] UOBPHQJGWSVXFS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- YBNBOGKRCOCJHH-UHFFFAOYSA-N hydroxy-[4-[hydroxy(dimethyl)silyl]phenyl]-dimethylsilane Chemical group C[Si](C)(O)C1=CC=C([Si](C)(C)O)C=C1 YBNBOGKRCOCJHH-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical compound C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 description 1
- RFGGTTPASBFBTB-UHFFFAOYSA-N methyl-[methyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C)O[Si](C)(C=1C=CC=CC=1)C1=CC=CC=C1 RFGGTTPASBFBTB-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 229920005593 poly(benzyl methacrylate) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 description 1
- 229920000182 polyphenyl methacrylate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- BSFLZHNGSJZLQC-UHFFFAOYSA-N trimethyl(triphenylsilyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)([Si](C)(C)C)C1=CC=CC=C1 BSFLZHNGSJZLQC-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
【発明の詳細な説明】
(1) 発明の技術分野
本発明はネガ型レジスト組成物およびレジスト
パターンの形成方法に関する。更に詳しく述べる
ならば、本発明は電子線、Ｘ線、イオンビームな
どの如き電離放射線により露光後、酸素プラズ
マ、アルゴンガスプラズマ、酸素―アルゴン混合
ガスプラズマ、酸素―弗素系ガス混合ガスプラズ
マなどを用いて現像することのできるネガ型レジ
スト組成物および該組成物を用いるレジストパタ
ーン形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION (1) Technical Field of the Invention The present invention relates to a negative resist composition and a method for forming a resist pattern. More specifically, the present invention is capable of applying oxygen plasma, argon gas plasma, oxygen-argon mixed gas plasma, oxygen-fluorine gas mixed gas plasma, etc. after exposure to ionizing radiation such as electron beams, X-rays, and ion beams. The present invention relates to a negative resist composition that can be developed using the resist composition, and a resist pattern forming method using the composition.
(2) 技術の背景および従来技術と問題点
従来、半導体集積回路等の電子デバイスの製造
におけるレジストパターンの形成には、現像液を
用いて現像するレジストが使用されている。この
ようなレジストとして、例えば、電子線ポジ型レ
ジストのポリメチルメタクリレートやネガ型のポ
リグリシジルメタクリレートなどがある。これら
の従来のレジストは、現像液を使用して現像する
ために、レジストが現像時に膨潤や収縮を起す欠
点があり、サブミクロンのパターンを形成するこ
とは困難であつた。(2) Background of the Technology, Prior Art, and Problems Conventionally, resists developed using a developer have been used to form resist patterns in the manufacture of electronic devices such as semiconductor integrated circuits. Examples of such resists include polymethyl methacrylate, which is a positive electron beam resist, and polyglycidyl methacrylate, which is a negative resist. Since these conventional resists are developed using a developer, they have the disadvantage that the resist swells and contracts during development, making it difficult to form submicron patterns.
(3) 発明の目的および構成
本発明の目的は上記の欠点を解消し、ドライ現
像によるレジストパターンの形成を可能にし、微
細レジストパターンの形成を容易にすることにあ
る。(3) Object and Structure of the Invention The object of the present invention is to eliminate the above-mentioned drawbacks, to enable the formation of a resist pattern by dry development, and to facilitate the formation of a fine resist pattern.
本発明によればネガ型レジスト組成物が提供さ
れるのであつて、この組成物は下記一般式，
又はで表わされる単量体の重合体又はこれらの
単量体の共重合体に、下記一般式，，，
，，又はで表わされるシリコン化合物を
１〜50重量％含有することを特徴とする。 According to the present invention, a negative resist composition is provided, and this composition has the following general formula:
A polymer of monomers or a copolymer of these monomers represented by the following general formula:
It is characterized by containing 1 to 50% by weight of a silicon compound represented by , , or.
