JPS6070443A - Formation of micropattern - Google Patents

Formation of micropattern

Info

Publication number
JPS6070443A
JPS6070443A JP58178116A JP17811683A JPS6070443A JP S6070443 A JPS6070443 A JP S6070443A JP 58178116 A JP58178116 A JP 58178116A JP 17811683 A JP17811683 A JP 17811683A JP S6070443 A JPS6070443 A JP S6070443A
Authority
JP
Japan
Prior art keywords
group
resist
radiation
polymer
substrate
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
JP58178116A
Other languages
Japanese (ja)
Inventor
Tsukasa Tada
宰 多田
Akitoshi Kumagai
熊谷 明敏
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.)
Toshiba Corp
Original Assignee
Toshiba Corp
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 Toshiba Corp filed Critical Toshiba Corp
Priority to JP58178116A priority Critical patent/JPS6070443A/en
Publication of JPS6070443A publication Critical patent/JPS6070443A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

PURPOSE:To enable formation of a resist micropattern good in adhesion to a substrate with a small amt. of radiation to be irradiated by using a resist made of a mixture of specified radiation decomposable type polymers. CONSTITUTION:A substrate is coated as a radiation sensitive resist film with a mixture of one of a polymer group A made of a homopolymer of a monomer represented by formula I in which R1 is methyl or Cl and R2 is haloalkyl, or its copolymer with another vinyl monomer, and one of a polymer group B made of a copolymer of a monomer represented by formula II in which R3 is <9C alkyl. After it is prebaked at a proper temp., this resist film is exposed to radiation in a desired pattern. A resist micropattern superior in adhesion to the substrate is obtained by developing it to remove the irradiated parts selectively. As the polymer usable as said [A] group, polyrifluoroethyl alpha-chloroacryate, polytrifluoroisopropyl alpha-chloroacrylate, etc. are enumerated, and the polymer usable as the [B] group, cpolymers of methyl methacrylate-methacrylic acid and ethyl methacrylate-methacrylic acid are enumerated.

Description

【発明の詳細な説明】 し発明の技術分野〕 本発明は着板上の重合体1jtjj漠に電子線、X線、
イオン粒子線等の放射線を照射し微細パターンを形成す
る方法に関し、特に改良した重合体薄膜を用いてパター
ンを形成する方法に関する。
DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention broadly relates to the use of electron beams, X-rays,
The present invention relates to a method of forming a fine pattern by irradiating radiation such as an ion particle beam, and particularly to a method of forming a pattern using an improved polymer thin film.

〔発明の技術的背景とその問題点〕[Technical background of the invention and its problems]

近年、半導体素子の高密度化に伴い放射線によるリソグ
ラフィー技術が導入されてきた。ところで放射線リソグ
ラフィーによるレジストパターン形成法は、基板上に放
射線感応レジスト膜を被覆し、このレジスト膜に放射線
を所望のパターンに照射した後、現像処理を施してレジ
スト膜にパターンを形成させ、その後このレジストパタ
ーンをマスクとして湿式或いはドライエツチングを施し
該基板IK所望のパターンを蝕刻形成するものである。
In recent years, lithography technology using radiation has been introduced as the density of semiconductor devices has increased. By the way, in the resist pattern formation method using radiation lithography, a radiation-sensitive resist film is coated on a substrate, this resist film is irradiated with radiation in a desired pattern, and then a development process is performed to form a pattern on the resist film. Wet or dry etching is performed using the resist pattern as a mask to form a desired pattern on the substrate IK.

これ迄高密度なポジ型放射線レジストとしてはポリトン
フルオロエチルα−クロルアクリレートなどの含ハロゲ
ンポジ型レジストが用いられてきたがこれらのレジスト
は特にシリコン、酸化シリコン窒化クリコンなどのシリ
コン系半導体電板との接着性が悪く、これら半導体基板
上でパターンを形成させた場合には基板との接着性不良
によるパターン変形が生じやすいという欠点があった。
Hitherto, halogen-containing positive resists such as polytonfluoroethyl α-chloroacrylate have been used as high-density positive radiation resists, but these resists are particularly suitable for silicon-based semiconductor substrates such as silicon, silicon oxide, silicon nitride, etc. They have poor adhesion with semiconductor substrates, and when patterns are formed on these semiconductor substrates, there is a drawback that pattern deformation is likely to occur due to poor adhesion with the substrate.

