JPH03223865A - Resist material - Google Patents

Resist material

Info

Publication number
JPH03223865A
JPH03223865A JP2019616A JP1961690A JPH03223865A JP H03223865 A JPH03223865 A JP H03223865A JP 2019616 A JP2019616 A JP 2019616A JP 1961690 A JP1961690 A JP 1961690A JP H03223865 A JPH03223865 A JP H03223865A
Authority
JP
Japan
Prior art keywords
group
carbon atoms
hydrogen atom
branched
resin
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.)
Granted
Application number
JP2019616A
Other languages
Japanese (ja)
Other versions
JP2747735B2 (en
Inventor
Fumiyoshi Urano
文良 浦野
Masaaki Nakahata
中畑 正明
Hirotoshi Fujie
藤江 啓利
Keiji Ono
桂二 大野
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.)
Fujifilm Wako Pure Chemical Corp
Original Assignee
Wako Pure Chemical Industries 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 Wako Pure Chemical Industries Ltd filed Critical Wako Pure Chemical Industries Ltd
Priority to JP2019616A priority Critical patent/JP2747735B2/en
Publication of JPH03223865A publication Critical patent/JPH03223865A/en
Application granted granted Critical
Publication of JP2747735B2 publication Critical patent/JP2747735B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Abstract

PURPOSE:To enhance light transmittance, heat resistance, and solution stability by forming a resist material with a heat-resistant resin composed of constituents each having a functional group chemically changeable and solubilizable in alkali by heating and constituents each imparting heat resistance to the resin, and a specified photosensitive compound. CONSTITUTION:The resist material comprises the heat-resistant resin composed of the constituents each having the functional group chemically changeable and solubilizable in alkali by heating under an atmosphere containing an acid and the constituent for imparting heat resistance to the resin, and the photosensitive material for generating the acid by exposure to light and represented by formula I, and a solvent for capable of dissolving both, and in formula I, each of Ro<1> - Ro<4> is H, halogen, 1 - 10 C straight, branched, or cyclic alkyl, 1 - 10 C haloalkyl, or the like, independent from each other, thus permitting light transmittance, heat resistance,a nd solution stability to be enhanced.

Description

【発明の詳細な説明】 [産業上の利用分野] 本開明は半導体素子等の製造に於て用いられるレジスト
材料に関する。詳しくは露光エネルギー源として400
nm現下の光源、例えば365nmの1線光。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resist material used in manufacturing semiconductor devices and the like. For details, see 400 yen as an exposure energy source.
nm Current light source, for example, 365 nm single line light.

300nm以下の遠紫外光、例えば24L4nmのKr
Fエキシマレーザ−光等を用いてポジ型のパターンを形
成する際のレジスト材料に関する。
Far ultraviolet light of 300 nm or less, for example 24L4 nm Kr
The present invention relates to a resist material for forming a positive pattern using F excimer laser light or the like.

[従来の技術] 近年、半導体デバイスの高密度集積化に伴い、微細加工
、中でもフォトリソグラフィに用いられる露光装置の光
源は益々、短波長化し、今ではKrFエキシマレーザ(
248,4nm)光が検討されるまでになってきている
。しかしながらこの波長に適したレジスト材料は未だ適
当なものが見出されていない。
[Prior Art] In recent years, with the high density integration of semiconductor devices, the light source of exposure equipment used for microfabrication, particularly photolithography, has become increasingly shorter in wavelength, and now KrF excimer laser (
248,4 nm) light is now being considered. However, a resist material suitable for this wavelength has not yet been found.

例えば、KrFエキシマレーザ光に対してかなり感光性
が高く、光透過率も良いと言われているMP2400(
シブレイ社製)を用いた場合、ベースポリマーのノボラ
ンク樹脂自身の露光光に対する大きな表酊吸収や感光剤
のナフトキノンジアジド系化合物の光反応性が良くない
為、現像後のパターン形状は非常に悪く使用出来ない。
For example, MP2400 (
When using Sibley Co., Ltd.), the pattern shape after development is very poor due to the large surface absorption of the base polymer Novolank resin itself to the exposure light and the poor photoreactivity of the naphthoquinone diazide compound as the photosensitive agent. Can not.

また、KrFエキシマレーザ光や遠紫外光を光源とする
レジスト物より成るレジスト材料が開発さ九ている。(
例えは、特開昭64−80944号公報;特開平115
4048号公報:特開平1−155339号公報等)。
In addition, resist materials have been developed that use KrF excimer laser light or far ultraviolet light as a light source. (
For example, JP-A-64-80944; JP-A-115
No. 4048: JP-A-1-155339, etc.).

感光性化合物と248.4nm付近で高い光透過性を有
する樹脂より成るパターン形成材料も開発されている。
A pattern forming material made of a photosensitive compound and a resin having high light transmittance around 248.4 nm has also been developed.

