JPH0427542B2 - - Google Patents

Info

Publication number
JPH0427542B2
JPH0427542B2 JP60277236A JP27723685A JPH0427542B2 JP H0427542 B2 JPH0427542 B2 JP H0427542B2 JP 60277236 A JP60277236 A JP 60277236A JP 27723685 A JP27723685 A JP 27723685A JP H0427542 B2 JPH0427542 B2 JP H0427542B2
Authority
JP
Japan
Prior art keywords
layer
resist composition
pattern
organic polymer
resist
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
Application number
JP60277236A
Other languages
Japanese (ja)
Other versions
JPS62135822A (en
Inventor
Fumitake Watanabe
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.)
NEC Corp
Original Assignee
Nippon Electric 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 Nippon Electric Co Ltd filed Critical Nippon Electric Co Ltd
Priority to JP60277236A priority Critical patent/JPS62135822A/en
Publication of JPS62135822A publication Critical patent/JPS62135822A/en
Publication of JPH0427542B2 publication Critical patent/JPH0427542B2/ja
Granted legal-status Critical Current

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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
    • G03F7/075Silicon-containing compounds
    • G03F7/0757Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はレジスト組成物およびパターン形成方
法に関し、特に半導体集積回路、磁気バブルメモ
リ等の製造に適するレジスト組成物およびパター
ン形成方法に関するものである。
[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a resist composition and a pattern forming method, and particularly to a resist composition and a pattern forming method suitable for manufacturing semiconductor integrated circuits, magnetic bubble memories, etc. .

〔従来の技術〕[Conventional technology]

最近、半導体集積回路、磁気バブルメモリ等の
製造に適する微細パターン形成法として、二層レ
ジスト法が提案されている。この方法は、基板上
に有機高分子層を形成した後、その上にシリコン
含有レジスト層を設け、次いて露光,現像,転写
を行つて微細パターンを形成する方法である。現
在、この二層レジスト法に適したシリコン含有レ
ジストの開発が盛んに行なわれている。そして、
この方法に用いるX線、電子線あるいは深紫外線
に感応するシリコン含有レジストとしてトリメチ
ルシリルスチレンあるいはその共重合体が提案さ
れている(特願昭57−123865)。
Recently, a two-layer resist method has been proposed as a fine pattern forming method suitable for manufacturing semiconductor integrated circuits, magnetic bubble memories, and the like. This method is a method in which an organic polymer layer is formed on a substrate, a silicon-containing resist layer is provided thereon, and then exposure, development, and transfer are performed to form a fine pattern. Currently, silicon-containing resists suitable for this two-layer resist method are being actively developed. and,
Trimethylsilylstyrene or a copolymer thereof has been proposed as a silicon-containing resist sensitive to X-rays, electron beams, or deep ultraviolet rays for use in this method (Japanese Patent Application No. 123,865/1983).

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

しかしながら、これらの材料のドライエツチン
グ耐性は必ずしも満足できるものではない。一般
にドライエツチング耐性が不十分の場合、(1)パタ
ーン転写時のエツチング条件が制限される、(2)エ
ツチング時間が長くなる、(3)マスクパターンが正
確に転写されない、いわゆる、パターン変換差を
生じる、等の問題を生じる。
However, the dry etching resistance of these materials is not always satisfactory. In general, when dry etching resistance is insufficient, (1) the etching conditions during pattern transfer are limited, (2) the etching time becomes longer, and (3) the mask pattern is not transferred accurately, resulting in so-called pattern conversion differences. arise, etc. problems.

本発明の目的は二層レジスト法に適したドライ
エツチング耐性の強いレジスト組成物およびその
使用方法を提供することにある。
An object of the present invention is to provide a resist composition suitable for a two-layer resist method and having strong dry etching resistance, and a method for using the same.

〔問題点を解決するための手段〕[Means for solving problems]

本発明は、下記一般式で示されるスチレン系重
合体からなるレジスト組成物および基板上に有機
高分子層を形成する工程と、該有機高分子層上に
レジスト組成物層を形成する工程と、リソグラフ
イ技術を用いて該レジスト組成物層に所望のパタ
ーンを形成する工程と、該パターンをマスクに前
記有機高分子層をドライエツチングする工程とか
らなり、前記レジスト組成物として下記一般式で
示されるスチレン系重合体からなるレジスト組成
物を用いるパターン形成方法である。
The present invention comprises a step of forming an organic polymer layer on a resist composition and a substrate made of a styrene polymer represented by the following general formula, a step of forming a resist composition layer on the organic polymer layer, It consists of a step of forming a desired pattern on the resist composition layer using lithography technology, and a step of dry etching the organic polymer layer using the pattern as a mask, and the resist composition is represented by the following general formula. This is a pattern forming method using a resist composition made of a styrene polymer.

