JPH0377989B2 - - Google Patents
Info
- Publication number
- JPH0377989B2 JPH0377989B2 JP58178086A JP17808683A JPH0377989B2 JP H0377989 B2 JPH0377989 B2 JP H0377989B2 JP 58178086 A JP58178086 A JP 58178086A JP 17808683 A JP17808683 A JP 17808683A JP H0377989 B2 JPH0377989 B2 JP H0377989B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- pmma
- sensitivity
- plasma resistance
- methylstyrene
- 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 - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000007261 regionalization Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 9
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- OQZQDGSYKKFLTE-UHFFFAOYSA-N 1-(4-azidophenyl)-3-phenylprop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C(=O)C=CC1=CC=CC=C1 OQZQDGSYKKFLTE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- ABBGIFCRZQRIAV-UHFFFAOYSA-N 4-(4-azidophenyl)but-3-en-2-one Chemical compound CC(=O)C=CC1=CC=C(N=[N+]=[N-])C=C1 ABBGIFCRZQRIAV-UHFFFAOYSA-N 0.000 description 1
- WNDDODBAIXQYJZ-UHFFFAOYSA-N OC(=O)C1=C(N=[N+]=[N-])CC(=S(=O)=O)C=C1 Chemical compound OC(=O)C1=C(N=[N+]=[N-])CC(=S(=O)=O)C=C1 WNDDODBAIXQYJZ-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
- 125000003118 aryl group Chemical group 0.000 description 1
- -1 azide compound Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 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
Description
発明の技術分野
本発明はパターン形成方法、より詳しくはリソ
グラフイ技術を利用し、レジストを用いるパター
ン形成方法に係る。
従来技術と問題点
リソグラフイー技術を微細加工用に利用するこ
とは公知である。半導体装置の微細化はジストを
電子線等で露光することの有利さを著しくしてい
る。メタクリル酸エステルのポリマー、例えばポ
リメチルメタクリレート（PMMA）は電子線感
応性のポジ形レジストとして検討がなされ、高解
像力を有するため、現在も広く用いられている。
しかし、この系では耐プラズマ性が非常に悪く、
また高感度も得られない。
ポリメタクリル酸エステルのエステル部位を嵩
高い（原子団が占める容積が大きい）アルキル基
や耐プラズマ性を持つと言われるベンゼン環等の
芳香環で置換したものも検討されているが、耐プ
ラズマ性や感度は殆んど改善されず、しかも解像
度はPMMAより低下する（Wayne M.Moreau，
SPIE Vol.333 Submicron Lithography，1982
年、参照）。
発明の目的
本発明は、以上の如き従来技術に鑑み、
PMMA系の高解像力を失なうことなく耐プラズ
マ性と感度を向上させてパターン形成に用いるこ
とを目的とする。
発明の構成
そして、上記目的を達成するために、本発明
は、メタクリル酸エステル（ここに、アルキル基
はメチル基またはエチル基である）とα−メチル
スチレンの共重合体をポジ型レジスト材料として
用いるパターン形成方法を提供する。
本発明は、PMMA系誘導体によつてではなく、
PMMA系との共重合によつて上記目的を達成す
るものである。共重合の相手としては放射線（Ｘ
線）分解性（α位に４級炭素を持つもの）で、芳
香環を持つという条件と共に、構造が単純であ
り、入手し易く、しかもPMMAと同等の高コン
トラスト性を持つということからα−メチルスチ
レンが好ましいものであつた。メタクリル酸エス
テルとα−メチルスチンの共重合比は20：80〜
80：20であることが好ましい。α−メチルスチレ
ンが少ないと耐プラズマ性が期待できず、多すぎ
ると、感度が低下するため、20〜80％の範囲内が
望ましい。この共重合体は下記の構造式で表わさ
れる。
しかし、この共重合体だけでは十分な感度が得
られず、５×10-5C／cm2以下である。従つて、こ
の共重合体単独のものは、PMMA系と同様に多
層のレジストのうちの１層として用いるなどする
ほかない。そこで、この共重合体と架橋剤を混合
して塗布し、予め架橋させて不溶化させておい
て、電子線等に選択的に露光して部分的に架橋を
分解させ、現像時に溶解性の強い溶媒で強制現像
すれば、結果としてレジスト材料の感度が向上し
たことになる。架橋剤としてはアジド化合物、例
えば４，4′−ジアジドカルコン：
ｐ−アジドベンザルアセトフエノン：
TECHNICAL FIELD OF THE INVENTION The present invention relates to a pattern forming method, and more particularly to a pattern forming method that utilizes lithography technology and uses a resist. Prior Art and Problems The use of lithographic techniques for microfabrication is known. The miniaturization of semiconductor devices has made it more advantageous to expose the resist with an electron beam or the like. Polymers of methacrylic acid esters, such as polymethyl methacrylate (PMMA), have been studied as electron beam-sensitive positive resists, and are still widely used because of their high resolution.