上記式〜中、R1は炭素数１〜６のアルキ
ル基、ベンジル基、フエニル基又はシクロヘキシ
ル基を表わし、R2はメチル基又はフエニル基を
表わし、はメチル基、フエニル基、ビフエニル
基、フエニルアミノ基、フエノキシ基、ベンジル
基、シアノ基、ビニル基又はアセトキシ基を表わ
し、Ｙは水素原子、ヒドロキシ基、アジド基、ビ
ニル基、メトキシ基、エトキシ基、ブトキシ基、
フエノキシ基、ハロゲン原子、ベンジル基、フエ
ニル基、メチル基、ｔ―ブチル基、ビフエニル基
又はアセトキシ基を表わし、Ｚはフエニル基、ヒ
ドロキシ基、ビニル基、メトキシ基、エトキシ
基、ブトキシ基、ベンジル基、メチル基、ｔ―ブ
チル基、フエノキシ基、ハロゲン原子、ビフエニ
ル基又はアセトキシ基を表わす。 In the above formulas, R 1 represents an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or a cyclohexyl group, R 2 represents a methyl group or a phenyl group, and represents a methyl group, a phenyl group, a biphenyl group, or a phenylamino group. group, phenoxy group, benzyl group, cyano group, vinyl group or acetoxy group, and Y represents a hydrogen atom, hydroxy group, azido group, vinyl group, methoxy group, ethoxy group, butoxy group,
Represents a phenoxy group, a halogen atom, a benzyl group, a phenyl group, a methyl group, a t-butyl group, a biphenyl group, or an acetoxy group, and Z is a phenyl group, a hydroxy group, a vinyl group, a methoxy group, an ethoxy group, a butoxy group, a benzyl group , methyl group, t-butyl group, phenoxy group, halogen atom, biphenyl group or acetoxy group.
本発明によればまた基板上にネガレジストパタ
ーンを形成する方法が提供されるのであつて、こ
の方法は前記基板上に上記のネガ型レジスト組成
物を塗布し、このレジスト層を電離放射線により
露光し、次いでこのレジスト層をリリーフ処理に
付した後プラズマにより現像することを特徴とす
る。 The present invention also provides a method for forming a negative resist pattern on a substrate, which method comprises applying the above negative resist composition onto the substrate, and exposing the resist layer to ionizing radiation. The resist layer is then subjected to a relief treatment and then developed using plasma.
上記の如き構成を有する本発明は即ち上記ポリ
マーとシリコン化合物が電離放射線により反応
し、もとのシリコン化合物より蒸気圧の低い化合
物に変化すること、及びプラズマ中において露光
部分のシリコン化合物がより耐プラズマ性の高い
物質に変化することに基づくものである。かかる
本発明においてより良好な選択エツチング比を達
成するためには露光後にレジスト層をリリーフ処
理することが必須となる。 The present invention having the above structure is characterized in that the polymer and the silicon compound react with ionizing radiation and change into a compound with a lower vapor pressure than the original silicon compound, and that the silicon compound in the exposed part becomes more resistant in plasma. This is based on the fact that it changes into a substance with high plasma properties. In order to achieve a better selective etching ratio in the present invention, it is essential to perform a relief treatment on the resist layer after exposure.