(例えば、特開平1−188852号公N ; Y、T
an1ら、5PIE’s 1989 Sympo、、1
086−03等)。第4図を用いて、このレジスト材料
によるパターン形成方法を示す。半導体基板1上にレジ
スト材料5を回転塗布し、1.0μmのレジスト材料膜
を得る(第4図(a))。なお、基板1上には酸化膜、
導電膜、絶縁膜が形成されている場合が多い。次に24
8.4nmのKrFエキシマレーザ光3でマスク4を介
し選択的に露光する(第4図(b))。そして最後に通
常のアルカリ現像液(0,24%テトラメチルアンモニ
ウムヒドロキシド水溶液)を用いて現像を行うことによ
りレジスト材料5の露光部を溶解除去しパターン5aを
得る(第4図(C))。このレジスト材料膜(1μm)
の露光前後の紫外線分光曲線を第5図に示す。使用樹脂
が1μm厚で70%であるのに対し、このレジスト材料
の露光後の透過率は4゜%と低く、十分な光線色性が得
られていないことがわかる。また、パターン形成実験の
結果、パターンのアスペクト比は約70度と十分なパタ
ーン形状は得られていない。更にこのレジスト材料膜基
を有する感光性化合物を含むレジスト材料を使用する場
合、−船釣にその感度は100〜300mJ/an2程
度であり、高出力の割にエネルギー効率が良くないKr
Fエキシマレーザ光(248,4nm)を用いての実用
化は困難な状況にある。また、近年、露光エネルギー量
を低減させる手段として露光により発生した酸を媒体と
する化学増幅型のレジスト材料が提案され[)1.It
oら、Polym、Eng、Sci、、23巻、101
2頁(1983年)コ、これに関して種々の報告がなさ
れている。(例えば、W、R,Brunsvoldら、
5PIE’51989 Sympo、、1086−4Q
 ; T、Neenanら、5PIE’s 1989S
ympo、、1086−01) 、しかしながら、これ
等化学増幅型レジスト材料に使用される樹脂は比較的、
芳香環を多く有することに起因して248.4nm付近
の光透過性が不十分であったり、樹脂の耐熱性が乏しい
等の問題がある。
(For example, Japanese Patent Application Laid-open No. 1-188852 N; Y, T
an1 et al., 5PIE's 1989 Sympo, 1
086-03 etc.). A pattern forming method using this resist material will be described using FIG. A resist material 5 is spin-coated onto the semiconductor substrate 1 to obtain a 1.0 μm resist material film (FIG. 4(a)). Note that on the substrate 1 there is an oxide film,
A conductive film and an insulating film are often formed. Next 24
It is selectively exposed to 8.4 nm KrF excimer laser light 3 through a mask 4 (FIG. 4(b)). Finally, development is performed using an ordinary alkaline developer (0.24% tetramethylammonium hydroxide aqueous solution) to dissolve and remove the exposed areas of the resist material 5, thereby obtaining a pattern 5a (FIG. 4(C)). . This resist material film (1 μm)
FIG. 5 shows the ultraviolet spectral curves before and after exposure. The transmittance of this resist material after exposure was as low as 4%, whereas the resin used had a thickness of 70% at a thickness of 1 μm, indicating that sufficient light chromaticity was not obtained. Further, as a result of pattern forming experiments, the aspect ratio of the pattern was about 70 degrees, and a sufficient pattern shape was not obtained. Furthermore, when using a resist material containing a photosensitive compound having a resist material film group, the sensitivity for boat fishing is approximately 100 to 300 mJ/an2, and Kr is not energy efficient despite its high output.
Practical implementation using F excimer laser light (248.4 nm) is difficult. In addition, in recent years, a chemically amplified resist material using acid generated during exposure as a medium has been proposed as a means of reducing the amount of exposure energy [2]. It
o et al., Polym, Eng, Sci, vol. 23, 101
2 (1983), various reports have been made regarding this. (For example, W. R. Brunsvold et al.
5PIE'51989 Sympo,, 1086-4Q
; T, Neenan et al., 5PIE's 1989S
ympo, 1086-01) However, the resins used in these chemically amplified resist materials are relatively
Due to the large number of aromatic rings, there are problems such as insufficient light transmittance around 248.4 nm and poor heat resistance of the resin.

