JPS6360899B2 - - Google Patents
Info
- Publication number
- JPS6360899B2 JPS6360899B2 JP8756781A JP8756781A JPS6360899B2 JP S6360899 B2 JPS6360899 B2 JP S6360899B2 JP 8756781 A JP8756781 A JP 8756781A JP 8756781 A JP8756781 A JP 8756781A JP S6360899 B2 JPS6360899 B2 JP S6360899B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- resist
- plasma
- biphenyl
- 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
- 239000007789 gas Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000006267 biphenyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- -1 cinnamoyl Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 1
- 238000010894 electron beam technology Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 206010073306 Exposure to radiation Diseases 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- OVOIHGSHJGMSMZ-UHFFFAOYSA-N ethenyl(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 OVOIHGSHJGMSMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 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 2
- 239000008096 xylene Substances 0.000 description 2
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XPBGTHZWXMZRON-UHFFFAOYSA-N C1(=CC=CC=C1)C(C[SiH3])(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(C[SiH3])(C1=CC=CC=C1)C1=CC=CC=C1 XPBGTHZWXMZRON-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 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
- XRRLRPCAMVHBDK-UHFFFAOYSA-N [cyano(dimethyl)silyl]formonitrile Chemical compound N#C[Si](C)(C)C#N XRRLRPCAMVHBDK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CUCDHIYTCSBMGZ-UHFFFAOYSA-N azido(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(N=[N+]=[N-])C1=CC=CC=C1 CUCDHIYTCSBMGZ-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PHSNFACJRATEMO-UHFFFAOYSA-N dibenzyl(dimethyl)silane Chemical compound C=1C=CC=CC=1C[Si](C)(C)CC1=CC=CC=C1 PHSNFACJRATEMO-UHFFFAOYSA-N 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- HCKMRFVWQPVCFY-UHFFFAOYSA-N diphenyl-bis(4-phenylphenyl)silane Chemical compound C1=CC=CC=C1C1=CC=C([Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 HCKMRFVWQPVCFY-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LMBXAKYWWMNNCR-UHFFFAOYSA-N n-[anilino(dimethyl)silyl]aniline Chemical compound C=1C=CC=CC=1N[Si](C)(C)NC1=CC=CC=C1 LMBXAKYWWMNNCR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- JLAVCPKULITDHO-UHFFFAOYSA-N tetraphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JLAVCPKULITDHO-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- UTXPCJHKADAFBB-UHFFFAOYSA-N tribenzyl(chloro)silane Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)(Cl)CC1=CC=CC=C1 UTXPCJHKADAFBB-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 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)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
【発明の詳細な説明】
本発明は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、Deep UV線等の放射線に
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ドライ現
像することを含むレジストパターンの形成方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a resist pattern. To explain in more detail, the present invention uses electron beams,
A resist pattern that involves dry development using oxygen plasma, argon gas plasma, oxygen-argon mixed gas plasma, oxygen-fluorine gas mixed gas plasma, etc. after exposure to radiation such as X-rays, ion beams, and deep UV rays. The present invention relates to a method of forming.
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。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
潤を収縮を起し、サブミクロンのパターンを形成
することは困難である。 2. Description of the Related Art 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 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, the resists swell and contract during development, making it difficult to form submicron patterns.
従つて、本発明の目的はドライ現像によるレジ
ストパターンの形成を可能にし、信頼性の高い微
細レジストパターンの形成を容易にすることにあ
る。 Therefore, an object of the present invention is to enable the formation of a resist pattern by dry development and to facilitate the formation of a highly reliable fine resist pattern.
本発明によれば基板上に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
前記基板上にガスプラズマによりエツチング可能
な物質を塗布し、この下部層上に分子構造中にビ
ニル、アリル、シンナモイル又はアクリル二重結
合を含む不飽和炭化水素結合を有する高分子材料
に下記一般式：
〔上式中、Ｘはそれぞれメチル基、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、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、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〕
で示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、このレジスト層
を電子線、Ｘ線、イオンビーム、DeeP UV線等
の放射線に露光し、次いでガスプラズマにより現
像した後、更に引続き前記下部層をガスプラズマ
によりエツチングすることを特徴とする。 According to the present invention, there is provided a method for forming a resist pattern on a substrate, which method includes coating the substrate with a material that can be etched by gas plasma, and applying vinyl in the molecular structure on the lower layer. The following general formula for polymeric materials having unsaturated hydrocarbon bonds, including allyl, cinnamoyl or acrylic double bonds: [In the above formula, X represents a methyl group, phenyl group, biphenyl group, phenylamino group, phenoxy group, benzyl group, cyano group, vinyl group, or acetoxy group, and Y represents a hydrogen atom, a hydroxy group, an azide group, or a vinyl group. , ethoxy group, butoxy group, phenoxy group, halogen atom, benzyl group,
Represents a phenyl group, methyl group, t-butyl group, biphenyl group or acetoxy group, and Z is a phenyl group, hydroxy group, benzyl group, methyl group, t-
Butyl group, phenoxy group, halogen atom, biphenyl group, or acetoxy group] A resist composition containing 1 to 50% by weight of a silicon compound represented by the following formula is applied, and this resist layer is exposed to electron beams, X-rays, or ion beams. , DeeP After exposure to radiation such as UV radiation and subsequent development with gas plasma, the lower layer is further etched with gas plasma.
