JP2593310B2 - Resist material - Google Patents
Resist materialInfo
- Publication number
- JP2593310B2 JP2593310B2 JP62118671A JP11867187A JP2593310B2 JP 2593310 B2 JP2593310 B2 JP 2593310B2 JP 62118671 A JP62118671 A JP 62118671A JP 11867187 A JP11867187 A JP 11867187A JP 2593310 B2 JP2593310 B2 JP 2593310B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- resist material
- polymerization
- seconds
- 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
Links
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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (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） 本発明は新規なレジスト材料、更に詳しくは高い解像
度を有し、耐ドライエツチング性に優れたネガ型の高エ
ネルギー線に感応するレジスト材料に関する。Description: FIELD OF THE INVENTION The present invention relates to a novel resist material, and more particularly, to a negative resist material having high resolution and excellent dry etching resistance, which is sensitive to negative high energy rays. .
（従来の技術） 一般に電子工業、印刷工業、精密機械工業等の分野、
例えば磁気バブル、集積回路、印刷版、シヤドーマスク
等の製造においては、レジスト被膜を使用し基板上にパ
ターンを形成する。即ちレジスト材料の溶液を例えば半
導体基板の表面に塗布し、必要に応じてベーキングして
レジスト被膜を基板上に形成した後に、高エネルギー線
を照射しレジスト被膜に所定のパターンの潜像を形成
し、その後、適当な現像液により現像する。(Prior art) In general, fields such as electronics industry, printing industry, precision machine industry,
For example, in the production of magnetic bubbles, integrated circuits, printing plates, shadow masks, and the like, a pattern is formed on a substrate using a resist film. That is, for example, a solution of a resist material is applied to the surface of a semiconductor substrate, and baked as necessary to form a resist film on the substrate, and then a high-energy ray is irradiated to form a latent image of a predetermined pattern on the resist film. Thereafter, development is performed with an appropriate developer.
従来、アセチレン系炭化水素又はその誘導体の重合体
からなるレジスト材料は余り知られていない。即ち例え
ばフエニルアセチレン単独重合体は一般に不安定である
ためレジスト材料として用いられることは知られていな
い。それ以外のポリアセチレン系重合体として例えば （Ｒは水素又はメチルを示す）で表わされる構造単位を
含有する重合体からなるレジスト材料があるが、このレ
ジスト材料はポジ型のレジスト材料である。Conventionally, a resist material comprising a polymer of an acetylene-based hydrocarbon or a derivative thereof has been scarcely known. That is, for example, phenylacetylene homopolymer is not known to be used as a resist material because it is generally unstable. Other polyacetylene-based polymers such as There is a resist material comprising a polymer containing a structural unit represented by (R represents hydrogen or methyl), and this resist material is a positive resist material.
（発明が解決しようとする問題点） 本発明の目的は安定性を有し、ネガ型のレジスト材料
として有用な新規なレジスト材料を提供することにあ
る。(Problems to be Solved by the Invention) An object of the present invention is to provide a novel resist material which has stability and is useful as a negative resist material.
（問題点を解決するための手段） 本発明は一般式 （Ｚはアリーレン基を示す）で表わされる構造単位を含
有する重合体からなるレジスト材料に係る。(Means for Solving the Problems) The present invention has a general formula The present invention relates to a resist material comprising a polymer containing a structural unit represented by the formula (Z represents an arylene group).
本発明で用いる重合体は真空中で電子線、γ線等の高
エネルギー線の照射により架橋し、ネガ型レジスト材料
として有用である。The polymer used in the present invention is crosslinked by irradiation with high energy rays such as electron beams and γ rays in a vacuum, and is useful as a negative resist material.