However, this system has very poor plasma resistance.
Also, high sensitivity cannot be obtained. Polymethacrylate esters in which the ester moiety is replaced with a bulky alkyl group (the volume occupied by the atomic group is large) or an aromatic ring such as a benzene ring that is said to have plasma resistance are also being considered; There is little improvement in sensitivity and resolution, and resolution is lower than that of PMMA (Wayne M.Moreau,
SPIE Vol.333 Submicron Lithography, 1982
year, see). Purpose of the Invention In view of the above-mentioned prior art, the present invention has been made to
The aim is to improve plasma resistance and sensitivity without losing the high resolution of the PMMA system, and to use it for pattern formation. Structure of the Invention In order to achieve the above object, the present invention uses a copolymer of methacrylic acid ester (herein, the alkyl group is a methyl group or ethyl group) and α-methylstyrene as a positive resist material. A pattern forming method for use in the present invention is provided. The present invention does not rely on PMMA-based derivatives, but
The above object is achieved by copolymerization with PMMA system. The copolymerization partner is radiation (X
α- Methylstyrene was preferred. The copolymerization ratio of methacrylic acid ester and α-methylstin is 20:80 ~
Preferably it is 80:20. If α-methylstyrene is too small, plasma resistance cannot be expected, and if it is too large, the sensitivity will decrease, so it is preferably in the range of 20 to 80%. This copolymer is represented by the following structural formula. However, this copolymer alone does not provide sufficient sensitivity, which is less than 5×10 −5 C/cm 2 . Therefore, this copolymer alone has no choice but to be used as one layer of a multilayer resist, similar to the PMMA type. Therefore, this copolymer and a crosslinking agent are mixed and applied, crosslinked and insolubilized in advance, and then selectively exposed to electron beams etc. to partially decompose the crosslinking, and when developed, the highly soluble Forced development with a solvent results in improved sensitivity of the resist material. As a crosslinking agent, an azide compound such as 4,4'-diazide chalcone: p-azidobenzalacetophenone:
【式】ｐ−アジ ド安息香酸：[Formula] p-Aji Dobenzoic acid:
【式】p.アジド アセトフエノン：[Formula] p.azide Acetophenone:
【式】ｐ−
スルフオニルアジド安息香酸：
[Formula] p-sulfonylazidobenzoic acid:
【式】などを用いることが
好ましい。
発明の実施例
例 １
α−メチルスチンとメタクリル酸メチルの40：
40の共重合体を作成し、これと４，4′−ジアジド
カルコンを80：20（重量比）でエチルセロソルブ
アセテートに溶解した。この混合溶液をフイルタ
リング後シリコンウエーハ上にスピンコートし、
膜厚0.5μmとした後、窒素雰囲気中で170℃にて
60分間ベークした。加速電圧20keVの電子線で選
択的に露光した後、メチルセロソルブで現像し
た。
感度7.2×10-6C／cm2で1μmライン／スペースを
解像した。
O2＋CF4ガス（５−95％）でプラズマ処理した
ところ（200W，0.1torr）、PMMAの約４倍の耐
プラズマ性を示した。
例 ２
メタクリル酸メチルの代りにメタクリル酸エチ
ルを用いて例１と同じ処理を行なつた。感度９×
10-6C／cm2で、1μmライン／スペースの解像度を
示し、O2＋CF4ガスに対しPMMAの約４倍の耐
プラズマ性を有した。
例 ３
架橋剤に、４−アジドベンザルアセトンを用い
例１と同様の処理をした。
D0＝810-6C／cm2のE.B.感度を示し、0.8μmライ
ン／スペースが得られた。耐プラズマ性（CF4／
O2：95／５）は、PMMAの約４倍であつた。
例 ４
α−メチルスチレン／メタクリル酸メチルコポ
リマー（40：60），≒６万を合成し、同様な
処理をした。D0＝5.2×10-5C／cm2で、1μmのライ
ン／スペースを解像した。O2／CF4（５／95）ガ
スに対する耐プラズマ性はPMMAの約３倍であ
つた。
発明の効果
以上の説明から明らかな通り、本発明により、
電子線露光で高感度、耐プラズマ性のポジ形レジ
ストを利用した微細パターンの形成が可能にな
る。[Formula] etc. are preferably used. Example 1 of the invention 40 of α-methylstin and methyl methacrylate:
A copolymer of No. 40 was prepared, and this copolymer and 4,4'-diazide chalcone were dissolved in ethyl cellosolve acetate at a ratio of 80:20 (weight ratio). This mixed solution was filtered and then spin coated onto a silicon wafer.
