JPH054665B2 - - Google Patents

Info

Publication number
JPH054665B2
JPH054665B2 JP61126591A JP12659186A JPH054665B2 JP H054665 B2 JPH054665 B2 JP H054665B2 JP 61126591 A JP61126591 A JP 61126591A JP 12659186 A JP12659186 A JP 12659186A JP H054665 B2 JPH054665 B2 JP H054665B2
Authority
JP
Japan
Prior art keywords
layer
resist
pattern
organic polymer
polymer layer
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
JP61126591A
Other languages
Japanese (ja)
Other versions
JPS62280839A (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 JP61126591A priority Critical patent/JPS62280839A/en
Publication of JPS62280839A publication Critical patent/JPS62280839A/en
Publication of JPH054665B2 publication Critical patent/JPH054665B2/ja
Granted 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
    • G03F7/075Silicon-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

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明はレジスト材料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材料およびパターン形
成方法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resist material and a pattern forming method, and more particularly to a resist material and a pattern forming method suitable for manufacturing semiconductor integrated circuits, magnetic bubble memories, and the like.

(従来の技術) 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方法として、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、次いで露光、現像、転
写を行つて微細パターンを形成するものである。
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。
(Prior Art) 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. In this method, after forming an organic polymer layer 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.

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57−12386号) (発明が解決しようとする問題点) 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。
Trimethylsilylstyrene or a copolymer thereof has been proposed as a silicon-containing resist sensitive to X-rays, electron beams, or deep ultraviolet rays.
(Japanese Patent Application No. 57-12386) (Problems to be Solved by the Invention) However, the dry etching resistance of these materials is not necessarily satisfactory. In general, when dry etching resistance is insufficient, (1) etching conditions during pattern transfer are restricted; (2)
Problems arise such as the etching time becomes long and (3) the mask pattern is not transferred accurately, resulting in so-called pattern conversion differences.

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 with strong dry etching resistance suitable for a two-layer resist method and a method for using the same.

(問題点を解決するための手段) 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材料および基板上に有機高
分子層を形成する工程、該有機高分子層上にレジ
スト層を形成する工程、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、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からなるパターン形
成方法において、前記レジスト層の材料として下
記一般式で示されるスチレン系重合体からなるレ
ジスト材料を用いることからなる。
(Means for Solving the Problems) The present invention provides a process for forming an organic polymer layer on a resist material and a substrate made of a styrene polymer represented by the following general formula, and a resist layer on the organic polymer layer. 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. A resist material made of a styrene polymer represented by the following general formula is used as the material.

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重合体は、クロルメチル
基を含む単量体とシリコン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、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、できるだけ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 styrene 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 polymer according to the present invention is used as a resist, and the higher the number, the higher the sensitivity. 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)
It 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シリコン原子を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、前記した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; the higher the silicon content, the stronger the etching resistance. Since the styrenic polymer according to the present invention contains a large amount of a monomer containing two silicon atoms, it has a large silicon content. As a result, the etching problems mentioned above can be significantly 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、n′,m′は正の整数を表わし、
R1,R2,R3,R4,R5,R6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、深紫外線あるいはイオンビームを照
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, m, n', m' represent positive integers,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent a lower alkyl group or a hydrogen atom. ) The styrenic polymer synthesized in this way has
After irradiation with radiation, electron beam, deep ultraviolet rays, or ion beam, only the irradiated area can be left by developing with an appropriate organic solvent, so the styrenic polymer according to the present invention can be used as a so-called negative resist. .

更に、本発明のレジスト材料を二層レジスト法
に適用するには、まず加工を施すべき基板上にス
ピンコート法等により厚い有機高分子層を設けた
後、本発明のレジスト材料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て所望の微
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。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できる。又、この厚い有
機高分子層をイオン打ち込みのマスクに用いるこ
ともできる。あるいはリフトオフプロセスへの適
用も可能である。
Furthermore, in order to apply the resist material of the present invention to the two-layer resist method, first a thick organic polymer layer is provided on the substrate to be processed by spin coating or the like, and then a layer made of the resist material of the present invention is applied. Formed on the organic polymer layer. Thereafter, a desired fine pattern is drawn using X-rays, electron beams, deep ultraviolet rays, etc., and then a desired fine negative pattern is obtained using an appropriate developer. Using the obtained fine pattern as a mask, the pattern can be transferred to the organic polymer layer by reactive ion etching using oxygen. Thereafter, the workpiece can be etched using the thick organic polymer layer with the fine pattern formed thereon as a mask. Moreover, 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.