本発明の一般式（１）においてＺは例えばフエニレン
基、ナフチレン基等のアリーレン基である。本発明で使
用する上記重合体は一般式（１）の１種の単位のみから
なる単独重合体、２種以上の一般式（１）の単位からな
る共重合体、或いは一般式（１）の単位と他の共重合可
能なアセチレン系化合物に由来する構造単位からなる共
重合体等を挙げることができる。上記アセチレン系化合
物としては、アセチレン、一般式CX≡CY（ＸはCl又は炭
素数１〜10のアルキル基、Ｙは炭素数１〜10のアルキル
基又はアリール基を示す）で表わされる化合物、例えば
１−クロロ−２−ブチルアセチレン、１−クロロ−２−
ヘキシルアセチレン、１−クロロ−２−オクチルアセチ
レン、１−クロロ−２−フエニルアセチレン、１−メチ
ル−２−フエニルアセチレン、１−ヘキシル−２−フエ
ニルアセチレン等を挙げることができる。上記共重合体
において一般式（１）の構造単位は約80重量％以上であ
ることが好ましい。In the general formula (1) of the present invention, Z is an arylene group such as a phenylene group and a naphthylene group. The polymer used in the present invention is a homopolymer composed of only one unit of the general formula (1), a copolymer composed of two or more units of the general formula (1), or a copolymer of the general formula (1). Copolymers comprising a unit and a structural unit derived from another copolymerizable acetylene-based compound can be exemplified. Examples of the acetylene-based compound include acetylene, a compound represented by the general formula CX≡CY (X represents Cl or an alkyl group having 1 to 10 carbon atoms, and Y represents an alkyl group or an aryl group having 1 to 10 carbon atoms), for example, 1-chloro-2-butylacetylene, 1-chloro-2-
Hexylacetylene, 1-chloro-2-octylacetylene, 1-chloro-2-phenylacetylene, 1-methyl-2-phenylacetylene, 1-hexyl-2-phenylacetylene and the like can be mentioned. In the above copolymer, the structural unit of the general formula (1) is preferably at least about 80% by weight.
本発明において一般式（１）の構造単位を有する重合
体を合成する重合反応の方式や条件は、任意に選択で
き、例えば塊状重合、溶液重合など各種の方式を採用す
ることができる。開始剤としては遷移金属化合物を用い
るのが最も好ましく、その他、放射線、熱などを用いて
も重合を開始させることができる。開始剤の使用量は、
単量体に対して１〜1000重量ppmの範囲から選ぶのが通
常であるが、この範囲に限定されるものではない。目的
重合体の重合度、反応時間、重合温度などの因子に依存
するからである。重合温度は通常−80〜250℃で、遷移
金属化合物を用いる場合、好ましくは−30〜100℃の範
囲である。溶液重合で使用できる溶媒としては、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素、テトラハ
イドロフラン、ジメチルホルムアミド、ジメチルスルホ
キシド、アセトニトリル、メチルエチルケトン、テトラ
ハイドロフラン、ジオキサン、二硫化炭素等の１種又は
２種以上の混合物を挙げることができる。In the present invention, the system and conditions of the polymerization reaction for synthesizing the polymer having the structural unit of the general formula (1) can be arbitrarily selected, and various systems such as bulk polymerization and solution polymerization can be adopted. It is most preferable to use a transition metal compound as the initiator, and it is also possible to initiate polymerization by using radiation, heat, or the like. The amount of initiator used is
Usually, it is selected from the range of 1 to 1000 ppm by weight based on the monomer, but is not limited to this range. This is because it depends on factors such as the degree of polymerization of the target polymer, the reaction time, and the polymerization temperature. The polymerization temperature is usually −80 to 250 ° C., and preferably −30 to 100 ° C. when a transition metal compound is used. Solvents that can be used in solution polymerization include one or two of aromatic hydrocarbons such as benzene, toluene, and xylene, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, acetonitrile, methylethylketone, tetrahydrofuran, dioxane, carbon disulfide, and the like. Mixtures of more than one species can be mentioned.
反応混合物から重合体を回収する場合も通常の方法が
採用されてよく、例えばアセトン、ベンゼン、トルエン
の如く重合体を溶解しうる溶剤に一旦溶解せしめたう
え、メタノールの如く重合体が溶解しない溶剤を加えて
重合体のみを再沈殿せしめればよい。When the polymer is recovered from the reaction mixture, a usual method may be employed.For example, once the polymer is dissolved in a solvent capable of dissolving the polymer such as acetone, benzene, and toluene, and then the solvent in which the polymer is not dissolved such as methanol is used. May be added to reprecipitate only the polymer.