一般式で示される単量体の重合体の例として
は、ポリメチルメタクリレート、ポリエチルメタ
クリレート、ポリｎ―プロピルメタクリレート、
ポリｉ―プロピルメタクリレート、ポリｎ―ブチ
ルメタクリレート、ポリsec―ブチルメタクリレ
ート、ポリｔ―ブチルメタクリレート、ポリｎ―
アミルメタクリレート、ポリｎ―ヘキシルメタク
リレート、ポリベンジルメタクリレート、ポリフ
エニルメタクリレート、ポリシクロヘキシルメタ
クリレートなどがある。また、一般式で示され
る単量体の重合体の例としては、ポリメチルイソ
プロペニルケトン、ポリフエニルイソプロペニル
ケトンなどがある。また、一般式で示される単
量体の重合体の例としてはポリα―メチルスチレ
ンがある。また、本発明においては、前記単量体
、単量体および単量体との共重合体を有利
に用いることもできる。 Examples of monomer polymers represented by the general formula include polymethyl methacrylate, polyethyl methacrylate, poly n-propyl methacrylate,
Poly i-propyl methacrylate, poly n-butyl methacrylate, poly sec-butyl methacrylate, poly t-butyl methacrylate, poly n-
Examples include amyl methacrylate, poly n-hexyl methacrylate, polybenzyl methacrylate, polyphenyl methacrylate, and polycyclohexyl methacrylate. Furthermore, examples of polymers of monomers represented by the general formula include polymethyl isopropenyl ketone and polyphenyl isopropenyl ketone. An example of a polymer of monomers represented by the general formula is polyα-methylstyrene. Further, in the present invention, the above-mentioned monomers, monomers, and copolymers with the monomers can also be advantageously used.
一般式で示されるシリコン化合物の例として
例えば１，２―ジメチル―１，１，２，２―テト
ラフエニルジシランがあり、一般式で示される
化合物の例として例えば、１，１，１―トリメチ
ル―２，２，２―トリフエニルジシランがあり、
一般式で示される化合物の例として、例えば
１，３―ジメチル―１，１，３，３―テトラフエ
ニルジシロキサン、１，３―ジビニル―１，１，
３，３―テトラフエニルジシロキサンおよび１，
３―エトキシ―１，１，３，３―テトラフエニル
ジシロキサンがあり、一般式で示される化合物
の例として、例えば１，１，５，５―テトラフエ
ニル―１，１，３，３―テトラメチルトリシロキ
サンがあり、一般式で示される化合物の例とし
て、例えばヘキサフエニルシクロトリシロキサン
があり、一般式で示される化合物の例として、
例えば１，４―ビス（ヒドロキシジメチルシリ
ル）ベンゼンがある。 Examples of silicon compounds represented by the general formula include 1,2-dimethyl-1,1,2,2-tetraphenyldisilane, and examples of compounds represented by the general formula include 1,1,1-trimethyl -2,2,2-triphenyldisilane,
Examples of compounds represented by the general formula include 1,3-dimethyl-1,1,3,3-tetraphenyldisiloxane, 1,3-divinyl-1,1,
3,3-tetraphenyldisiloxane and 1,
Examples of compounds represented by the general formula include 3-ethoxy-1,1,3,3-tetraphenyldisiloxane, such as 1,1,5,5-tetraphenyl-1,1,3,3-tetra An example of a compound represented by the general formula is hexaphenylcyclotrisiloxane, and an example of a compound represented by the general formula is methyltrisiloxane.
For example, there is 1,4-bis(hydroxydimethylsilyl)benzene.
本発明に係るパターン形成方法は通常の方法に
従い、次の如き操作により実施することができ
る。即ち、第１図のイに示す如く、先ず基板１上
にレジスト層２を形成する。例えば、スピンコー
ト法によりレジス組成液を塗布し、60〜80℃の温
度で10〜30分間プリベークする。次に、これをロ
に示す如く、電子線等に露光する。これにより、
レジスト層２の露光部分３に含まれるシリコン化
合物は蒸気圧のより低い化合物に変化する。次
に、第１図のハの如く、これをリリーフ処理に付
する。このリリーフ処理は加熱処理、真空処理又
は真空加熱処理のいずれであつてもよい。これに
より、未露光部分のシリコン化合物の一部又はも
のほとんどが除去される。次いで、レジスト層２
をドライ現像に付する。即ち、レジスト層２を酸
素プラズマ等によりプラズマ処理することにより
未露光部分は除去され、ニに示す如く露光部分３
が所望のレジストパターンとして残される。 The pattern forming method according to the present invention can be carried out according to a conventional method by the following operations. That is, as shown in FIG. 1A, first, a resist layer 2 is formed on a substrate 1. For example, a resist composition liquid is applied by a spin coating method and prebaked at a temperature of 60 to 80°C for 10 to 30 minutes. Next, as shown in (B), this is exposed to an electron beam or the like. This results in
The silicon compound contained in the exposed portion 3 of the resist layer 2 changes to a compound with a lower vapor pressure. Next, as shown in FIG. 1C, this is subjected to relief treatment. This relief treatment may be heat treatment, vacuum treatment, or vacuum heat treatment. This removes some or most of the silicon compound in the unexposed areas. Next, resist layer 2
is subjected to dry development. That is, by plasma-treating the resist layer 2 with oxygen plasma or the like, the unexposed portion is removed, and the exposed portion 3 is removed as shown in D.
