JPS6279445A - Resist material - Google Patents

Resist material

Info

Publication number
JPS6279445A
JPS6279445A JP21913785A JP21913785A JPS6279445A JP S6279445 A JPS6279445 A JP S6279445A JP 21913785 A JP21913785 A JP 21913785A JP 21913785 A JP21913785 A JP 21913785A JP S6279445 A JPS6279445 A JP S6279445A
Authority
JP
Japan
Prior art keywords
methacrylamide
resist material
carboxylic acid
resist
sensitivity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP21913785A
Other languages
Japanese (ja)
Inventor
Yoshitaka Tsutsumi
堤　義高
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Toyo Soda Manufacturing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Soda Manufacturing Co Ltd filed Critical Toyo Soda Manufacturing Co Ltd
Priority to JP21913785A priority Critical patent/JPS6279445A/en
Publication of JPS6279445A publication Critical patent/JPS6279445A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)

Abstract

PURPOSE:To improve the sensitivity of the titled material in a formation of a positive type resist pattern by incorporating methacrylamide and a specific unsatd. carboxylic acid to a polymer component of the resist material. CONSTITUTION:As the polymer component of the resist material, one may use the methacrylamide and the unsatd. carboxylic acid shown by formula I. The positive pattern is obtd. by coating a substrate with an aqueous ammonia solution of the copolymer composed of such as the methacrylamide and the methacrylic acid, and then by heating it to evaporate ammonia and a lower amine followed by irradiating radiation rays and developing it with a water. The titled resist having the high sensitivity is obtd. by bonding, intermolecular or intramolecular, of the prescribed amide and carboxylic acid.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電子線又はＸ線等の高エネルギー線圧対し、感
応性を有するポジ型レジスト材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a positive resist material that is sensitive to high energy beam pressure such as electron beams or X-rays.

〔従来の技術〕[Conventional technology]

サブミクロンオーダーの微細加工のために、電子線、Ｘ
線等を用いたリソグラフィー技術が導入されている。ポ
ジタイプのレジスト材としてはポリメチルメタクリレー
ト（以下ＰＭＭＡと略す）がよく知られている。ＰＭＭ
Ａは、高解像性を有する材料であるが、感度が低い。Electron beam, X
Lithography technology using lines, etc. has been introduced. Polymethyl methacrylate (hereinafter abbreviated as PMMA) is well known as a positive type resist material. PMM
A is a material with high resolution but low sensitivity.

そこで、ＰＭＭＡを基本として高感度化を計るために１
α位またはエステル部分をハロゲン等の電子吸引基で置
換したレジスト材が知られている。Therefore, in order to increase the sensitivity based on PMMA, we
Resist materials in which the α-position or ester moiety is substituted with an electron-withdrawing group such as a halogen are known.

また、メタクリル酸、メタクリル酸クロリドあるいはメ
タクリルアミド等は前処理として熱架橋を施すことによ
り、感度の向上がみられる。しかし、現実には、より一
層の高感度なレジストが望まれている。Furthermore, sensitivity can be improved by thermally crosslinking methacrylic acid, methacrylic acid chloride, methacrylamide, etc. as a pretreatment. However, in reality, a resist with even higher sensitivity is desired.

〔解決すべき課題〕〔Problems to be solved〕

従って、サブミクＵンレベルの微細加工に用いる実用的
なポジタイプのレジスト材料として、電子線、Ｘ線に対
して感度及び解像度が高い材料の提供が求められている
。Therefore, there is a need to provide a material with high sensitivity and resolution to electron beams and X-rays as a practical positive type resist material for use in submicron level microfabrication.

〔解決するための手段〕[Means to solve]

本発明者らは、このような要求性能を満足するレジスト
材に関して鋭意研究を行った結果、アミドとカルボン酸
とを同時に含む重合体が満足できる性能を有することを
見出し本発明に至った。The inventors of the present invention conducted intensive research on resist materials that satisfy such required performance, and as a result, they discovered that a polymer containing both an amide and a carboxylic acid has satisfactory performance, leading to the present invention.

すなわち、本発明はメタクリルアミドと不飽和カルボン
酸、とくに式（１）に示される不飽和カルボン酸により
構成される重合体からなるレジスト材である。That is, the present invention is a resist material made of a polymer composed of methacrylamide and an unsaturated carboxylic acid, particularly an unsaturated carboxylic acid represented by formula (1).

Ｙ＝Ｏ−Ｚ　　　（１１ 〔発明の構成〕 本発明のレジスト材料であるメタクリルアミドと式（１
）に示される不飽和カルボン酸により構成される重合体
は、各々の単独重合体の混合あるいは共重合（特開５８
−２３２４参照）により得られるＯ 本発明によるレジスト材料のパターン形成方法は特に限
定されないが、以下の方法が好ましい。Y=O-Z (11 [Structure of the invention] Methacrylamide, which is the resist material of the present invention, and the formula (1
) The polymers composed of unsaturated carboxylic acids shown in
Although the method for forming a pattern of the resist material according to the present invention is not particularly limited, the following method is preferred.

レジスト材料をアルカリ水溶液、好ましくはアンモニア
あるいは低級アミン水溶液として基板上に塗布する。そ
の後、加熱によりアンモニア、低級アミンを蒸発させる
。放射線照射後、水にて現像することＫよりポジパター
ンを得るものである。A resist material is applied onto the substrate as an alkaline aqueous solution, preferably an ammonia or lower amine aqueous solution. Thereafter, ammonia and lower amines are evaporated by heating. After irradiation with radiation, a positive pattern is obtained by developing with water.