〔発明の目的J 本発明は上記実情に鑑みなされたもので、改良されたレ
ジスト膜を用いることによって感度や解像性を低下させ
ることなく基板との接着性に優れた微細レジストパター
ン全形成し得る方法を提供しようとするものである。
[Objective of the Invention J The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to completely form a fine resist pattern with excellent adhesion to a substrate without reducing sensitivity or resolution by using an improved resist film. We are trying to provide a way to obtain it.

〔発明の概要〕[Summary of the invention]

すなわち本発明は(AJ群より選ばれる1種類以上の重
合体とCBJ群より選ばれる1種類以上の重合体との混
合物を放射線用レジスト膜として基板上に形成させ、適
当な温度でプリベーク処理を施した後、このレジスト膜
に放射線を所望の)くターンに照射し、現像処理を施す
ことによって照射した部分全選択的に除去し基板との接
着性の優れた微細レジストパターンを形成させることt
−特徴とするものである。
That is, the present invention (forms a mixture of one or more polymers selected from the AJ group and one or more polymers selected from the CBJ group on a substrate as a radiation resist film, and prebakes at an appropriate temperature). After applying radiation, the resist film is irradiated with radiation in a desired number of turns and developed to selectively remove all the irradiated areas to form a fine resist pattern with excellent adhesion to the substrate.
-It is a characteristic.

但し く但し亀はメチル基ないしは塩素原子、島は−・ロゲン
化アルキル基を示す) (1)式で示されるモノマーの単独重合体或いはそれと
他のビニル糸上ツマ−との共重合体からなる重合体群。
(However, the tortoise represents a methyl group or a chlorine atom, and the island represents a rogenated alkyl group) (1) Consists of a homopolymer of the monomer represented by the formula or a copolymer of it and other vinyl yarn threads. Polymer group.

CB、1群 (但し−は炭素数が8個以下のアルキル基を示す)(2
)式で示される七ツマ−とメタクリル酸との共重合体か
らなる重合体群。
CB, Group 1 (- indicates an alkyl group having 8 or less carbon atoms) (2
) A group of polymers consisting of a copolymer of hetamine and methacrylic acid represented by the formula.

本発明に於て(A)群として用いる重合体としてはポリ
トリフルオロエチルα−クロルアクリレート、ポリトリ
ノルオロイングロビルα−クロルアクリレート、ポリト
リフルオロt−ブチルα−クロルアクリレート、ポリ1
−メトキントリフルオロエチルα−クロルアクリレート
、ポリトリフルオロエチルメタクリレート、ポリトリク
ロルエチルメタクリレート、ポリへキサフルオロブチル
メタクリレート等を挙げることができる。
In the present invention, the polymers used as Group (A) include polytrifluoroethyl α-chloroacrylate, polytrinoroloinglovir α-chloroacrylate, polytrifluoro t-butyl α-chloroacrylate, poly1
-methquin trifluoroethyl α-chloroacrylate, polytrifluoroethyl methacrylate, polytrichloroethyl methacrylate, polyhexafluorobutyl methacrylate, and the like.

(B)群として用いるレジストとしては、メチルメタク
リレート−メタクリル酸共重合体、エチルメタクリレー
ト−メタクリル酸共重合体、イソプロピルメタクリレー
ト−メタクリル酸共重合体。
The resists used in group (B) include methyl methacrylate-methacrylic acid copolymer, ethyl methacrylate-methacrylic acid copolymer, and isopropyl methacrylate-methacrylic acid copolymer.

t−ブチルメタクリレート−メタクリル酸共重合体、n
−ブチルメタクリレート−メタクリル酸共重合体、イソ
ペンチルメタクリレート−メタクリル酸共重合体等を挙
げることができる。
t-butyl methacrylate-methacrylic acid copolymer, n
-butyl methacrylate-methacrylic acid copolymer, isopentyl methacrylate-methacrylic acid copolymer, and the like.

CBJ群として用いる重合体の分子量は高分子量である
必要はなく、塗布溶媒に溶けやすいことが好ましく、分
子量としては百方以下であることが好ましい。またCB
)群として用いる重合体のメタクリル酸の共重合体比率
が大きくなると有機6媒への溶解性が低下するため、メ
タクリル酸の共重合体比率が30モルチ以下であること
が好ましい。
The molecular weight of the polymer used as the CBJ group does not need to be high, but it is preferable that it is easily soluble in the coating solvent, and the molecular weight is preferably 100 or less. Also CB
If the copolymer ratio of methacrylic acid in the polymer used as the group ) increases, the solubility in the organic hexa-medium decreases, so it is preferable that the copolymer ratio of methacrylic acid is 30 molar or less.