一般式 (式中、n,mは正の整数を表わし、R1,R2
R3,R4,R5は低級アルキル基もしくは水素原子
を表わす。) 〔作用〕 本発明によるスチレン系重合体は、クロルメチ
ル基を含む単量体とケイ素原子を含む単量体とか
ら構成されている。クロルメチル基は、本発明に
よるスチレン系重合体をレジストとして用いる時
に感度をもたせる点で効果があり、これが多いほ
ど高感度になる。しかしながら、クロルメチル基
の導入は後述するドライエツチング耐性の低下を
もたらすために、なるべく少ない方が好ましい。
又、感度向上の面においても、導入量が増すにつ
れてその効果は激減するので、m/(n+m)の
値として、0.01〜0.2程度が好ましい。
general formula (In the formula, n and m represent positive integers, and R 1 , R 2 ,
R 3 , R 4 and R 5 represent a lower alkyl group or a hydrogen atom. ) [Function] The styrenic polymer according to the present invention is composed of a monomer containing a chloromethyl group and a monomer containing a silicon atom. The chloromethyl group is effective in providing sensitivity when the styrenic polymer according to the present invention is used as a resist, and the more chloromethyl groups there are, the higher the sensitivity becomes. However, since the introduction of chloromethyl groups leads to a decrease in dry etching resistance, which will be described later, it is preferable to introduce as few chloromethyl groups as possible.
Also, in terms of improving sensitivity, the effect decreases dramatically as the amount introduced increases, so the value of m/(n+m) is preferably about 0.01 to 0.2.

一方、酸素を用いたドライエツチングにおいて
は、そのエツチング耐性と被エツチング材料のシ
リコン含有量とは強く相関しており、シリコン含
有量が高いほどエツチング耐性が強くなる。本発
明によるスチレン系重合体はケイ素原子を2個含
む単量体を多く含むために、シリコン含有量が多
くなる。その結果、前記エツチング上の問題をか
なり低減できる。
On the other hand, in dry etching using oxygen, there is a strong correlation between the etching resistance and the silicon content of the etched material, and the higher the silicon content, the stronger the etching resistance. Since the styrenic polymer according to the present invention contains a large amount of monomer containing two silicon atoms, it has a large silicon content. As a result, the etching problems mentioned above can be considerably reduced.

本発明によるスチレン系重合体は次のような方
法で合成される。
The styrenic polymer according to the present invention is synthesized by the following method.

(式中、n,mは正の整数を表わし、R1,R2
R3,R4,R5は低級アルキル基もしくは水素原子
を表わす。) このようにして合成したスチレン系重合体にX
線,電子線あるいは深紫外線を照射後、適当な有
機溶剤で現像することにより、照射部分のみを残
すことができるので、本発明によるスチレン系重
合体は、いわゆる、ネガ型レジストとして使用で
きる。
(In the formula, n and m represent positive integers, and R 1 , R 2 ,
R 3 , R 4 and R 5 represent a lower alkyl group or a hydrogen atom. ) The styrenic polymer synthesized in this way has
After irradiation with beams, electron beams, or deep ultraviolet rays, only the irradiated areas can be left by developing with a suitable organic solvent, so the styrenic polymer according to the present invention can be used as a so-called negative resist.

更に、本発明のレジスト組成物を二層レジスト
法に適用するには、まず加工を施すべき基板上に
スピン塗布法等により、厚い有機高分子層を設け
た後、本発明のレジスト組成物からなる層を前記
有機高分子層の上に形成する。その後、X線、電
子線あるいは深紫外線等を用いて、所望の微細パ
ターンを描画した後、適当な現像液を用いると、
所望の微細なネガパターンが得られる。得られた
微細パターンをマスクとして、酸素を用いた反応
性イオンエツチングにより、有機高分子層にパタ
ーン転写を行うことができる。
Furthermore, in order to apply the resist composition of the present invention to a two-layer resist method, first a thick organic polymer layer is provided on the substrate to be processed by spin coating, and then the resist composition of the present invention is applied. A layer is formed on the organic polymer layer. After that, a desired fine pattern is drawn using X-rays, electron beams, deep ultraviolet rays, etc., and then an appropriate developer is used.
A desired fine negative pattern can be obtained. Using the obtained fine pattern as a mask, the pattern can be transferred to the organic polymer layer by reactive ion etching using oxygen.