is left as a desired resist pattern.
本発明によればプラズマに対して選択エツチン
グ比及び残膜率が大きく、しかもドライ現像可能
なネガ型レジストが得られる。 According to the present invention, it is possible to obtain a negative resist that has a high selective etching ratio and a high residual film rate with respect to plasma, and can be dry-developable.
以下、実施例および比較例により本発明を更に
詳しく説明する。これらの実施例で用いたポリマ
ーの分子量は８〜45×104であり、分散度
Mw／は1.4〜3.2の範囲であつた。感度は現像
後の膜厚が初期膜厚の50％となるときの露光量で
示し、残膜率は現像後の膜厚が一定になるときの
正規化膜厚で示す。 Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The molecular weight of the polymers used in these examples was 8 to 45 x 104 , and the degree of dispersion was
Mw/ ranged from 1.4 to 3.2. The sensitivity is expressed as the exposure amount when the film thickness after development becomes 50% of the initial film thickness, and the residual film rate is expressed as the normalized film thickness when the film thickness after development becomes constant.
(4) 発明の実施例
実施例 １
ポリイソブチルメタクリレート（Pi―BMA）
に１，４―ビス（ヒドロキシジメチルシリル）ベ
ンを20重量％の量で加え、シクロヘキサノンに溶
解した。これをシリコンウエーハ上にスピナーに
より塗布し、60℃で10分間熱処理した。レジスト
層の膜厚は0.73μmであつた。次に加速電圧20kV
の電子線で露光リリーフ処理として１×
10-6Torrで３時間の減圧処理を行なつた。次に
これを、平行平板型リアクテイブイオンエツチン
グ装置に入れ、６×10-5Torrに減圧後、酸素を
導入し0.4Torr下に、印加電圧0.3W／cm2、印加高
周波数13.56MHzの条件で現像した。７分間の現
像時間後未露光部の膜厚が０となつた。このとき
の残存膜厚を測定し、感度および残膜率を求め
た。感度は５×10-5C／cm2で残膜率は96％であつ
た。(4) Examples of the invention Example 1 Polyisobutyl methacrylate (Pi-BMA)
1,4-bis(hydroxydimethylsilyl)ben was added in an amount of 20% by weight and dissolved in cyclohexanone. This was applied onto a silicon wafer using a spinner and heat treated at 60°C for 10 minutes. The thickness of the resist layer was 0.73 μm. Then acceleration voltage 20kV
1x as exposure relief treatment with electron beam
Decompression treatment was carried out at 10 -6 Torr for 3 hours. Next, this was placed in a parallel plate type reactive ion etching device, and after reducing the pressure to 6 × 10 -5 Torr, oxygen was introduced under the conditions of 0.4 Torr, applied voltage of 0.3 W/cm 2 , and applied high frequency of 13.56 MHz. It was developed with After a development time of 7 minutes, the film thickness in the unexposed area became 0. The remaining film thickness at this time was measured, and the sensitivity and remaining film rate were determined. The sensitivity was 5×10 −5 C/cm 2 and the residual film rate was 96%.