また、感光性化合物に関しては、例えばトップェニルス
ルホニウムテトラフルオロボレイトのようなオニウム塩
の場合は溶液安定性が乏しくレジスト材料をm製した直
後ではその本来の性能を発揮するが半導体製造ラインに
於て実用化することは困難であると言われているし、2
,6−シニトロベンジルのスルホン酸エステルの場合は
化合物としての安定性は認められるが露光により生成す
る2−ニトロ−6−ニトロツベンズアルデヒドが一般に
使われている現像液(テトラメチルアンモニウムヒドロ
キシド水溶液)に溶解しないため、現像処理後、露光部
にスカムが残存したり、パターン形状が悪くなる等の問
題が生ずる。また、トリス(メタンスルホニルオキシ)
ベンゼンは前記感光性化合物と比べて感度が低いため化
学増幅型レジストの感光性化合物としては適さない。
Regarding photosensitive compounds, for example, onium salts such as tophenylsulfonium tetrafluoroborate have poor solution stability and exhibit their original performance immediately after the resist material is manufactured, but on a semiconductor manufacturing line. It is said that it is difficult to put it into practical use.
In the case of sulfonic acid ester of 6-cinitrobenzyl, stability as a compound is recognized, but 2-nitro-6-nitrotubenzaldehyde, which is produced by exposure to light, is a commonly used developer (tetramethylammonium hydroxide aqueous solution). ), problems such as scum remaining in exposed areas and poor pattern shape occur after development. Also, tris(methanesulfonyloxy)
Benzene is not suitable as a photosensitive compound for chemically amplified resists because its sensitivity is lower than that of the photosensitive compounds described above.

[発明が解決しようとする問題点コ N20 このように l II ll  基を有する感光性化合
物を−C−C− 含むレジスト材料の場合には、感光性化合物の光ればな
らないことから、良好なパターン形状が得られ難く、且
つ露光エネルギー量を多く必要とする。また、化学増幅
型レジスト材料については樹脂の248.4nm付近の
光透過性を改善するか、樹脂の耐熱性を向上させない限
り使用に供し得ないし、また同時に感光性化合物に関し
てはより低い露光エネルギー量で酸を発生し、且つ溶液
安定性があり、しかも光反応により発生した酸が高い透
過性を有することが求められている。
[Problems to be Solved by the Invention] N20 As described above, in the case of a resist material containing a -C-C- photosensitive compound having an l II ll group, since the photosensitive compound must glow, a good It is difficult to obtain a pattern shape, and a large amount of exposure energy is required. In addition, chemically amplified resist materials cannot be used unless the light transmittance of the resin near 248.4 nm is improved or the heat resistance of the resin is improved, and at the same time, the amount of exposure energy is lower for photosensitive compounds. There is a need for a material that can generate an acid in a chemical reaction, has solution stability, and has high permeability to the acid generated by a photoreaction.

[発明の目的コ 本発明は上記した如き状況に鑑みなされたもので、i線
光や、遠紫外光、例えばKrFエキシマレーザ光等によ
る露光後に高い透過性を有し、且つ耐熱性を有する樹脂
と、高感度(低露光エネルギー量)で効率良く酸を発生
し、且つ溶液中で安定で、しかも光反応により発生した
酸が高い透過性を有する感光性化合物を含んで成るレジ
スト材料を提供することを目的とする。
[Object of the Invention] The present invention was made in view of the above-mentioned situation, and it provides a resin that has high transparency after exposure to i-line light, far ultraviolet light, such as KrF excimer laser light, and has heat resistance. and a resist material comprising a photosensitive compound that efficiently generates acid with high sensitivity (low exposure energy amount), is stable in solution, and has high permeability to acid generated by photoreaction. The purpose is to

[発明の構成コ 上記目的を達成するため、本発明は下記の構成より成る
[Configuration of the Invention] In order to achieve the above object, the present invention consists of the following configuration.

「酸雰囲気下で加熱により化学変化を受けてアルカリ可
溶性となる官能基を有する成分と樹脂に耐熱性を付与す
る成分とから構成される耐熱性樹脂と、露光により酸を
発生する下記−数式[IIで示される感光性化合物と、
この両者を溶解可能な溶剤とを含んで成ることを特徴と
するレジスト材料。
"A heat-resistant resin consisting of a component having a functional group that undergoes a chemical change when heated in an acid atmosphere and becomes alkali-soluble, and a component that imparts heat resistance to the resin, and a heat-resistant resin that generates an acid upon exposure to light. A photosensitive compound represented by II;
A resist material comprising a solvent capable of dissolving both.

6 [式中、Rδ、R6、R(1,Reは夫々独立して水素
原子、ハロゲン原子、炭素数1〜10の直鎖状1分枝状
又は環状のアルキル基、炭素数1〜10のハロアルキル
基、炭素数1〜lOの直鎖状又は分枝状のアルコキシ基
、炭素数2〜IOのアルケニル基、炭素数7〜lOのア
ラルキル基、フェニル基、置換フェニル基(置換基は、
ハロゲン原子、炭素数1〜10の直鎖状1分枝状又は環
状のアルキル基、炭素数1〜10のハロアルキル基、炭
素数1〜10の直鎖状又は分枝状のアルコキシ基、ニト
ロ基、ニトリル基又はアミド基。)を表わす。また、R
♂とR6、R6とR♂及びR(lとReは夫々独立して
、互いに結合して脂環。
6 [In the formula, Rδ, R6, R(1, Re each independently represent a hydrogen atom, a halogen atom, a linear monobranched or cyclic alkyl group having 1 to 10 carbon atoms, Haloalkyl group, linear or branched alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, phenyl group, substituted phenyl group (substituents are:
Halogen atom, linear monobranched or cyclic alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms, nitro group , nitrile group or amide group. ). Also, R
Male and R6, R6 and R♂ and R (l and Re are each independently bonded to each other to form an alicyclic ring.