この方法によると、水にて現像できるため、パターンに
膨潤がなく解像度が高いこと、さらに作業環境の面等で
利点がある。According to this method, since development can be performed with water, the pattern does not swell and has high resolution, and is also advantageous in terms of working environment.

本発明のレジスト材料が高感度であるのは、分子内ある
いは分子間のアミドとカルボン酸との会合によるものと
考えられる。The high sensitivity of the resist material of the present invention is thought to be due to the intramolecular or intermolecular association of amide and carboxylic acid.

〔実施例〕〔Example〕

以下、本発明を実施例により説明する。 The present invention will be explained below using examples.

実施例１ ００ＮＨ！０ＯＯＨ で示されるメタクリルアミド／メタクリル酸共重合体（
ｍ／ｎ＝５１５．Ｍｗ＝五５Ｘ１　ｏ’　）のアンモニ
ア水溶液をシリコンウェハ（直径３インチ）Ｋ塗布し、
１２０℃で２０分間プリベークし、厚さ１μｍのレジス
ト膜を形成した。電子線の選択的露光後、水で現像した
。Example 1 00NH! Methacrylamide/methacrylic acid copolymer (0OOH)
m/n=515. A silicon wafer (3 inches in diameter) was coated with an aqueous ammonia solution of Mw=55×1 o',
Prebaking was performed at 120° C. for 20 minutes to form a resist film with a thickness of 1 μm. After selective exposure to electron beam, it was developed with water.

その結果、感度ｒ４＝２−　ＯＸｌ　０’″”ａ／ｃｒ
ｄが達成された。As a result, sensitivity r4=2-OXl 0'''”a/cr
d was achieved.

実施例２ メタクリルアミド／メタクリル酸共重合体（ｍ／ｎ＝５
１５．Ｍｗ＝ａＯＸ１０’）のアンモニア水溶液を用い
て例１同様の処理を繰り返した。Example 2 Methacrylamide/methacrylic acid copolymer (m/n=5
15. The same treatment as in Example 1 was repeated using an ammonia aqueous solution with Mw=aOX10').

その結果、感度Ｄ０＝五〇×１０−’Ｑ〆イを達成した
。As a result, sensitivity D0=50×10-'Q〆a was achieved.

解像度は１．０μｍ（ライン／スペース）であった。The resolution was 1.0 μm (line/space).

実施例３ ポリメタクリルアミド（Ｍｗ＝５．０ＸＩ　Ｇ’　）と
ポリトリフ／Ｉ／オロメチルアクリル酸（Ｍｗ＝五８×
１０’　）との１対１ブレンド体のアンモニア水溶液を
用いて例１同様の処理を操り返した。Example 3 Polymethacrylamide (Mw=5.0XI G') and Polytrif/I/Oromethylacrylic acid (Mw=58
The same procedure as in Example 1 was repeated using a 1:1 blend of aqueous ammonia with 10').

ソノ結果、感度Ｄ０＝　１．５　Ｘ　１１ｒ”　Ｏ／ｍ
ヲ達成した。Sono result, sensitivity D0 = 1.5 x 11r” O/m
I achieved it.

〔発明の効果〕〔Effect of the invention〕

以上の説明から明らかなように、本発明のレジスト材料
により、ポジ型レジストパターンの形成において感度を
向上させることが可能になった。As is clear from the above description, the resist material of the present invention makes it possible to improve the sensitivity in forming a positive resist pattern.

Claims (2)

【特許請求の範囲】[Claims] （１）重合体成分がメタクリルアミド及び不飽和カルボ
ン酸からなるレジスト材料。(1) A resist material whose polymer components are methacrylamide and unsaturated carboxylic acid. （２）不飽和カルボン酸が一般式 ▲数式、化学式、表等があります▼ ｛Ｘ：−Ｈ、−ＣＨ＿３、−ＣＯＯＨ、−Ｃｌ、−ＣＦ
＿３、−ＣＮ Ｙ：＝ＣＨ＿２、＝ＣＨＣＨ＿３、＝ＣＨＣＯＯＨＺ：
＝ＣＯＯＨ、−ＣＨ＿２ＣＯＯＨ、−ＣＨ＿２ＣＨ＿２
ＣＯＯＨ、▲数式、化学式、表等があります▼、▲数式
、化学式、表等があります▼｝ で示すことのできる特許請求範囲第（１）項記載のレジ
スト材料。(2) Unsaturated carboxylic acids have the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {X: -H, -CH_3, -COOH, -Cl, -CF
_3, -CN Y:=CH_2,=CHCH_3,=CHCOOHZ:
=COOH, -CH_2COOH, -CH_2CH_2
COOH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼} A resist material according to claim 1, which can be represented by:
JP21913785A 1985-10-03 1985-10-03 Resist material Pending JPS6279445A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21913785A JPS6279445A (en) 1985-10-03 1985-10-03 Resist material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21913785A JPS6279445A (en) 1985-10-03 1985-10-03 Resist material

Publications (1)

Publication Number Publication Date
JPS6279445A true JPS6279445A (en) 1987-04-11

Family

ID=16730807

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21913785A Pending JPS6279445A (en) 1985-10-03 1985-10-03 Resist material

Country Status (1)

Country Link
JP (1) JPS6279445A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153103A (en) * 1990-03-13 1992-10-06 Fujitsu Limited Resist composition and pattern formation process
JPH04115163U (en) * 1991-03-25 1992-10-12 株式会社タイヘイ産商 Cold storage box

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153103A (en) * 1990-03-13 1992-10-06 Fujitsu Limited Resist composition and pattern formation process
JPH04115163U (en) * 1991-03-25 1992-10-12 株式会社タイヘイ産商 Cold storage box

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