本発明は、上記ポリマーにシリコン化合物を含
有せしめたレジスト材料がプラズマ処理に対し著
しくエツチング速度が低下すること、および上記
レジスト材料に電子線等の放射線を露光するとプ
ラズマ処理時のエツチング速度が増加することの
知見に基づくものである。 The present invention provides that the etching rate of the resist material containing a silicon compound in the polymer decreases significantly when subjected to plasma treatment, and that the etching rate increases during plasma treatment when the resist material is exposed to radiation such as an electron beam. This is based on knowledge of the matter.
本発明に使用可能な分子構造中に不飽和炭化水
素結合を有する高分子材料としては、１，３―ブ
タジエン、イソプレン等のアルカジエンの重合体
およびこれらの環化物またはこれらのアルカジエ
ンと共重合可能なモノマーとの共重合体、ジアリ
ルオルソフタレート、ジアリルイソフタレート、
ジアリルテレフタレート等のジカルボン酸ジアリ
ルエステル重合体、トリアリルシアヌレート、ト
リアリルイソシアヌール等の重合体およびこれら
の共重合体、ポリケイ皮酸ビニル等のシンナモイ
ル基を有する高分子材料、側鎖または末端にアク
リル基またはメタクリル基を有する高分子材料、
不飽和ポリエステル等がある。 Examples of polymeric materials having unsaturated hydrocarbon bonds in the molecular structure that can be used in the present invention include polymers of alkadienes such as 1,3-butadiene and isoprene, and cyclized products thereof or copolymerizable with these alkadienes. Copolymers with monomers, diallyl orthophthalate, diallyl isophthalate,
Dicarboxylic acid diallyl ester polymers such as diallyl terephthalate, polymers such as triallyl cyanurate, triallylisocyanurate, and their copolymers, polymeric materials having cinnamoyl groups such as polyvinyl cinnamate, and polymers with side chains or terminals. polymeric material having acrylic or methacrylic groups,
Examples include unsaturated polyester.
一方、本発明に使用可能な一般式で示される
シリコン化合物としてはビス（ｐ―ビフエニル）
ジフエニルシラン、ビス（フエニルアミノ）ジメ
チルシラン、ｔ―ブチルジメチルクロロシラン、
ｔ―ブチルジフエニルクロロシラン、ジベンジル
ジメチルシラン、ジシアノジメチルシラン、ジフ
エニルシランジオール、テトラアセトキシシラ
ン、テトラフエノキシシラン、テトラフエニルシ
ラン、トリベンジルクロロシラン、トリフエニル
クロロシラン、トリフエニルエチルシラン、トリ
フエニルフルオロシラン、トリフエニルシラン、
トリフエニルシラノール、トリフエニルシリルア
ジド、トリフエニルビニルシラン等がある。 On the other hand, as a silicon compound represented by the general formula that can be used in the present invention, bis(p-biphenyl)
Diphenylsilane, bis(phenylamino)dimethylsilane, t-butyldimethylchlorosilane,
t-Butyldiphenylchlorosilane, dibenzyldimethylsilane, dicyanodimethylsilane, diphenylsilanediol, tetraacetoxysilane, tetraphenoxysilane, tetraphenylsilane, tribenzylchlorosilane, triphenylchlorosilane, triphenylethylsilane, triphenylchlorosilane enylfluorosilane, triphenylsilane,
Examples include triphenylsilanol, triphenylsilyl azide, and triphenylvinylsilane.
本発明の方法を添附図面を参照しながら更に説
明する。即ち、本発明の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。
先ず第１図のイに示す如く、基板１上に下部層２
を形成する。これは、プラズマによりエツチング
することが可能な物質、例えばポリビニルカルバ
ゾール、ポリスチレン、フエノール樹脂、環化ポ
リイソプレン樹脂、ポリイミド樹脂など、をスピ
ンコートやプラズマ重合などに適用することによ
り行うことができる。次いでこの下部層２の上に
上部レジスト層３を形成する。例えば、スピンコ
ート法によりレジスト組成液を塗布し、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。次に、レジス
ト層３のドライ現像と下部層２のドライエツチン
グを行う。先ず、酸素プラズマ等によるプラズマ
処理により上部レジスト層３の露光部分４が除去
されて第１図のハに示す状態となるが、引続いて
プラズマ処理を施すと更に下部層２がエツチング
されて第１図のニに示す如く所望のパターンが形
成されるのである。 The method of the invention will be further explained with reference to the accompanying drawings. That is, the method of the present invention can be carried out according to a conventional method by the following operations.