ヘテロ芳香環、芳香環又はヘテロ芳香環を成していても
良い。]」 本発明のレジスト材料は露光エネルギー量を出来るだけ
低減させるため、化学増幅を利用したものである。即ち
、本発明のレジスト材料は露光により酸発生剤から発生
した酸の雰囲気下、加熱により化学変化を受けてアルカ
リ可溶性となる官能基を有する成分と、樹脂に耐熱性を
付与する成分即ち加熱に対し樹脂全体が軟化することを
抑止する機能を有する成分とから構成される耐熱性樹脂
(以下、「本発明に係る樹脂」と略記する。)と新規な
感光性化合物とを併せ用いる点に特徴を有する新規なレ
ジスト材料である。本発明に係る酸雰囲気下、加熱によ
りアルカリ可溶性となる官能基を有する成分(以下、「
特定の官能基を有する成分」と略記する。)としては例
えば酸で脱離する保護基を有するP−ヒドロキシスチレ
ン誘導体やP−ヒドロキシ−α−メチルスチレン誘導体
等のモノマーが挙げられる。具体例としては例えばP−
メトキシスチレン、P−イソプロポキシスチレン、p−
tere〜ブトキシスチレン、P−メトキシメトキシス
チレン、P−イソプロポキシメトキシスチレン、P−テ
トラヒドロピラニルオキシスチレン、P−テトラヒドロ
フラニルオキシスチレン、P〜トリメチルシリルオキシ
スチレン、ρ−tert−ブトキシカルボニルオキシス
チレン、P−イソプロポキシカルボニルオキシスチレン
、或はこれ等P−ヒドロキシスチレン誘導体と同様の保
護基を有するP−ヒドロキシ−α−メチルスチレン誘導
体等が挙げられるが、勿論これらに限定されるものでは
ない。また、樹脂に耐熱性を付与する成分としてはこの
成分の使用により樹脂全体が100℃以上の加熱、より
好ましくは140℃以上の加熱でも軟化することを抑止
出来るものであればいずれにても良いが1例えばp−ヒ
ドロキシスチレン、P−クロルスチレン、スチレン、α
−メチルスチレン、フマロニトリル、マレイン酸モノイ
ソプロピル、マレイン酸モノtert−ブチル。
It may form a heteroaromatic ring, an aromatic ring, or a heteroaromatic ring. ]'' The resist material of the present invention utilizes chemical amplification in order to reduce the amount of exposure energy as much as possible. That is, the resist material of the present invention contains a component having a functional group that undergoes a chemical change upon heating in an acid atmosphere generated from an acid generator upon exposure and becomes alkali-soluble, and a component that imparts heat resistance to the resin, i.e., a component that imparts heat resistance to the resin. On the other hand, it is characterized by the combined use of a heat-resistant resin (hereinafter abbreviated as "resin according to the present invention") composed of a component that has the function of suppressing the softening of the entire resin and a novel photosensitive compound. This is a new resist material with A component having a functional group that becomes alkali-soluble by heating in an acid atmosphere according to the present invention (hereinafter referred to as "
Abbreviated as "component having a specific functional group." ) include monomers such as P-hydroxystyrene derivatives and P-hydroxy-α-methylstyrene derivatives having a protecting group that can be removed with acid. As a specific example, for example, P-
Methoxystyrene, P-isopropoxystyrene, p-
te~butoxystyrene, P-methoxymethoxystyrene, P-isopropoxymethoxystyrene, P-tetrahydropyranyloxystyrene, P-tetrahydrofuranyloxystyrene, P~trimethylsilyloxystyrene, ρ-tert-butoxycarbonyloxystyrene, P- Examples include isopropoxycarbonyloxystyrene, P-hydroxy-α-methylstyrene derivatives having the same protective group as P-hydroxystyrene derivatives, but are not limited thereto. Further, as a component that imparts heat resistance to the resin, any component may be used as long as the use of this component can prevent the entire resin from softening even when heated to 100°C or higher, more preferably 140°C or higher. is 1 such as p-hydroxystyrene, p-chlorostyrene, styrene, α
- methylstyrene, fumaronitrile, monoisopropyl maleate, mono-tert-butyl maleate.

マレイン酸ジしert−ブチル、マレイン酸モノシクロ
へキシル−無水マレイン酸、N−フェニルマレイミド、
N−置換フェニルマレイミド、N−メチルマレイミド、
N−n−ブチルマレイミド等のモノマーがより一般的な
ものとして挙げられる。
Di-ert-butyl maleate, monocyclohexyl maleate-maleic anhydride, N-phenylmaleimide,
N-substituted phenylmaleimide, N-methylmaleimide,
Monomers such as N-n-butylmaleimide are more common.