(実施例) 以下、実施例に基き詳細に説明する。(Example) Hereinafter, a detailed explanation will be given based on examples.

実施例 1 (1) 単量体の合成 300ml三つ口フラスコ中に、粉砕したAlCl326.7
g(0.2モル)とヘキサメチルジシラン29.3g
(0.2モル)を仕込み、室温で攪拌しながらアセチ
ルクロライド15.7g(0.2モル)を2〜3時間か
けて滴下した。途中、溶液は均一になつた。滴下
終了後、更に1時間室温で反応を続けた。その
後、減圧蒸留により、目的とするクロロペンタメ
チルジシランを得た。収量27g(81%)沸点71
℃/100mmHg 次に、乾燥窒素ガスで三つ口フラスコ内を置換
後、グリニヤール用マグネシウム1.5g(0.06グ
ラム原子)および脱水した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)と脱水したTHF50ml
からなる溶液を攪拌しながら滴下し、反応させ
た。次いで、50〜60℃に保ちながら、先ほど合成
したクロロペンタメチルジシラン1.7g(0.05モ
ル)と脱水したTHF15mlからなる溶液を滴下し、
反応させた。滴下後、加温を止めて、約1時間攪
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。エーテル除去後、減圧蒸留で目的とす
る単量体を得た。収量5.3g(45%)沸点75〜77
℃/0.45mmHg (2) 重合体の合成 (1)で合成した単量体4.7g、クロロメチル化ス
チレン0.3g、AIBN30mg、ベンゼン5mlを重合
管に仕込み、脱気後、70℃で15時間かけて重合反
応を行つた。反応後、メタノール中に反応溶液を
投入することにより、白色ポリマーを得た。メチ
ルエチルケトン−メタノール系を用いて、常法に
より分別精鉄を行つた。収量2.2g(44%)GPC
より求めた重量平均分子量は約105000、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。
Example 1 (1) Synthesis of monomer In a 300ml three-necked flask, pulverized AlCl 3 26.7
g (0.2 mol) and 29.3 g of hexamethyldisilane
(0.2 mol) was charged, and 15.7 g (0.2 mol) of acetyl chloride was added dropwise over 2 to 3 hours while stirring at room temperature. During the process, the solution became homogeneous. After the dropwise addition was completed, the reaction was continued for another 1 hour at room temperature. Thereafter, the desired chloropentamethyldisilane was obtained by distillation under reduced pressure. Yield 27g (81%) Boiling point 71
C/100 mmHg Next, after purging the inside of the three-necked flask with dry nitrogen gas, 1.5 g (0.06 gram atom) of Grignard magnesium and 10 ml of dehydrated THF were charged.
After adding a small amount of ethyl bromide, 8 g (0.06 mol) of P-chlorostyrene and 50 ml of dehydrated THF
A solution consisting of was added dropwise with stirring to cause a reaction. Next, while maintaining the temperature at 50 to 60°C, a solution consisting of 1.7 g (0.05 mol) of chloropentamethyldisilane synthesized earlier and 15 ml of dehydrated THF was added dropwise.
Made it react. After the dropwise addition, heating was stopped and the mixture was stirred for about 1 hour. Next, after adding 100 ml of water, ether extraction was performed, and the ether layer was dried with magnesium sulfate. After removing the ether, the desired monomer was obtained by distillation under reduced pressure. Yield 5.3g (45%) Boiling point 75-77
°C/0.45mmHg (2) Polymer synthesis 4.7g of the monomer synthesized in (1), 0.3g of chloromethylated styrene, 30mg of AIBN, and 5ml of benzene were charged into a polymerization tube, and after degassing, the mixture was heated at 70℃ for 15 hours. A polymerization reaction was carried out. After the reaction, a white polymer was obtained by pouring the reaction solution into methanol. Fractional refining of iron was carried out by a conventional method using a methyl ethyl ketone-methanol system. Yield 2.2g (44%) GPC
The weight average molecular weight determined was approximately 105,000, and the polydispersity was approximately 1.4. Furthermore, from 1 H-NMR, it was confirmed that the polymer had the composition shown below, 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
スピンコート法により、0.3μm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、イソプロパノールに1分順次浸漬し
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 0.3 μm thick polymer layer according to the present invention was formed on a Si substrate by spin coating. Using an electron beam exposure device,
After irradiation of approximately 20 μC/cm 2 , the sample was sequentially immersed in a developing solution of THF:EtOH=1:1 for 1 minute and 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、スピンコート法によりMP−1300
(シプレー社製)を塗布し、250℃で1時間加熱処
理した。この時、MP−1300層の厚みは約1.5μm
であつた。次いで、このMP−1300層の上に実施
例2で調製したレジスト溶液を用いて、約0.3μm
厚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12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 MP-1300 was coated on a Si substrate by spin coating.
(manufactured by Shipley) was applied and heat treated at 250°C for 1 hour. At this time, the thickness of the MP-1300 layer is approximately 1.5μm.
It was hot. Next, the resist solution prepared in Example 2 was used on this MP-1300 layer to form a layer of about 0.3 μm.
A thick layer of polymer according to the invention was formed. Example 2
Similarly, a submicron negative pattern was obtained using an electron beam exposure device. Furthermore, etching was performed for 12 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) 本発明によつて、シリコン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
た。更にこ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
グによる厚い有機高分子層のエツチングのマスク
として十分な耐性を示し、有機高分子層へのパタ
ーン転写が精度良く行なわれた。
(Effects of the Invention) According to the present invention, a negative resist composition made of a styrene polymer containing silicon atoms was obtained. Furthermore, the pattern obtained by exposing and developing this resist composition has sufficient resistance as a mask for etching a thick organic polymer layer by dry etching, and the pattern can be transferred to the organic polymer layer with high precision. It was.