本発明において上記重合体の分子量は、電子線に対し
て高感度という点からは分子量が高い方が好ましい。し
かし、著しく分子量が高い場合、現像時の膨潤が大きく
なり形成されるレジストパターンの解像度が低下する。
この為、重量平均分子量で10000〜2000000の範囲がよ
く、特に好ましくは、100000〜1500000の範囲である。In the present invention, the molecular weight of the polymer is preferably higher from the viewpoint of high sensitivity to an electron beam. However, when the molecular weight is extremely high, the swelling at the time of development becomes large, and the resolution of the formed resist pattern decreases.
For this reason, the weight average molecular weight is preferably in the range of 10,000 to 2,000,000, and particularly preferably in the range of 100,000 to 1,500,000.
更に、一般にネガ型のレジストにおける重合体の分子
量及び分子量分布は小さいほど解像度が向上するが、本
発明のレジストは、構造的に膨潤しにくい状態にあるた
め、分子量及び分子量分布の影響は受けにくい。Further, generally, the resolution is improved as the molecular weight and the molecular weight distribution of the polymer in the negative resist are smaller, but the resist of the present invention is hardly affected by the molecular weight and the molecular weight distribution because the resist of the present invention is in a state where it is hard to swell structurally. .
本発明の重合体のうち好ましいものはオルソ位にCF3
が置換したフエニル基を有するもの及び８位にCF3が置
換したナフチル基を有するものである。尚、本発明の重
合体の一部は特開昭60-166309号に記載されている。Preferred among the polymers of the present invention are CF 3 at the ortho position.
Are substituted phenyl groups and those having a naphthyl group substituted with CF 3 at the 8-position. A part of the polymer of the present invention is described in JP-A-60-166309.
本発明のレジスト材料は通常ベンゼン、トルエン、キ
シレン、モノクロルベンゼン等の芳香族化合物溶媒、ト
リクロロエタン、テトラクロロエタン等のクロロ脂肪族
炭化水素溶媒、メチルイソブチルケトン、エチルセロソ
ルブ、セロソルブアセテート等の極性溶媒に溶解して使
用される。この場合、濃度には限定はないが、一般には
５〜30重量％の範囲で用いるのが好ましい。The resist material of the present invention is usually dissolved in an aromatic compound solvent such as benzene, toluene, xylene and monochlorobenzene, a chloroaliphatic hydrocarbon solvent such as trichloroethane and tetrachloroethane, and a polar solvent such as methyl isobutyl ketone, ethyl cellosolve and cellosolve acetate. Used as In this case, the concentration is not limited, but it is generally preferable to use it in the range of 5 to 30% by weight.
本発明のレジスト材料は上記重合体から構成され、こ
の材料からなるレジスト被膜は公知の方法によつて現像
される。現像液は公知のものが使用でき、具体的にはア
セトン、メチルエチルケトン（MEK）、メチルイソブチ
ルケトンなどのケトン類またはこれとメタノール、イソ
ブロパノール（IPA）などのアルコール類との混合物、
酢酸エチル、酢酸イソアミルなどの脂肪酸エステル類ま
たはこれとアルコール類との混合物、モノクロルベンゼ
ン、トルエン、キシレンなどの芳香族炭化水素類または
これとアルコール類との混合物等を挙げることができ
る。The resist material of the present invention is composed of the above-mentioned polymer, and a resist film made of this material is developed by a known method. Known developers can be used. Specifically, acetone, methyl ethyl ketone (MEK), ketones such as methyl isobutyl ketone or a mixture thereof with alcohols such as methanol and isopropanol (IPA),
Examples thereof include fatty acid esters such as ethyl acetate and isoamyl acetate or mixtures thereof with alcohols, aromatic hydrocarbons such as monochlorobenzene, toluene and xylene, and mixtures thereof with alcohols.
（発明の効果） 本発明は高い解像度を有し、耐ドライエツチング性に
優れたネガ型の新規なレジスト材料を提供する。(Effects of the Invention) The present invention provides a novel negative resist material having high resolution and excellent dry etching resistance.