First, as shown in FIG.
form. This can be done by applying a substance that can be etched by plasma, such as polyvinyl carbazole, polystyrene, phenolic resin, cyclized polyisoprene resin, polyimide resin, etc., to spin coating or plasma polymerization. Next, an upper resist layer 3 is formed on this lower layer 2. For example, apply the resist composition solution using a spin coating method, and
Pre-bake for 10-30 minutes at a temperature of . Next, this is exposed to an electron beam or the like as shown in (B). Next, dry development of the resist layer 3 and dry etching of the lower layer 2 are performed. First, the exposed portion 4 of the upper resist layer 3 is removed by plasma treatment using oxygen plasma or the like, resulting in the state shown in FIG. A desired pattern is formed as shown in Figure 1D.
本発明によれば、プラズマ処理により微細なレ
ジストパターンを精度よく形成することができ
る。更に、本発明の如く二層構造のパターン形成
層とすることにより被加工基板のエツチングにお
いてたとえ、そのガスプラズマに対しレジスト層
が弱い酸性であつても下部層を選択することによ
り、レジストパターンによりパターンが転写され
た下部層がマスクとなり良好な結果を得ることが
できる。また、下部層のエツチングの際にエツチ
ング条件の選択によりパターンの形状をコントロ
ールすることも可能である。 According to the present invention, a fine resist pattern can be formed with high accuracy by plasma processing. Furthermore, by using a two-layer pattern forming layer as in the present invention, even when etching a substrate to be processed, even if the resist layer is weakly acidic to the gas plasma, by selecting the lower layer, the resist pattern can be more easily etched. The lower layer to which the pattern has been transferred serves as a mask, and good results can be obtained. Furthermore, it is also possible to control the shape of the pattern by selecting etching conditions when etching the lower layer.
以下、実施例により本発明を更に説明する。 The present invention will be further explained below with reference to Examples.
実施例 １
シリコン基板上にポリイミド樹脂を1μmの厚さ
に塗布し、350℃で１時間加熱した。その上に環
化ポリイソプレンにトリフエニルシランを22％の
重量比で加え、キシレンに溶解したレジスト液を
0.5μmの厚さに塗布し、60℃で30分間、窒素気流
中で加熱した。次に加速電圧30KVの電子線にて
1.5×10-4C／cm2の露光をした後、平行平板型プラ
ズマエツチング装置内に入れ、６×10-5Torrま
で減圧し、装置内を排気した後、酸素を導入し
た。酸素ガス圧力0.4Torr、印加周波数13.56M
Hz、印加電力0.33W／cm2の条件で15分間プラズマ
処理すると露光部のレジストが現像され、続いて
20分間のエツチングにて２層目が完全にエツチン
グされた。この時の残存膜厚は約1.5μであつた。Example 1 Polyimide resin was applied to a thickness of 1 μm on a silicon substrate and heated at 350° C. for 1 hour. On top of that, triphenylsilane was added to the cyclized polyisoprene at a weight ratio of 22%, and a resist solution dissolved in xylene was added.
It was applied to a thickness of 0.5 μm and heated at 60° C. for 30 minutes in a nitrogen stream. Next, using an electron beam with an accelerating voltage of 30KV
After exposure to light of 1.5×10 −4 C/cm 2 , it was placed in a parallel plate type plasma etching device, the pressure was reduced to 6×10 −5 Torr, the inside of the device was evacuated, and oxygen was introduced. Oxygen gas pressure 0.4Torr, applied frequency 13.56M
Hz, applied power 0.33W/ cm2 for 15 minutes, the resist in the exposed area is developed, and then
The second layer was completely etched after 20 minutes of etching. The remaining film thickness at this time was approximately 1.5μ.
実施例 ２
シリコン基板上にフエノールホルムアミド樹脂
を1μmの厚さに塗布し、200℃で１時間加熱した。
その上に環化ポリイソプレンにトリフエニルビニ
ルシランを22％の重量比で加え、キシレンに溶解
したレジスト液を0.5μmの厚さに塗布し、60℃で
30分間、窒素気流中で加熱した。この層構造のレ
ジストを実施例１と同様に露光した後、実施例１
と同条件でプラズマ処理した。現像時間８分間で
露光部のレジストが現像され、続いて７分間で第
２層目が完全にエツチングされた。この時の残存
膜厚は約1.4μmであつた。Example 2 Phenolformamide resin was applied to a thickness of 1 μm on a silicon substrate and heated at 200° C. for 1 hour.