実施例 ２
ポリイソプロピルメタクリレートを用い実施例
１と同様に試料を作り実施例１と同様にドライ現
像を行なつた。ただし、レジストの膜厚は0.6μm
とした。現像時間は８分間であつた。この時の感
度は７×10-5／cm2残膜率は92％であつた。Example 2 A sample was prepared in the same manner as in Example 1 using polyisopropyl methacrylate, and dry development was performed in the same manner as in Example 1. However, the resist film thickness is 0.6μm
And so. The development time was 8 minutes. The sensitivity at this time was 7×10 -5 /cm 2 and the remaining film rate was 92%.
実施例 ３
ポリイソブチルメタクリレート（PiBMA）に
１，３―ジビニル―１，１，３，３―テトラフエ
ニルジシロキサンを20％の重量比で加え、実施例
１と同様に試料を作つた。膜厚は1.1μmであつ
た。電子線の露光後１×10-5Torrで３時間の減
圧処理を行なつた後実施例１と同様に現像した。
現像時間は９分30秒であつた。この時の感度は
6.8×10-5C／cm2で残膜率は90％であつた。Example 3 A sample was prepared in the same manner as in Example 1 by adding 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane to polyisobutyl methacrylate (PiBMA) at a weight ratio of 20%. The film thickness was 1.1 μm. After exposure to an electron beam, the film was subjected to a vacuum treatment at 1×10 −5 Torr for 3 hours, and then developed in the same manner as in Example 1.
The development time was 9 minutes and 30 seconds. The sensitivity at this time is
The residual film rate was 90% at 6.8×10 -5 C/cm 2 .
実施例 ４
ポリイソブチルメタクリレート（PiBMA）に
１，２―ジメチル―１，１，２，２―テトラフエ
ニルジシランを20％の重量比で加え実施例１と同
様にして試料を作つた。ただし膜厚は0.9μmであ
つた。電子線の露光後１×10-5Torrで２時間の
減圧処理を行なつた後実施例１と同様に現像し
た。現像時間は11分20秒であつた。この時の感度
は８×10-5C／cm2であり、残膜率は87％であつ
た。Example 4 A sample was prepared in the same manner as in Example 1 by adding 1,2-dimethyl-1,1,2,2-tetraphenyldisilane to polyisobutyl methacrylate (PiBMA) at a weight ratio of 20%. However, the film thickness was 0.9 μm. After exposure to an electron beam, the film was subjected to a vacuum treatment at 1×10 −5 Torr for 2 hours, and then developed in the same manner as in Example 1. The development time was 11 minutes and 20 seconds. The sensitivity at this time was 8×10 -5 C/cm 2 and the residual film rate was 87%.
比較例 １
ポリメチルメタクリレート（PMMA）にトリ
フエニルシランを23.1重量％の量で加え、シクロ
ヘキサノンに溶解した。重合体の濃度は約11重量
％であつた。これをシリコンウエーハ上にスピナ
ーにより2500〜3500r.p.mの回転速度で塗布し、
60〜80℃で10〜30分間熱処理した。得られたレジ
スト層の膜厚は１〜1.4μmであつた。次に、加速
電圧20kVの電子線で露光後（全露光時間25分）、
平行平板型リアクテイブイオンエツチング装置に
より、６×10-5Torrの減圧後導入した酸素圧
0.4Torr下に、印加電力0.22〜0.33W／cm2、印加
高周波数13.56MHzの条件で現像した。21分30秒
の現像時間後未露光部膜厚が０となつた。このと
きの残存膜厚を測定し、感度及び残膜率を求め
た。感度は5.6×10-4C／cm2であり、残膜率は82％
であつた。Comparative Example 1 Triphenylsilane was added to polymethyl methacrylate (PMMA) in an amount of 23.1% by weight and dissolved in cyclohexanone. The concentration of polymer was approximately 11% by weight. This is applied onto a silicon wafer using a spinner at a rotation speed of 2500 to 3500 rpm.