本発明に使用する基板としては、例えば不純物をドープ
したシリコン基板単独、或いはこの基板を母材として酸
化シリコン層を介して多結晶7リコン膜を設けたものな
どの半導体基板、ガリウムヒ素等の化合物半導体基板、
または透明ガラス板上にクロム膜、或いは酸化クロム膜
を積層したものなどのマスク基板等を挙げることができ
る。
Substrates used in the present invention include, for example, a single silicon substrate doped with impurities, a semiconductor substrate such as one in which a polycrystalline 7-licon film is provided via a silicon oxide layer using this substrate as a base material, and a compound such as gallium arsenide. semiconductor substrate,
Alternatively, a mask substrate such as a chromium film or a chromium oxide film laminated on a transparent glass plate can be used.

〔発明の効果〕〔Effect of the invention〕

しかして本発明に用いるレジストは、親水性があり、基
板との接着性を強める一〇〇〇H基をもつ共重合体をレ
ジストの成分として含有するため。
However, the resist used in the present invention is hydrophilic and contains as a component a copolymer having 1000H groups that strengthens the adhesiveness with the substrate.

基板との接着性の良好なレジスト膜を形成することが可
能となる。但し本レジストに於けるCBJ群の共重合体
の混合比率が増大しすぎると、CAJ群に属する重合体
の本来の性質である感度、解像度という特性が損なわれ
るため、CBJ群の共重合体の混合比率がlO重量多以
下であることが好ましい。即ち本発明によれば、上記の
条件で混合された重合体を放射線用ポジ型レジストとし
て用いることによって、少ない照射量で基板との接着性
の良好な微細レジストパターンを容易に得ることが可能
となる。
It becomes possible to form a resist film with good adhesion to the substrate. However, if the mixing ratio of the CBJ group copolymers in this resist increases too much, the original properties of the CAJ group polymers, such as sensitivity and resolution, will be impaired. It is preferable that the mixing ratio is 10% by weight or less. That is, according to the present invention, by using the polymer mixed under the above conditions as a positive resist for radiation, it is possible to easily obtain a fine resist pattern with good adhesion to the substrate with a small irradiation dose. Become.

〔発明の実施例〕[Embodiments of the invention]

実施例1 ポリトリフルオロエチルα−クロルアクリレート(分子
量60万)とメチルメタクリレート−メタクリル酸共重
合体(80:20)(分子−1ijt1万)を95:5
(重量比)の割合で混合したレジストを、酸化シリコン
膜を形成させたシリコン基板上にスピンコーティングに
よって1μの膜厚に塗布し、200°01時間のプリベ
ーク処理を行った。
Example 1 Polytrifluoroethyl α-chloroacrylate (molecular weight 600,000) and methyl methacrylate-methacrylic acid copolymer (80:20) (molecule-1ijt 10,000) in a ratio of 95:5
A resist mixed at a ratio of (weight ratio) was applied to a film thickness of 1 μ by spin coating on a silicon substrate on which a silicon oxide film was formed, and prebaked at 200° C. for 1 hour.

また比較例として同様な方法で酸化シリコン基板上にポ
リトリフルオロエテルα−クロルアクリレートを1μの
膜厚で形成させた。
Further, as a comparative example, polytrifluoroether α-chloroacrylate was formed to a thickness of 1 μm on a silicon oxide substrate by the same method.