しかる後、微細パターンが形成された厚い有機
高分子層をマスクに被加工材をエツチングするこ
とが出来る。又、この厚い有機高分子層をイオン
打込みのマスクに用いることも出来る。或は、厚
い高分子有機層が得られることを利用してリフト
オフプロセスにも適用出来る。
Thereafter, the workpiece can be etched using the thick organic polymer layer with the fine pattern formed thereon as a mask. Further, this thick organic polymer layer can also be used as a mask for ion implantation. Alternatively, it can also be applied to a lift-off process by taking advantage of the fact that a thick polymeric organic layer can be obtained.

〔実施例〕〔Example〕

以下、実施例に基き本発明を詳細に説明する。 Hereinafter, the present invention will be explained in detail based on Examples.

実施例 1 (1) 単量体の合成 は次のような方法で合成した。Example 1 (1) Synthesis of monomer was synthesized in the following way.

乾燥窒素ガスでフラスコ内を置換後、グリニ
ヤール用マグネシウム1.5g(0.06グラム原子)
および乾燥THF10mlを仕込んだ。少量のエチ
ルブロマイドを加えた後、p−クロルスチレン
8g(0.06モル)と乾燥THF50mlからなる溶
液を滴下し、反応させた。
After replacing the inside of the flask with dry nitrogen gas, 1.5 g (0.06 gram atom) of magnesium for Grignard
and 10 ml of dry THF. After adding a small amount of ethyl bromide, a solution consisting of 8 g (0.06 mol) of p-chlorostyrene and 50 ml of dry THF was added dropwise to react.

次いで、約50℃に保ちながら、クロルペンタ
メチルジシルメチレン9g(0.05モル)と乾燥
THF15mlからなる溶液を滴下して反応させた。
滴下後、約1時間室温で撹拌した。次いで、水
を100ml加えた後、エーテル抽出を行い、エー
テル層を硫酸マグネシウムで乾燥させた。
Next, while maintaining the temperature at approximately 50°C, add 9 g (0.05 mol) of chlorpentamethyldisylmethylene and dry.
A solution consisting of 15 ml of THF was added dropwise to react.
After the dropwise addition, the mixture was stirred at room temperature for about 1 hour. Next, after adding 100 ml of water, ether extraction was performed, and the ether layer was dried with magnesium sulfate.

エーテル除去後、減圧蒸留で生成物を得た。 After removing the ether, the product was obtained by vacuum distillation.

収量5.2g(収率42%)沸点104℃/2mmHg
であつた。
Yield 5.2g (yield 42%) Boiling point 104℃/2mmHg
It was hot.

(2) 重合体の合成 (1)で合成した単量体4.7g、クロルメチル化
スチレン0.3g、AIBN30mg、ベンゼン5mlを
重合管に仕込み、脱気後、70℃に保ち、15時間
をかけて重合反応を行つた。反応後、MeOH
中に反応溶液を投入することにより、白色ポリ
マーを得た。
(2) Synthesis of polymer 4.7 g of the monomer synthesized in (1), 0.3 g of chloromethylated styrene, 30 mg of AIBN, and 5 ml of benzene were charged into a polymerization tube, and after degassing, polymerization was carried out at 70°C for 15 hours. The reaction was carried out. After reaction, MeOH
By pouring the reaction solution into the solution, a white polymer was obtained.

MEK−MeOHを用いて、常法により分別精
製を行つた。収量は2.2g(収率44%)であつ
た。
Fractional purification was performed using MEK-MeOH using a conventional method. The yield was 2.2 g (yield 44%).

GPCにより求めた重量平均分子量は約
83000、多分散度は約1.4であつた。又、1H−
NMRから、ほぼ仕込み比通りの下記組成のポ
リマーであることを確認した。
The weight average molecular weight determined by GPC is approximately
83000, and the polydispersity was approximately 1.4. Also, 1 H−
From NMR, it was confirmed that the polymer had the following composition, which was almost the same as the charging ratio.

実施例 2 実施例1で合成した重合体1gをキシレン10ml
に溶解させて、レジスト溶液とした。Si基板上に
スピン塗布法により、0.2μm厚の本発明による重
合体層を形成した。電子線露光装置を用いて、約
20μC/cm2照射後、THF:EtOH=1:1の現像
液に1分間、次いで、イソプロパノールに1分間
浸漬した。その結果、Si基板上にほとんど膜べり
のないネガパターンが得られた。
Example 2 1 g of the polymer synthesized in Example 1 was added to 10 ml of xylene.
A resist solution was prepared by dissolving the resist solution. A 0.2 μm thick polymer layer according to the present invention was formed on a Si substrate by spin coating. Using an electron beam exposure device, approx.
After irradiation with 20 μC/cm 2 , it was immersed in a developing solution of THF:EtOH=1:1 for 1 minute and then in isopropanol for 1 minute. As a result, a negative pattern with almost no film loss was obtained on the Si substrate.