Heat treated at 60-80°C for 10-30 minutes. The thickness of the obtained resist layer was 1 to 1.4 μm. Next, after exposure to an electron beam with an accelerating voltage of 20 kV (total exposure time 25 minutes),
Oxygen pressure introduced after reducing the pressure to 6×10 -5 Torr using a parallel plate type reactive ion etching device
Development was carried out under the conditions of 0.4 Torr, applied power of 0.22 to 0.33 W/cm 2 , and applied high frequency of 13.56 MHz. After a development time of 21 minutes and 30 seconds, the film thickness in the unexposed area became 0. The remaining film thickness at this time was measured, and the sensitivity and remaining film rate were determined. Sensitivity is 5.6×10 -4 C/cm 2 and residual film rate is 82%
It was hot.
(5) 発明の効果
以上の実施例および比較例からも明らかなよう
に、本発明に係るレジスト組成物は高感度で、残
膜率が高く、サブミクロンのパターンを与える効
果を奏する。(5) Effects of the Invention As is clear from the above Examples and Comparative Examples, the resist composition according to the present invention has high sensitivity, a high residual film rate, and is effective in providing submicron patterns.
第１図は本発明に係る方法の工程を模式的に示
すフローシートである。図中、１は基板、２はレ
ジスト層、３は露光部分である。
FIG. 1 is a flow sheet schematically showing the steps of the method according to the present invention. In the figure, 1 is a substrate, 2 is a resist layer, and 3 is an exposed portion.
Claims (1)
の重合体又はこれらの単量体の共重合体に、下記
一般式，，，，，又はで表わされ
るシリコン化合物を１〜50重量％含有せしめてな
るネガ型レジスト組成物。 上記式〜中、R1は炭素数１〜６のアルキ
ル基、ベンジル基、フエニル基又はシクロヘキシ
ル基を表わし、R2はメチル基又はフエニル基を
表わし、Ｘはメチル基、フエニル基、ビフエニル
基、フエニルアミノ基、フエノキシ基、ベンジル
基、シアノ基、ビニル基又はアセトキシ基を表わ
し、Ｙは水素原子、ヒドロキシ基、アジド基、ビ
ニル基、メトキシ基、エトキシ基、ブトキシ基、
フエノキシ基、ハロゲン原子、ベンジル基、フエ
ニル基、メチル基、ｔ―ブチル基、ビフエニル基
又はアセトキシ基を表わし、Ｚはフエニル基、ヒ
ドロキシ基、ビニル基、メトキシ基、エトキシ
基、ブトキシ基、ベンジル基、メチル基、ｔ―ブ
チル基、フエノキシ基、ハロゲン原子、ビフエニ
ル基又はアセトキシ基を表わす。 ２ 基板上にネガレジストパターンを形成するに
当り、前記基板上に下記一般式，又は 〔上記式および中、R1は炭素数１〜６の
アルキル基、ベンジル基、フエニル基又はシクロ
ヘキシル基を表わし、R2はメチル基又はフエニ
ル基を表わす。〕 で示される重合体又はこれらの共重合体に下記一
般式〜： 〔上記式〜中、はメチル基、フエニル
基、ビフエニル基、フエニルアミノ基、フエノキ
シ基、ベンジル基、シアノ基、ビニル基又はアセ
トキシ基を表わし、Ｙは水素原子、ヒドロキシ
基、アジド基、ビニル基、メトキシ基、エトキシ
基、ブトキシ基、フエノキシ基、ハロゲン原子、
ベンジル基、フエニル基、メチル基、ｔ―ブチル
基、ビフエニル基又はアセトキシ基を表わし、Ｚ
はフエニル基、ヒドロキシ基、ビニル基、メトキ
シ基、エトキシ基、ブトキシ基、ベンジル基、メ
チル基、ｔ―ブチル基、フエノキシ基、ハロゲン
原子、ビフエニル基又はアセトキシ基を表わす。〕 で表わされるシリコン化合物を１〜50重量％含有
せしめたレジスト組成物を塗布し、得られたレジ
スト層を電離放射線により露光し、次いでこのレ
ジスト層をリリーフ処理に付した後、プラズマに
より現像することを特徴とするレジストパターン
形成方法。[Scope of Claims] 1. A polymer of monomers represented by the following general formula, or, or a copolymer of these monomers, and a silicon compound represented by the following general formula, , , , or 1 to A negative resist composition containing 50% by weight. In the above formulas, R 1 represents an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or a cyclohexyl group, R 2 represents a methyl group or a phenyl group, and X represents a methyl group, a phenyl group, a biphenyl group, represents a phenylamino group, phenoxy group, benzyl group, cyano group, vinyl group or acetoxy group, Y is a hydrogen atom, hydroxy group, azido group, vinyl group, methoxy group, ethoxy group, butoxy group,