After reducing the film thickness to 0.5μm, at 170℃ in a nitrogen atmosphere.
Bake for 60 minutes. After selective exposure to an electron beam with an accelerating voltage of 20 keV, development was performed with methyl cellosolve. It resolved 1 μm lines/spaces with a sensitivity of 7.2×10 −6 C/cm 2 . When plasma treated with O 2 + CF 4 gas (5-95%) (200 W, 0.1 torr), it showed about 4 times the plasma resistance of PMMA. Example 2 The same procedure as in Example 1 was carried out using ethyl methacrylate instead of methyl methacrylate. Sensitivity 9x
It exhibited a resolution of 1 μm line/space at 10 -6 C/cm 2 and had plasma resistance about 4 times that of PMMA against O 2 + CF 4 gas. Example 3 The same treatment as in Example 1 was carried out using 4-azidobenzalacetone as a crosslinking agent. It exhibited an EB sensitivity of D 0 =810 −6 C/cm 2 and a line/space of 0.8 μm was obtained. Plasma resistance (CF 4 /
O 2 :95/5) was about 4 times that of PMMA. Example 4 α-methylstyrene/methyl methacrylate copolymer (40:60), ≒60,000, was synthesized and treated in the same manner. 1 μm lines/spaces were resolved with D 0 =5.2×10 −5 C/cm 2 . The plasma resistance against O 2 /CF 4 (5/95) gas was approximately three times that of PMMA. Effects of the Invention As is clear from the above explanation, the present invention provides
Electron beam exposure enables the formation of fine patterns using highly sensitive, plasma-resistant positive resists.
Claims (1)
アルキル基であり該アルキル基はメチル基または
エチル基である）とα−メチルスチレンの共重合
体をポジ型レジスト材料として用いることを特徴
とするパターン形成方法。 ２ 前記共重合体と架橋剤の混合物をレジスト材
料として用いることを特徴とする特許請求の範囲
第１項記載のパターン形成方法。[Claims] 1. Use of a copolymer of methacrylic acid ester (herein, the ester is an alkyl group, and the alkyl group is a methyl group or an ethyl group) and α-methylstyrene as a positive resist material. Characteristic pattern formation method. 2. The pattern forming method according to claim 1, wherein a mixture of the copolymer and a crosslinking agent is used as a resist material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58178086A JPS6070442A (en) | 1983-09-28 | 1983-09-28 | Formation of pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58178086A JPS6070442A (en) | 1983-09-28 | 1983-09-28 | Formation of pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6070442A JPS6070442A (en) | 1985-04-22 |
| JPH0377989B2 true JPH0377989B2 (en) | 1991-12-12 |
Family
ID=16042378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58178086A Granted JPS6070442A (en) | 1983-09-28 | 1983-09-28 | Formation of pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6070442A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617085A (en) * | 1985-09-03 | 1986-10-14 | General Electric Company | Process for removing organic material in a patterned manner from an organic film |
| JP2645561B2 (en) * | 1987-12-19 | 1997-08-25 | 富士通株式会社 | Resist material |
| JP2023179310A (en) * | 2022-06-07 | 2023-12-19 | 栗田工業株式会社 | Depolymerizable copolymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52128132A (en) * | 1976-04-20 | 1977-10-27 | Fujitsu Ltd | Positive type electron beam sensitive composition |
| JPS57161743A (en) * | 1981-03-12 | 1982-10-05 | Philips Nv | Method of applying resist pattern on substrate and resist material mixture |
| JPS5848046A (en) * | 1981-09-17 | 1983-03-19 | Matsushita Electric Ind Co Ltd | Resist material for use in far ultraviolet exposure |
| JPS5879062A (en) * | 1981-11-05 | 1983-05-12 | Dainippon Printing Co Ltd | Electron radiation curing coating agent |
| JPS58116532A (en) * | 1981-12-29 | 1983-07-11 | Fujitsu Ltd | Pattern formation |
-
1983
- 1983-09-28 JP JP58178086A patent/JPS6070442A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52128132A (en) * | 1976-04-20 | 1977-10-27 | Fujitsu Ltd | Positive type electron beam sensitive composition |
| JPS57161743A (en) * | 1981-03-12 | 1982-10-05 | Philips Nv | Method of applying resist pattern on substrate and resist material mixture |
| JPS5848046A (en) * | 1981-09-17 | 1983-03-19 | Matsushita Electric Ind Co Ltd | Resist material for use in far ultraviolet exposure |
| JPS5879062A (en) * | 1981-11-05 | 1983-05-12 | Dainippon Printing Co Ltd | Electron radiation curing coating agent |
| JPS58116532A (en) * | 1981-12-29 | 1983-07-11 | Fujitsu Ltd | Pattern formation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6070442A (en) | 1985-04-22 |
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