次に上記2種類のレジン) 、fflにビーム径0.1
μ、加速d圧20KVの遊子ビームを0.5μライフ 
1.0μ、X、/<−ス、長さ100μのパターン状K
 10μC/dの照射量で照射し、MIBK(メチルイ
ソブチルケトン)−IPA(イングロビルアルコール)
(65:35体積比)混合液からなる現像液によってパ
ターンを形成させた。形成されたパターンを観察したと
ころ、本発明による混合レジストパターンの方はパター
ン流れがなく0.5μの微細パターンが形成されていた
が、ボIJ ) ’Jフルオロエチルα−クロルアクリ
レート単独か′ら成るレジストの方は一部にパターン流
れが認められた。その後CF4−)(、(70:30 
分圧比)混合ガスを用いて上記混合レジストパターンを
マスクトシたドライエツチングを行い、酸素プラズマで
レジストヲ除去したところレジストパターンが鮮明にe
ABシリコン基板上に転写されていることが確認された
Next, add the above two types of resin), beam diameter 0.1 to ffl
μ, acceleration d pressure 20KV playback beam 0.5μ life
1.0μ, X, /<-s, length 100μ pattern K
MIBK (methyl isobutyl ketone)-IPA (inglovir alcohol) was irradiated with a dose of 10 μC/d.
A pattern was formed using a developer consisting of a mixed solution (65:35 volume ratio). When the formed pattern was observed, it was found that the mixed resist pattern according to the present invention had no pattern flow and a fine pattern of 0.5 μm was formed. Pattern flow was observed in some parts of the resist. Then CF4-)(,(70:30
Partial pressure ratio) Dry etching was performed using a mixed gas to mask the mixed resist pattern, and when the resist was removed with oxygen plasma, the resist pattern was clearly visible.
It was confirmed that the image was transferred onto the AB silicon substrate.

実施例2 ポリトリノルオロイングロビルα−クロルアクリレート
(分子量100万)とメチルメタクリレート−メタクリ
ル酸共重合体(80:20)(分子量1万)を95:5
(重量比)の割合で混合したレジストを、シリコン基板
上にスピンコーティングによって1μの膜厚に塗布し、
180°01時間のプリベーク処理を行った。また比較
例として同様な方法でシリコン基板上にポリトリフルオ
ロインプロビルα−クロルアクリレートを1μの膜厚で
形成させた。
Example 2 Polytrinofluoroinglovir α-chloroacrylate (molecular weight 1 million) and methyl methacrylate-methacrylic acid copolymer (80:20) (molecular weight 10,000) were mixed in a 95:5 ratio.
A resist mixed at a ratio of (weight ratio) is applied to a film thickness of 1μ on a silicon substrate by spin coating,
Pre-baking treatment was performed for 180°01 hour. In addition, as a comparative example, polytrifluoroimprovil α-chloroacrylate was formed to a thickness of 1 μm on a silicon substrate by the same method.

次に上記2種類のレジスト膜にビーム径0.1μ加速電
圧20KVの電子ビームを0.5μライフ 1.0μス
ペース、長さ100μのパターン状に10μΩ侃(7)
[射景で照射し、MIBK(メチルイソブチルケトン)
=IPA(イングロビルアルコール)(50:50体積
比)混合液からなる現像液によってパターンを形成させ
た。形成されたパターンを観察したところ混合レジスト
パターンの方ハパp−7流れがなく0.5μの微細パタ
ーンが形成されていたが、ポリトリフルオロインプロビ
ルα−クロルアクリレート単独から成るレジストの方は
かなりの部分にパターン流れが認められた。その後CF
402 (96: 4分圧比)混合ガスを用いで上記混
合レジストパターンをマスクとしてドライエツチングを
行い、酸素プラズマでレジストを除去したところレジス
トパターンがバ;を明にシリコン基板上に転写されてい
ることが確認てれた。
Next, an electron beam with a beam diameter of 0.1μ and an acceleration voltage of 20KV is applied to the above two types of resist films in a pattern with a life of 0.5μ, a space of 1.0μ, and a length of 100μ with a 10μΩ resistance (7).
[MiBK (methyl isobutyl ketone)
A pattern was formed using a developer consisting of a mixed solution of = IPA (Inglovir alcohol) (50:50 volume ratio). When we observed the formed patterns, we found that the mixed resist pattern had no Hapa p-7 flow and a fine pattern of 0.5 μm was formed, but the resist consisting of polytrifluoroimprovyl α-chloroacrylate alone had a much smaller pattern. Pattern flow was observed in the area. Then CF
Dry etching was performed using a 402 (96:4 partial pressure ratio) mixed gas using the above mixed resist pattern as a mask, and when the resist was removed with oxygen plasma, the resist pattern was clearly transferred onto the silicon substrate. was confirmed.

以上詳述した如く、特定の放射線分解型重合体の混合物
からなるレジン) fc用いることによって少い放射線
照射量で基板との接着性の良好な微細レジストパターン
の形成が可能となり、もって半導体基板、マスク基板な
どの微細加工に有効に利用できる実用性の高い微細パタ
ーン形成法を提供できるものである。
As detailed above, by using a resin made of a mixture of specific radiation-decomposable polymers (FC), it is possible to form a fine resist pattern with good adhesion to the substrate with a small amount of radiation irradiation. It is possible to provide a highly practical fine pattern forming method that can be effectively used for fine processing of mask substrates and the like.