（実施例） 以上に実施例及び試験例を挙げて説明する。(Examples) The examples and test examples are described above.
実施例１ 70mgのタングステンヘキサカルボニルと20mlの四塩化
炭素を入れた重合容器中に、30分間乾燥窒素を流し系内
を窒素置換した後40℃に保ちながら100Wの高圧水銀灯に
より40分間紫外線照射を行つた。照射後、（２−トリフ
ルオロメチルフエニル）アセチレンを4.4g加え、40℃に
保ちながら窒素気流中24時間の重合を行つた。重合後メ
タノール中に重合溶液を加え、重合体を沈殿させた。沈
殿した重合体は、テトラヒドロフランに溶解させ、これ
をメタノール中に加えて再沈、精製を行つた。得られた
重合体は減圧乾燥を行つた。収率は93％であつた。重合
体の分子量はTHFを展開溶媒とするゲルパーミエーシヨ
ンクロマトグラフイーを用い、ポリスチレン換算により
測定した。その結果、重量平均分子量（ｗ）は99000
0、数平均分子量（ｎ）は280000であつた。Example 1 After flowing dry nitrogen into a polymerization vessel containing 70 mg of tungsten hexacarbonyl and 20 ml of carbon tetrachloride for 30 minutes to replace the inside of the system with nitrogen, and while maintaining the temperature at 40 ° C., irradiation with ultraviolet light was performed for 40 minutes using a 100 W high-pressure mercury lamp. I went. After the irradiation, 4.4 g of (2-trifluoromethylphenyl) acetylene was added, and polymerization was carried out for 24 hours in a nitrogen stream while maintaining the temperature at 40 ° C. After the polymerization, the polymerization solution was added to methanol to precipitate the polymer. The precipitated polymer was dissolved in tetrahydrofuran, added to methanol, and reprecipitated and purified. The obtained polymer was dried under reduced pressure. The yield was 93%. The molecular weight of the polymer was measured in terms of polystyrene using gel permeation chromatography using THF as a developing solvent. As a result, the weight average molecular weight (w) was 99000
0, the number average molecular weight (n) was 280,000.
上記重合体をエチルセロソルブに溶解させ５重量％の
溶液とした。これを0.5μｍのポリテトラフルオロエチ
レン製メンブランフイルターにより過を行いシリコン
ウエハー上に滴下した。最初500rpmにて５秒間、次に20
00prmにて90秒間の回転を行い、重合体被膜を形成し
た。その後、対流式オーブン中にて、140℃で30分間の
プリベークを行つた。膜厚を測定すると、0.4μｍであ
つた。次にエリオニクス社製電子線露光装置（ERE-302
型）を用い、照射電流1nAの条件下、各種形状のパター
ンを電子線により描画した。次いで、トルエンとイソプ
ロピルアルコールの混合溶媒（混合重量比3:1）を用い
て、23℃にて30秒間の現像を行い、トルエンとイソプロ
ピルアルコールの混合溶液（混合重量比1:1）を用い
て、23℃にて15秒間の１回目のリンスを行い、イソプロ
ピルアルコールを用い、23℃にて30秒間の２回目のリン
スを行つた。その結果、電子線照射部分がシリコンウエ
ハー上に残存しており、ネガ型レジストであることがわ
かつた。ゲル化に必要な最小電子線量（Di）は6.3μC/c
m2であり、初期膜厚の半分の膜厚を得るのに必要な電子
線量（D0.5）は10μC/cm2、Di×ｗ＝6.2C/cm2であつ
た。ガンマー値は2.2であつた。又、0.7μｍラインアン
ドスペースは完全に解像していた。The above polymer was dissolved in ethyl cellosolve to form a 5% by weight solution. This was filtered with a 0.5 μm polytetrafluoroethylene membrane filter and dropped on a silicon wafer. First at 500 rpm for 5 seconds, then 20
Rotation was performed at 00 prm for 90 seconds to form a polymer film. Thereafter, prebaking was performed at 140 ° C. for 30 minutes in a convection oven. When the film thickness was measured, it was 0.4 μm. Next, an electron beam exposure system manufactured by Elionix (ERE-302)
) And patterns of various shapes were drawn by an electron beam under the condition of an irradiation current of 1 nA. Next, using a mixed solvent of toluene and isopropyl alcohol (mixed weight ratio of 3: 1), development is performed at 23 ° C. for 30 seconds, and a mixed solution of toluene and isopropyl alcohol (mixed weight ratio of 1: 1) is used. The first rinse was performed at 23 ° C. for 15 seconds, and the second rinse was performed at 23 ° C. for 30 seconds using isopropyl alcohol. As a result, it was found that the electron beam irradiated portion remained on the silicon wafer and was a negative resist. Minimum electron dose (Di) required for gelation is 6.3μC / c
m 2 , and the electron dose (D 0.5 ) required to obtain a film thickness that was half the initial film thickness was 10 μC / cm 2 and Di × w = 6.2 C / cm 2 . The gamma value was 2.2. The 0.7 μm line and space was completely resolved.