On top of that, add triphenylvinylsilane to cyclized polyisoprene at a weight ratio of 22%, apply a resist solution dissolved in xylene to a thickness of 0.5 μm, and heat at 60°C.
Heated in a nitrogen stream for 30 minutes. After exposing the resist with this layered structure in the same manner as in Example 1, Example 1
Plasma treatment was performed under the same conditions. The resist in the exposed area was developed in a developing time of 8 minutes, and the second layer was completely etched in a subsequent 7 minutes. The remaining film thickness at this time was approximately 1.4 μm.
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。図において、１は基板、
２は下部層、３は上部レジスト層、そして４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 lower layer, 3 is an upper resist layer, and 4 is an exposed portion.
Claims (1)
り、前記基板上にガスプラズマによりエツチング
可能な物質を塗布し、この下部層上に分子構造中
にビニル、アリル、シンナモイル又はアクリル二
重結合を含む不飽和炭化水素結合を有する高分子
材料に下記一般式： 〔上式中、Ｘはそれぞれメチル基、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、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、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〕 で示されるシリコン化合物を１〜50重量％含有せ
しめてなるレジスト組成物を塗布し、このレジス
ト層を放射線に露光し、次いでガスプラズマによ
り現像した後、更に引続き前記下部層をガスプラ
ズマによりエツチングすることを特徴とする方
法。[Scope of Claims] 1. In forming a resist pattern on a substrate, a substance that can be etched by gas plasma is applied to the substrate, and a material containing vinyl, allyl, cinnamoyl or acrylic diamide in the molecular structure is applied on the lower layer. The following general formula for polymeric materials having unsaturated hydrocarbon bonds including heavy bonds: [In the above formula, X represents a methyl group, phenyl group, biphenyl group, phenylamino group, phenoxy group, benzyl group, cyano group, vinyl group, or acetoxy group, and Y represents a hydrogen atom, a hydroxy group, an azide group, or a vinyl group. , ethoxy group, butoxy group, phenoxy group, halogen atom, benzyl group,
Represents a phenyl group, methyl group, t-butyl group, biphenyl group or acetoxy group, and Z is a phenyl group, hydroxy group, benzyl group, methyl group, t-
butyl group, phenoxy group, halogen atom, biphenyl group, or acetoxy group] A resist composition containing 1 to 50% by weight of a silicon compound represented by the following formula is applied, this resist layer is exposed to radiation, and then gas A method characterized in that, after the development with the plasma, the lower layer is subsequently etched with a gas plasma.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8756781A JPS57202533A (en) | 1981-06-09 | 1981-06-09 | Formation of pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8756781A JPS57202533A (en) | 1981-06-09 | 1981-06-09 | Formation of pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57202533A JPS57202533A (en) | 1982-12-11 |
| JPS6360899B2 true JPS6360899B2 (en) | 1988-11-25 |
Family
ID=13918562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8756781A Granted JPS57202533A (en) | 1981-06-09 | 1981-06-09 | Formation of pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57202533A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57211143A (en) * | 1981-06-23 | 1982-12-24 | Oki Electric Ind Co Ltd | Formation of micropattern |
| JPS5891632A (en) * | 1981-11-27 | 1983-05-31 | Oki Electric Ind Co Ltd | Formation of microscopic pattern |
| US4552833A (en) * | 1984-05-14 | 1985-11-12 | International Business Machines Corporation | Radiation sensitive and oxygen plasma developable resist |
| GB8427149D0 (en) * | 1984-10-26 | 1984-12-05 | Ucb Sa | Resist materials |
| US4782008A (en) * | 1985-03-19 | 1988-11-01 | International Business Machines Corporation | Plasma-resistant polymeric material, preparation thereof, and use thereof |
| JPH0727221B2 (en) * | 1985-07-24 | 1995-03-29 | 日本電信電話株式会社 | Pattern formation method |
| JPH07107605B2 (en) * | 1985-07-26 | 1995-11-15 | 日本電信電話株式会社 | Pattern formation method |
| JP2598923B2 (en) * | 1987-10-16 | 1997-04-09 | 正隆 村原 | Method of developing resist material |
| JP2506133B2 (en) * | 1987-11-18 | 1996-06-12 | 日本電信電話株式会社 | Pattern formation method |
| US4999280A (en) * | 1989-03-17 | 1991-03-12 | International Business Machines Corporation | Spray silylation of photoresist images |
| JP2504832B2 (en) * | 1989-06-16 | 1996-06-05 | シャープ株式会社 | Method of forming resist pattern |
-
1981
- 1981-06-09 JP JP8756781A patent/JPS57202533A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57202533A (en) | 1982-12-11 |
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