本発明に係る樹脂は例えば下記−数式[■]又は[II
I]であられすことが出来る。
The resin according to the present invention is, for example, the following formula [■] or [II
I] can bring you blessings.

[式中、R1はメチル基、イソプロピル基、tertブ
チル基、メトキシメチル基、インプロポキシメチル基、
テトラヒドロピラニル基、テトラヒドロフラニル基、ト
リメチルシリル基、terL−ブトキシカルボニル基又
はイソプロボキシカルホニル基を表わし、R2は水素原
子、ハロゲン原子又はメチル基を表わし、R3は水素原
子、P−ヒドロキシフェニル基、p−クロルフェニル基
、フェニル基、シアノ基又は−COOR7(但し、R7
は炭素数3〜10の分岐状又は環状のアルキル基、又は
水素原子を表わす。
[Wherein, R1 is a methyl group, isopropyl group, tert-butyl group, methoxymethyl group, impropoxymethyl group,
It represents a tetrahydropyranyl group, a tetrahydrofuranyl group, a trimethylsilyl group, a terL-butoxycarbonyl group or an isoproboxycarbonyl group, R2 represents a hydrogen atom, a halogen atom or a methyl group, and R3 represents a hydrogen atom or a P-hydroxyphenyl group. , p-chlorophenyl group, phenyl group, cyano group or -COOR7 (however, R7
represents a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a hydrogen atom.

)を表わし、R4及びR6は夫々独立して水素原子、メ
チル基又はハロゲン原子を表わし、R5は水素原子、シ
アン基又は−COOR8(但し、R8は炭素数3〜10
の分岐状又は環状のアルキル基、又は水素原子を表わす
。)を表わし、R9は水素原子又は−COOR10(但
し、Rloは炭素数3〜10の分岐状又は環状のアルキ
ル基、又は水素原子を表わす。)を表わし、k及びlは
夫々独立して自然数を表わす。コ[式中、Xは酸素原子
又は:l:N−(CH2)q〜R1′(但し、8口は炭
素数1〜10の直鎖状1分枝状又は環状のアルキル基又
は置換基を有していても良いフェニル基を表わし、qは
0又は自然数を表わす。)を表わし、1′及びPは夫々
独立して0又は自然数を表わし、R1,R2,R3,R
4,R5,H6,R9及びkは前記と同じ。] これら−数式[II]又は[m]で表わされる化合物は
1本発明に係る樹脂の代表的なものであるが、本発明に
係る樹脂は勿論これらの化合物に限定されるものではな
い。
), R4 and R6 each independently represent a hydrogen atom, a methyl group, or a halogen atom, and R5 represents a hydrogen atom, a cyan group, or -COOR8 (however, R8 has 3 to 10 carbon atoms).
represents a branched or cyclic alkyl group, or a hydrogen atom. ), R9 represents a hydrogen atom or -COOR10 (wherein Rlo represents a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a hydrogen atom), and k and l each independently represent a natural number. represent [In the formula, represents an optional phenyl group, q represents 0 or a natural number), 1' and P each independently represent 0 or a natural number, R1, R2, R3, R
4, R5, H6, R9 and k are the same as above. ] These compounds represented by the formula [II] or [m] are representative of the resins according to the present invention, but the resins according to the present invention are of course not limited to these compounds.

本発明に係る樹脂の具体例としては例えば、P−イソプ
ロポキシスチレンとα−メチルスチレン共重合体、P−
テトラヒドロピラニルオキシスチレンとP−ヒドロキシ
スチレン共重合体、p−tert−ブトキシスチレンと
P−ヒドロキシスチレン共重合体、p−tert−ブト
キシカルボニルオキシスチレンとマレイン酸モノシクロ
ヘキシルエステル共重合体、p−tert−ブトキシカ
ルボニルオキシスチレンとα−メチルスチレン共重合体
、p−tert−ブトキシスチレンとフマロニトリル共
重合体、P−メトキシメトキシスチレンとp−クロルス
チレン共重合体、P−メトキシメトキシスチレンとマレ
イン酸モノシクロヘキシルエステル及び無水マレイン酸
との共重合体、p−テトラヒドロフラニルオキシスチレ
ンとN−メチルマレイミド共重合体、p −tert−
ブトキシカルボニルオキシスチレンとP−ヒドロキシス
チレン及び無水マレイン酸との共重合体、p−テトラヒ
ドロピラニルオキシスチレンとP−ヒドロキシスチレン
及びフマロニトリルとの共重合体、p−tert−ブト
キシカルボニルオキシスチレンとP−ヒドロキシスチレ
ン及びN−ブチルマレイミドとの共重合体、P−テトラ
ヒドロピラニルオキシスチレンとP−ヒドロキシスチレ
ン及びN−フェニルマレイミドとの共重合体等が挙げら
れるが、これ等に限定されるものではない。
Specific examples of the resin according to the present invention include P-isopropoxystyrene and α-methylstyrene copolymer, P-isopropoxystyrene and α-methylstyrene copolymer,
Tetrahydropyranyloxystyrene and P-hydroxystyrene copolymer, p-tert-butoxystyrene and P-hydroxystyrene copolymer, p-tert-butoxycarbonyloxystyrene and maleic acid monocyclohexyl ester copolymer, p-tert -Butoxycarbonyloxystyrene and α-methylstyrene copolymer, p-tert-butoxystyrene and fumaronitrile copolymer, P-methoxymethoxystyrene and p-chlorostyrene copolymer, P-methoxymethoxystyrene and monocyclohexyl maleate copolymer with ester and maleic anhydride, p-tetrahydrofuranyloxystyrene and N-methylmaleimide copolymer, p-tert-
Copolymer of butoxycarbonyloxystyrene, P-hydroxystyrene and maleic anhydride, copolymer of p-tetrahydropyranyloxystyrene, P-hydroxystyrene and fumaronitrile, p-tert-butoxycarbonyloxystyrene and P- Examples include, but are not limited to, copolymers of hydroxystyrene and N-butylmaleimide, copolymers of P-tetrahydropyranyloxystyrene, P-hydroxystyrene, and N-phenylmaleimide, etc. .