実施例 3 Si基板上に、スピン塗布法によりノボラツク樹
脂層を形成し、250℃で1時間加熱処理した。こ
の時、ノボラツク樹脂層の厚みは約1.5μmであつ
た。次いで、このノボラツク樹脂層の上に、実施
例2で調整したレジスト溶液を用いて、約0.2μm
の本発明による重合体層を形成した。実施例2と
同様に、電子線露光装置を用いて、サブミクロン
のネガパターンを得た。更に、反応性イオンエツ
チング装置(アネルバ社製DEM−451)を用い
て、酸素流量5SCCM、2.0Pa、0.16W/cm2の条件
で7分間エツチングを行つた。SEM観察の結果、
上層のサブミクロンのパターンが精度良く、下層
に転写されていることが分つた。
Example 3 A novolak resin layer was formed on a Si substrate by spin coating, and heat treated at 250°C for 1 hour. At this time, the thickness of the novolak resin layer was approximately 1.5 μm. Next, the resist solution prepared in Example 2 is applied onto this novolak resin layer to a thickness of about 0.2 μm.
A polymer layer according to the present invention was formed. As in Example 2, a submicron negative pattern was obtained using an electron beam exposure apparatus. Furthermore, etching was performed for 7 minutes using a reactive ion etching device (DEM-451 manufactured by Anelva Corporation) under conditions of an oxygen flow rate of 5 SCCM, 2.0 Pa, and 0.16 W/cm 2 . As a result of SEM observation,
It was found that the submicron pattern on the upper layer was transferred to the lower layer with good accuracy.

〔発明の効果〕 本発明によれば、ケイ素原子を含むスチレン系
重合体からなるネガ型レジスト組成物が得られ、
更に、本発明のレジスト組成物を露光、現像する
ことによつて得られるパターンはドライエツチン
グにより、厚い有機高分子層をエツチングする際
のマスクとして充分な耐性を示し、有機高分子層
へのパターン転写を精度良く行なうことができる
効果を有するものである。
[Effects of the Invention] According to the present invention, a negative resist composition made of a styrene polymer containing silicon atoms can be obtained,
Furthermore, the pattern obtained by exposing and developing the resist composition of the present invention has sufficient resistance as a mask when etching a thick organic polymer layer by dry etching, and can be used as a mask when etching a thick organic polymer layer. This has the effect that transfer can be performed with high precision.

Claims (1)

【特許請求の範囲】 1 一般式 (式中、n,mは正の整数を表わし、R1,R2
R3,R4,R5は低級アルキル基もしくは水素原子
を表わす。)で示されるスチレン系重合体からな
ることを特徴とするレジスト組成物。 2 基板上に有機高分子層を形成する工程と、該
有機高分子層上にレジスト組成物層を形成する工
程と、リソグラフイ技術を用いて該レジスト組成
物層に所望のパターンを形成する工程と該パター
ンをマスクに前記有機高分子層をドライエツチン
グする工程とからなり、前記レジスト組成物とし
て一般式 (式中、n,mは正の整数を表わし、R1,R2
R3,R4,R5は低級アルキル基もしくは水素原子
を表わす。)で示されるスチレン系重合体からな
るレジスト組成物を用いることを特徴とするパタ
ーン形成方法。
[Claims] 1. General formula (In the formula, n and m represent positive integers, and R 1 , R 2 ,
R 3 , R 4 and R 5 represent a lower alkyl group or a hydrogen atom. ) A resist composition comprising a styrenic polymer represented by: 2. A step of forming an organic polymer layer on a substrate, a step of forming a resist composition layer on the organic polymer layer, and a step of forming a desired pattern on the resist composition layer using lithography technology. and a step of dry etching the organic polymer layer using the pattern as a mask. (In the formula, n and m represent positive integers, and R 1 , R 2 ,
R 3 , R 4 and R 5 represent a lower alkyl group or a hydrogen atom. ) A pattern forming method characterized by using a resist composition made of a styrene polymer.
JP60277236A 1985-12-09 1985-12-09 Resist composition and pattern forming method Granted JPS62135822A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60277236A JPS62135822A (en) 1985-12-09 1985-12-09 Resist composition and pattern forming method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60277236A JPS62135822A (en) 1985-12-09 1985-12-09 Resist composition and pattern forming method

Publications (2)

Publication Number Publication Date
JPS62135822A JPS62135822A (en) 1987-06-18
JPH0427542B2 true JPH0427542B2 (en) 1992-05-12

Family

ID=17580713

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60277236A Granted JPS62135822A (en) 1985-12-09 1985-12-09 Resist composition and pattern forming method

Country Status (1)

Country Link
JP (1) JPS62135822A (en)

Also Published As

Publication number Publication date
JPS62135822A (en) 1987-06-18

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