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材料。 2 基板上に有機高分子層を形成する工程、該有
機高分子層上にレジスト層を形成する工程、リソ
グラフイ技術を用いて該レジスト層に所望のパタ
ーンを形成する工程、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からな
るパターン形成方法において、前記レジスト層の
材料として一般式 (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
るレジスト材料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 material comprising a styrenic polymer represented by: 2. A step of forming an organic polymer layer on a substrate, a step of forming a resist layer on the organic polymer layer, a step of forming a desired pattern on the resist layer using lithography technology, and a step of using the pattern as a mask. In the pattern forming method comprising the step of dry etching the organic polymer layer, the material of the resist layer has a 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 pattern forming method characterized by using a resist material made of a styrene polymer.
JP61126591A 1986-05-30 1986-05-30 Resist material and pattern forming method Granted JPS62280839A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61126591A JPS62280839A (en) 1986-05-30 1986-05-30 Resist material and pattern forming method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61126591A JPS62280839A (en) 1986-05-30 1986-05-30 Resist material and pattern forming method

Publications (2)

Publication Number Publication Date
JPS62280839A JPS62280839A (en) 1987-12-05
JPH054665B2 true JPH054665B2 (en) 1993-01-20

Family

ID=14938972

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61126591A Granted JPS62280839A (en) 1986-05-30 1986-05-30 Resist material and pattern forming method

Country Status (1)

Country Link
JP (1) JPS62280839A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100504436B1 (en) * 2000-12-29 2005-07-29 주식회사 하이닉스반도체 Polymer for photoresist and prepartion thereof
US7326514B2 (en) * 2003-03-12 2008-02-05 Cornell Research Foundation, Inc. Organoelement resists for EUV lithography and methods of making the same

Also Published As

Publication number Publication date
JPS62280839A (en) 1987-12-05

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