本発明に係る樹脂は、上記特定の官能基を有する成分(
モノマー)1種又は2種以上と樹脂に耐熱性を付与する
成分(モノマー)1種又は2種以上とを共重合体製造法
の常法に従って共重合させることにより容易に得ること
ができる。即ち、上記特定の官能基を有する成分(モノ
マー)1種又は2種以上と樹脂に耐熱性を付与する成分
(モノマー)1種又は2種以上とを例えばベンゼン、ト
ルエン等の有機溶媒中、ラジカル重合開始剤[例えばア
ゾビスイソブチロニトリル 2,2′−アゾビス(2,
4−ジメチルワレロニトリル)、2,2′−アゾビス(
2−メチルプロピオン酸メチル)等のアゾ系重合開始剤
や過酸化ベンゾイル、過酸化ラウロイル等の過酸化物系
重合開始剤等]の存在下、窒素気流中50〜100℃で
1〜lO時間重合反応させればよく、反応後は高分子化
合物取得法の常法に従って後処理を行ないこれを単離す
ればよい。
The resin according to the present invention comprises a component having the above-mentioned specific functional group (
It can be easily obtained by copolymerizing one or more monomers and one or more components (monomers) that impart heat resistance to the resin according to a conventional method for producing copolymers. That is, one or more components (monomers) having the above-mentioned specific functional groups and one or more components (monomers) that impart heat resistance to the resin are combined with radicals in an organic solvent such as benzene or toluene. Polymerization initiator [e.g. azobisisobutyronitrile 2,2'-azobis(2,
4-dimethylvaleronitrile), 2,2'-azobis(
Polymerization in the presence of an azo polymerization initiator such as (methyl 2-methylpropionate) or a peroxide polymerization initiator such as benzoyl peroxide, lauroyl peroxide, etc. at 50 to 100°C in a nitrogen stream for 1 to 10 hours. It is sufficient to carry out the reaction, and after the reaction, post-treatment may be carried out according to a conventional method for obtaining a polymer compound, and the product may be isolated.

本発明に係る樹脂は、また、市販のポリ(P−ビニルフ
ェノール)のような重合体に前記特定の官能基を化学反
応により適宜導入する方法によっても容易に得ることが
できることは言うまでもない。
It goes without saying that the resin according to the present invention can also be easily obtained by appropriately introducing the specific functional group into a commercially available polymer such as poly(P-vinylphenol) through a chemical reaction.

本発明に係る樹脂の重量平均分子量(M%l)は通常1
 、000〜40,000程度、好ましくは3,000
〜20,000程度である。
The weight average molecular weight (M%l) of the resin according to the present invention is usually 1
, about 000 to 40,000, preferably 3,000
~20,000.

本発明で用いられる一般式[I]で示さ九る感光性化合
物に於て、R♂、 R5,R(3,R8で示されるハロ
ゲン原子及びハロアルキル基のハロゲンとしては、塩素
、臭素、弗素、沃素が挙げられ、直鎖状。
In the photosensitive compound represented by general formula [I] used in the present invention, the halogen atom and haloalkyl group represented by R♂, R5, R(3, R8) include chlorine, bromine, fluorine, Iodine is mentioned, and it is linear.