実施例２ タングステンヘキサカルボニル1.23g、四塩化炭素87.
5ml及び２−トリフルオロメチルフエニルアセチレン11.
9gを使用した以外は実施例１と全く同様にして重合を行
つた。収率は92％であつた。ｗは176000、ｎは4300
0であつた。Example 2 1.23 g of tungsten hexacarbonyl, carbon tetrachloride 87.
5 ml and 2-trifluoromethylphenylacetylene 11.
Polymerization was carried out in exactly the same manner as in Example 1 except that 9 g was used. The yield was 92%. w is 176000, n is 4300
It was 0.
上記重合体をエチルセロソルブに溶解させ８重量％の
溶液とした。これを0.5μｍのポリテトラフルオロエチ
レン製メンブランフイルターにより過を行いシリコン
ウエハー上に滴下した。最初500rpmにて５秒間、次に20
00rpmにて90秒間の回転を行い、重合体被膜を形成し
た。その後、対流式オーブン中にて、140℃で30分間の
プリベークを行つた。膜厚を測定すると、0.42μｍであ
つた。次に実施例１と同じ方法で、電子線による描画を
行い、現像、リンスをし、パターン形成を行つた。ゲル
化に必要な最小電子線量（Di）は50μC/cm2であり、初
期膜厚の半分の膜厚を得るのに必要な電子線量（D0.5）
は100μC/cm2、Di×ｗ＝8.8C/cm2であつた。ガンマー
値は1.7であつた。又、0.25μｍラインアンドスペース
は完全に解像していた。The above polymer was dissolved in ethyl cellosolve to form an 8% by weight solution. This was filtered with a 0.5 μm polytetrafluoroethylene membrane filter and dropped on a silicon wafer. First at 500 rpm for 5 seconds, then 20
Rotation was performed at 00 rpm for 90 seconds to form a polymer film. Thereafter, prebaking was performed at 140 ° C. for 30 minutes in a convection oven. When the film thickness was measured, it was 0.42 μm. Next, in the same manner as in Example 1, drawing by an electron beam was performed, development and rinsing were performed, and a pattern was formed. The minimum electron dose (Di) required for gelation is 50 μC / cm 2 , and the electron dose (D 0.5 ) required to obtain half the initial film thickness
Was 100 μC / cm 2 and Di × w = 8.8 C / cm 2 . The gamma value was 1.7. The 0.25 μm line and space was completely resolved.
実施例３ テトラフエニル錫（SnPh4）43mg（0.1m mol）のトル
エン溶液（8ml）に六塩化タングステン（WCl6）40mg
（0.1m mol）を加えた触媒に、１−エチニル−５−（ト
リフルオロメチル）ナフタレン2.2g（10m mol）のトル
エン溶液（2ml）を加え、窒素気流中室温で1.5時間撹拌
した。内容液は黒青紫色ゴム状となり殆ど固化した。こ
れをメタノール中に注ぎ、析出した重合体を回収し、減
圧乾燥を行なつた。収率はほぼ100％であつた。ｗは1
541000、ｎは169000であつた。Example 3 40 mg of tungsten hexachloride (WCl 6 ) was added to a toluene solution (8 ml) of 43 mg (0.1 mmol) of tetraphenyltin (SnPh 4 ).