Represents a phenoxy group, a halogen atom, a benzyl group, a phenyl group, a methyl group, a t-butyl group, a biphenyl group, or an acetoxy group, and Z is a phenyl group, a hydroxy group, a vinyl group, a methoxy group, an ethoxy group, a butoxy group, a benzyl group , methyl group, t-butyl group, phenoxy group, halogen atom, biphenyl group or acetoxy group. 2. When forming a negative resist pattern on a substrate, the following general formula or [In the above formula and inside, R 1 represents an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or a cyclohexyl group, and R 2 represents a methyl group or a phenyl group. ] The following general formula ~: [In the above formulas ~ represents a methyl group, a phenyl group, a biphenyl group, a phenylamino group, a phenoxy group, a benzyl group, a cyano group, a vinyl group, or an acetoxy group, and Y represents a hydrogen atom, a hydroxy group, an azide group, a vinyl group, Methoxy group, ethoxy group, butoxy group, phenoxy group, halogen atom,
represents a benzyl group, phenyl group, methyl group, t-butyl group, biphenyl group or acetoxy group, Z
represents a phenyl group, a hydroxy group, a vinyl group, a methoxy group, an ethoxy group, a butoxy group, a benzyl group, a methyl group, a t-butyl group, a phenoxy group, a halogen atom, a biphenyl group, or an acetoxy group. ] A resist composition containing 1 to 50% by weight of the silicon compound represented by is applied, the resulting resist layer is exposed to ionizing radiation, this resist layer is then subjected to relief treatment, and then developed with plasma. A resist pattern forming method characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22761182A JPS59121042A (en) | 1982-12-28 | 1982-12-28 | Negative type resist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22761182A JPS59121042A (en) | 1982-12-28 | 1982-12-28 | Negative type resist composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59121042A JPS59121042A (en) | 1984-07-12 |
| JPH0150894B2 true JPH0150894B2 (en) | 1989-11-01 |
Family
ID=16863645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22761182A Granted JPS59121042A (en) | 1982-12-28 | 1982-12-28 | Negative type resist composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59121042A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022172929A1 (en) | 2021-02-09 | 2022-08-18 | 信越化学工業株式会社 | Gelatine-containing device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2571072B2 (en) * | 1987-10-16 | 1997-01-16 | 日本電信電話株式会社 | Pattern forming material and multilayer wiring board using the same |
| JP2794607B2 (en) * | 1990-03-22 | 1998-09-10 | ソニー株式会社 | Pattern forming method using photobleachable material composition |
| JP2850460B2 (en) * | 1990-03-24 | 1999-01-27 | ソニー株式会社 | Pattern formation method |
-
1982
- 1982-12-28 JP JP22761182A patent/JPS59121042A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022172929A1 (en) | 2021-02-09 | 2022-08-18 | 信越化学工業株式会社 | Gelatine-containing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59121042A (en) | 1984-07-12 |
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