分枝状又は環状のアルキル基のアルキル基、ハロアルキ
ル基のアルキル基及び直鎖状又は分枝状のアルコキシ基
のアルキル基としては、例えばメチル基、エチル基、プ
ロピル基、ブチル基、アミル基、ヘキシル基、オクチル
基、デシル基等炭素数1〜10のアルキル基が挙げられ
、アルケニル基としては、例えばビニル基、1−プロペ
ニル基、2−プロペニル基(アリル基)、2−ブテニル
基、イソプロペニル基、1,3−ブタジェニル基、2−
ヘンテニル基、■−ヘキセニル基等炭素数2〜10のア
ルケニル基が挙げられ、アラルキル基としては、例えば
ベンジル基、フェネチル基、フェニルプロピル基。
Examples of the alkyl group of a branched or cyclic alkyl group, the alkyl group of a haloalkyl group, and the alkyl group of a linear or branched alkoxy group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, Alkyl groups having 1 to 10 carbon atoms such as hexyl group, octyl group, decyl group, etc. are mentioned, and examples of alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 2-butenyl group, iso propenyl group, 1,3-butadienyl group, 2-
Examples include alkenyl groups having 2 to 10 carbon atoms such as hentenyl group and -hexenyl group. Examples of aralkyl group include benzyl group, phenethyl group, and phenylpropyl group.

フェニルブチル基等炭素数7〜10のアラルキル基が挙
げられる。また、置換フェニル基の置換基であるハロゲ
ン原子及びハロアルキル基のハロゲンとしては、塩素、
臭素、弗素、沃素が挙げられ、直鎖状2分枝状又は環状
のアルキル基のアルキル基、ハロアルキル基のアルキル
基及び直鎖状又は分枝状のアルコキシ基のアルキル基と
しては1例えばメチル基、エチル基、プロピル基、ブチ
ル基。
Examples include aralkyl groups having 7 to 10 carbon atoms such as phenylbutyl group. In addition, halogen atoms as substituents of substituted phenyl groups and halogens of haloalkyl groups include chlorine,
Examples include bromine, fluorine, and iodine, and examples of the alkyl group of a linear bibranched or cyclic alkyl group, an alkyl group of a haloalkyl group, and an alkyl group of a linear or branched alkoxy group include 1, for example, a methyl group. , ethyl group, propyl group, butyl group.

アミル基、ヘキシル基、オクチル基、デシル基等炭素数
1〜10のアルキル基が挙げられる。
Examples include alkyl groups having 1 to 10 carbon atoms such as amyl group, hexyl group, octyl group, and decyl group.

本発明者らは露光により酸を発生する感光性化合物につ
いて鋭意研究の途上、露光によりブリーチする感光性化
合物、即ち上記−数式[Iコで示される感光性化合物を
用いた場合には、その内部セル効果により、従来の感光
性化合物を用いた場合よりも露光後の透過性が著しく改
善され、解像度が大幅に向上することを見出し、本発明
を完成するに至った。
In the course of intensive research on photosensitive compounds that generate acid when exposed to light, the present inventors discovered that when using a photosensitive compound that bleaches when exposed to light, that is, a photosensitive compound represented by the above formula [I], the internal The present inventors have discovered that due to the cell effect, the transmittance after exposure is significantly improved and the resolution is significantly improved compared to when conventional photosensitive compounds are used, and the present invention has been completed.

本発明で用いられる溶剤としては、樹脂と感光性化合物
の両者を溶解可能なものであれば何れにても良いが、通
常は385r+m及び248.4nm付近に吸収を有し
ないものがより好ましく用いられる。より具体的にはエ
チルセロソルブアセテート、メチルセロソルブアセテー
ト、ジエチレングリコールジメチルエーテル、乳酸エチ
ル、乳酸メチル、ジオキサン又はエチレングリコールモ
ノイソプロピルエーテル等が挙げられるが勿論これ等に
限定されるものではない。
The solvent used in the present invention may be any solvent as long as it can dissolve both the resin and the photosensitive compound, but it is usually more preferable to use a solvent that does not have absorption in the vicinity of 385r+m and 248.4nm. . More specific examples include ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether, ethyl lactate, methyl lactate, dioxane, and ethylene glycol monoisopropyl ether, but are not limited thereto.

本発明に係る樹脂は30Or+m以上の波長領域で光の
吸収がなく + 365nmO1線光には極めて高い光
透過性を有している。また、酸発生剤についてもi線光
でも酸が発生する事が確認されており、化学増幅作用が
利用出来る。従って、本発明のレジスト材料は化学増幅
方法を利用して低露光量のKrFエキシマレーザ光(2
48,4nm)やi線光(365nm)を用いてパター
ン形成可能なレジスト材料である。
The resin according to the present invention does not absorb light in a wavelength range of 30 Or+m or more, and has extremely high light transmittance for +365 nm O1 line light. It has also been confirmed that acid generators generate acids even with i-line light, and chemical amplification can be used. Therefore, the resist material of the present invention utilizes a chemical amplification method to produce a low exposure amount of KrF excimer laser light (2
It is a resist material that can be patterned using i-line light (365 nm) or i-line light (365 nm).