Claims (1)

【特許請求の範囲】[Claims] (1) 電子線、X線、イオン粒子線等の放射線によっ
て微細パターンを形成させる方法に於て、(A)群より
選ばれる1種類以上の重合体とLBJ群より選ばれるl
 fm類以上の重合体との混合物をボ(AJ群 (但しR1はメチル基または塩素浮子、E2は−・ログ
ン化アルキル基を示す) (1)式で示されるモノマーの単独重合体或いはそれと
他のビニル系モノマーとの共重合体から成る重合体群 C83群 重合体から成る重合体群 (2+ [、AJ群が一般式(3)で示される重合体群
1 (但し[R4ば−CH2CFs 、 −Ci−1(C)
J3 ) CB”3 、−C(Ci(3)2 CF3、
−CH2CF2CHF2 、−CH(OCH3)C1偽
基を示す。) であり、CBJ群がメチルメタクリレートとメタクリル
酸との共重合体群であることを特徴とする特許請求の範
囲第1項記載のCタ細バターkb’x、”’71 。
(1) In a method of forming a fine pattern using radiation such as an electron beam, an X-ray, or an ion particle beam, one or more polymers selected from the group (A) and l selected from the LBJ group are used.
A homopolymer of the monomer represented by the formula (1) or other monomers (AJ group (where R1 is a methyl group or chlorine float, E2 is a -logonated alkyl group) is a mixture with a polymer of fm class or higher. Polymer group C83 consisting of a copolymer with vinyl monomers Polymer group 1 consisting of a polymer (2+ [, AJ group is represented by the general formula (3) (However, [R4ba-CH2CFs, -Ci-1(C)
J3) CB”3, -C(Ci(3)2 CF3,
-CH2CF2CHF2, -CH(OCH3)C1 pseudogroup. ) and the CBJ group is a copolymer group of methyl methacrylate and methacrylic acid.
JP58178116A 1983-09-28 1983-09-28 Formation of micropattern Pending JPS6070443A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58178116A JPS6070443A (en) 1983-09-28 1983-09-28 Formation of micropattern

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58178116A JPS6070443A (en) 1983-09-28 1983-09-28 Formation of micropattern

Publications (1)

Publication Number Publication Date
JPS6070443A true JPS6070443A (en) 1985-04-22

Family

ID=16042934

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58178116A Pending JPS6070443A (en) 1983-09-28 1983-09-28 Formation of micropattern

Country Status (1)

Country Link
JP (1) JPS6070443A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62223750A (en) * 1986-03-26 1987-10-01 Toray Ind Inc Radiation sensitive positive type resist and such resist composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62223750A (en) * 1986-03-26 1987-10-01 Toray Ind Inc Radiation sensitive positive type resist and such resist composition

Similar Documents

Publication Publication Date Title
JP2824350B2 (en) Device manufacturing method
JP3368888B2 (en) Organometallic polymers and uses thereof
JPS60229026A (en) Manufacture of electronic device
JPS5949536A (en) Formation of micropattern
JPH02191957A (en) Resist composition
US4476217A (en) Sensitive positive electron beam resists
US4268607A (en) Method of patterning a resist layer for manufacture of a semiconductor element
JPS58118641A (en) Radiation sensitive positive type resist for forming fine pattern
JPS6070443A (en) Formation of micropattern
US4414313A (en) Sensitive positive electron beam resists
JPH0480377B2 (en)
JPS58214148A (en) Resist material and formation of micropattern
JPS608842A (en) Formation of pattern
JPS5828571B2 (en) Resist formation method for microfabrication
JPH0358104B2 (en)
JPH07196743A (en) Radiation-sensitive material and method for forming pattern
JPS6111738A (en) Formation of fine pattern
JPS58113932A (en) Resist material and formation of resist micropattern using it
JPH087441B2 (en) Positive type high sensitivity radiation sensitive resist
JPH0682215B2 (en) Radiation resist and pattern forming method using the same
JPS60252348A (en) Formation of pattern
JPS6259950A (en) Ionizing radiation sensitive positive type resist
JP2548308B2 (en) Pattern formation method
JPS5999720A (en) Forming method of resist image
JPS60138541A (en) Formation of pattern