(0.1 mmol) was added to the catalyst, and a toluene solution (2 ml) of 1-ethynyl-5- (trifluoromethyl) naphthalene (2.2 g, 10 mmol) was added, followed by stirring at room temperature for 1.5 hours in a nitrogen stream. The content liquid became black-blue-purple rubber-like and almost solidified. This was poured into methanol, and the precipitated polymer was recovered and dried under reduced pressure. The yield was almost 100%. w is 1
541000, n was 169,000.
上記重合体をメチルイソブチルケトンに溶解させ５重
量％の溶液とした。これを0.5μｍのポリテトラフルオ
ロエチレン製メンブランフイルターにより過を行いシ
リコンウエハー上に滴下した。200rpmにて180秒間の回
転を行い、重合体被膜を形成した。その後、対流式オー
ブン中にて、120℃、30分間のプリベークを行つた。膜
厚を測定すると、0.5μｍであつた。次に照射電流値を3
nAと変更した以外は実施例１と同じ方法で、電子線によ
る描画を行つた。次いでジメチルホルムアミドを用い
て、23℃にて30秒間の現像を行い、ジメチルホルムアミ
ドとイソプロピルアルコールの混合溶液（混合重量比1:
1）を用いて、23℃にて15秒間の１回目のリンスを行
い、イソプロピルアルコールを用い、23℃にて30秒間の
２回目のリンスを行つた。その結果、電子線照射部分が
シリコンウエハー上に残存しており、ネガ型レジストで
あることがわかつた。ゲル化に必要な最小電子線量（D
i）は86μC/cm2であり、初期膜厚の半分の膜厚を得るの
に必要な電子線量（D0.5）は140μC/cm2、Di×ｗ＝13
3C/cm2であつた。ガンマー値は2.5であつた。又、1.0μ
ｍラインアンドスペースは完全に解像していた。The above polymer was dissolved in methyl isobutyl ketone to form a 5% by weight solution. This was filtered with a 0.5 μm polytetrafluoroethylene membrane filter and dropped on a silicon wafer. Rotation was performed at 200 rpm for 180 seconds to form a polymer film. Thereafter, prebaking was performed at 120 ° C. for 30 minutes in a convection oven. When the film thickness was measured, it was 0.5 μm. Next, set the irradiation current value to 3
Drawing by an electron beam was performed in the same manner as in Example 1 except that nA was changed. Next, using dimethylformamide, development was performed at 23 ° C. for 30 seconds, and a mixed solution of dimethylformamide and isopropyl alcohol (mixing weight ratio 1:
Using 1), the first rinse was performed at 23 ° C. for 15 seconds, and the second rinse was performed at 23 ° C. for 30 seconds using isopropyl alcohol. As a result, it was found that the electron beam irradiated portion remained on the silicon wafer and was a negative resist. Minimum electron dose required for gelation (D
i) is 86 μC / cm 2 , the electron dose (D 0.5 ) required to obtain a film thickness that is half of the initial film thickness is 140 μC / cm 2 , and Di × w = 13
It was 3 C / cm 2 . The gamma value was 2.5. Also, 1.0μ
m-line and space were completely resolved.
試験例１ 実施例１及び３で形成した重合体被膜を用いて耐ドラ
イエツチング性の試験を行つた。使用装置は日電アネル
バ社製DEM-451型、平行平板型ドライエツチング装置を
用いた。電極間距離85mm、使用ガスCF4、圧力13Pa、流
量100SCCM、RF電力100W、プレート電圧200V、プレート
温度10℃の条件下で、耐ドライエツチング性の試験を行
つた。ポリメチルメタクリレート（PMMA）のエツチング
速度を１としたときの相対エツチング速度を第１表に示
す。これより耐ドライエツチング性が良好なことがわか
る。Test Example 1 A dry etching resistance test was performed using the polymer films formed in Examples 1 and 3. The apparatus used was a DEM-451 model manufactured by Nidec Anelva, a parallel plate type dry etching apparatus. A dry etching resistance test was performed under the conditions of a distance between electrodes of 85 mm, a gas used of CF 4 , a pressure of 13 Pa, a flow rate of 100 SCCM, an RF power of 100 W, a plate voltage of 200 V, and a plate temperature of 10 ° C. Table 1 shows relative etching rates when the etching rate of polymethyl methacrylate (PMMA) is set to 1. This indicates that the dry etching resistance is good.
試験例２ 実施例２で形成した重合体被膜を用いて、熱安定性の
試験を行つた。100℃、140℃及び160℃の温度の雰囲気
中に30分間のプリベークを行い、実施例２に示したのと
全く同じ方法で電子線照射、現像を行つた。次に初期膜
厚の半分の膜厚を得るのに必要な電子線照射量（D0.5）
を測定し、プリベース温度との関係を調べた。結果を第
２表に示す。これよりプリベーク温度の範囲が100℃か
ら160℃において熱安定性が良好なことがわかる。 Test Example 2 Using the polymer film formed in Example 2, a heat stability test was performed. Prebaking was performed in an atmosphere at a temperature of 100 ° C., 140 ° C. and 160 ° C. for 30 minutes, and electron beam irradiation and development were performed in exactly the same manner as described in Example 2. Next, the amount of electron beam irradiation required to obtain a film thickness that is half the initial film thickness (D 0.5 )
Was measured, and the relationship with the pre-base temperature was examined. The results are shown in Table 2. This shows that the thermal stability is good when the prebake temperature is in the range of 100 ° C to 160 ° C.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 植田 昭男 愛知県名古屋市昭和区池端町２―19 (72)発明者 奥原 邦夫 愛知県犬山市大字羽黒字西五反田14−13 (72)発明者 田丸 真司 大阪府吹田市千里山西３丁目31番10号 (72)発明者 平 一夫 大阪府吹田市千里丘西18−１ 審査官 山鹿 勇次郎 (56)参考文献 特開 昭61−55647（ＪＰ，Ａ) 特開 昭60−247640（ＪＰ，Ａ) 特開 昭60−166309（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akio Ueda 2-19 Ikehata-cho, Showa-ku, Nagoya-shi, Aichi Prefecture (72) Inventor Kunio Okuhara 14-13, Nishi-Gotanda, Oguro, Inuyama-shi, Aichi Prefecture (72) Inventor Tamaru Shinji 3-31-10 Senriyamanishi, Suita-shi, Osaka (72) Inventor Kazuo Taira 18-1 Senriokanishi, Suita-shi, Osaka Examiner Yujiro Yamaga (56) References JP-A-61-55647 (JP, A) JP-A-60-247640 (JP, A) JP-A-60-166309 (JP, A)
Claims (2)
する重合体からなるレジスト材料。(1) General formula (Z represents an arylene group) A resist material comprising a polymer containing a structural unit represented by the following formula:
１項に記載のレジスト材料。2. The resist material according to claim 1, wherein Z is a naphthylene group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62118671A JP2593310B2 (en) | 1987-05-14 | 1987-05-14 | Resist material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62118671A JP2593310B2 (en) | 1987-05-14 | 1987-05-14 | Resist material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63282732A JPS63282732A (en) | 1988-11-18 |
| JP2593310B2 true JP2593310B2 (en) | 1997-03-26 |
Family
ID=14742330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62118671A Expired - Lifetime JP2593310B2 (en) | 1987-05-14 | 1987-05-14 | Resist material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2593310B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2863018B2 (en) * | 1991-02-26 | 1999-03-03 | 株式会社日立製作所 | Fine processing method by dry etching and resist mask resin composition for dry etching |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166309A (en) * | 1984-02-09 | 1985-08-29 | Agency Of Ind Science & Technol | Polyphenylacetylene compound having fluorine or trifluoromethyl group |
| JPS60247640A (en) * | 1984-05-24 | 1985-12-07 | Fujitsu Ltd | Formation of negative type resist pattern |
| JPS6155647A (en) * | 1984-08-27 | 1986-03-20 | Nippon Telegr & Teleph Corp <Ntt> | Material for forming pattern and its using method |
-
1987
- 1987-05-14 JP JP62118671A patent/JP2593310B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63282732A (en) | 1988-11-18 |
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