[作用] 本発明の作用について説明すると、先ず、KrFエキシ
マレーザ光、i線光等で露光された部位は例えば下記(
A)で示される光反応に従って酸が発生する。
[Function] To explain the function of the present invention, first, a region exposed to KrF excimer laser light, i-line light, etc. is exposed to, for example, the following (
Acid is generated according to the photoreaction shown in A).

露光工程に続いて加熱処理すると下記(B)の反応式に
従って樹脂の官能基が酸により化学変化を受け、アルカ
リ可溶性となり、現像の際、現像液に溶出してくる。
When heat treatment is performed subsequent to the exposure step, the functional groups of the resin undergo a chemical change by the acid according to the reaction formula (B) below, and become alkali-soluble, which is eluted into the developer during development.

他方、未露光部は酸が発生しない為、加熱処理しても化
学変化は起らず、アルカリ可溶性基の発現はない。また
、樹脂自身の耐熱性が高い為、加熱処理時、樹脂の軟化
は認められない。このように本発明のレジスト材料を用
いてパターン形成を行った場合には露光部と未露光部と
の間でアルカリ現像液に対して大きな溶解度差を生じ、
しかも、未露光部の樹脂が加熱処理時、軟化しないので
その結果、良好なコントラストを有したポジ型のパター
ンが形成される。また、前記反応式(B)で示されるよ
うに露光で発生した酸は触媒的に作用する為、露光は必
要な酸を発生させるだけでよく、露光エネルギー量の低
減が可能となる。
On the other hand, since no acid is generated in the unexposed area, no chemical change occurs even after heat treatment, and no alkali-soluble groups are expressed. Furthermore, since the resin itself has high heat resistance, no softening of the resin is observed during heat treatment. When a pattern is formed using the resist material of the present invention in this way, a large difference in solubility in an alkaline developer occurs between the exposed and unexposed areas.
Moreover, since the resin in the unexposed areas does not soften during the heat treatment, a positive pattern with good contrast is formed. Further, as shown in the reaction formula (B), since the acid generated by exposure acts catalytically, exposure only needs to generate the necessary acid, making it possible to reduce the amount of exposure energy.

[実施例コ 以下に実施例、参考例を挙げて本発明を更に詳細に説明
するが1本発明はこれ等により何ら制約を受けるもので
はない。
[Example] The present invention will be explained in more detail with reference to Examples and Reference Examples below, but the present invention is not limited by these in any way.

参考例 1゜ p−tert−ブトキシスチレン88g及びフマロニト
リル39gを2,2′−アゾビス(2−メチルプロピオ
ン酸メチル)の存在下、トルエン溶媒中、窒素気流下、
90℃で2時間重合反応させた。反応後、反応液をメタ
ノール中に注入して晶析させ、析出品を濾取、乾燥して
p−tert−ブトキシスチレン−フマロニトリル共重
合体(■約10,000) 120gを得た。
Reference Example 1 88 g of p-tert-butoxystyrene and 39 g of fumaronitrile were mixed in a toluene solvent under a nitrogen stream in the presence of 2,2'-azobis(methyl 2-methylpropionate),
A polymerization reaction was carried out at 90°C for 2 hours. After the reaction, the reaction solution was poured into methanol to cause crystallization, and the precipitated product was collected by filtration and dried to obtain 120 g of p-tert-butoxystyrene-fumaronitrile copolymer (about 10,000).

実施例 1゜ 下記の組成から成るレジス P−むert−ブトキシスチレン− フマロニトリル共重合体 (参考例1で得られた化合物) ト材料を調製した。Example 1゜ Regis consisting of the following composition P-mert-butoxystyrene- fumaronitrile copolymer (Compound obtained in Reference Example 1) A sheet material was prepared.

ジエチレングリコールジメチルエーテル15.0g第1
図を用いて上記レジスト材料を使用したパターン形成方
法を説明する。半導体等の基板1上に上記レジスト材料
2を回転塗布し、90℃、90秒間ホットプレートでソ
フトベーク後、1.0μmの膜厚のレジスト材料膜を得
た(第1図(a))。次に248.4naのKrFエキ
シマレーザ光3をマスク4を介して選択的に露光した(
第1図(b))。そして130℃、90秒間ホットプレ
ートでベーク後、アルカリ現像液(2,38%テトラメ
チルアンモニウムヒドロキシド水溶液)で60秒間現像
することにより、レジスト材料2の露光部のみを溶解除
去し、ポジ型パターン2aを得た(第1図(C))。こ
のレジスト材料膜(1μm)の露光前後の紫外線分光曲
線を第2図に示す。露光前は約65%−の透過率が、露
光後は約80%と高い透過性を示している。また、コノ
時ノボジ型パターンのアスペクト比は約88度の灯影状
の0.25μmラインアンドスペースパターンであった
。更にこのレジスト材料膜(1μl11)のγ特性を第
3図に示す。この材料は最小露光量的2011IJ/a
112という高感度であった。
Diethylene glycol dimethyl ether 15.0g 1st
A pattern forming method using the above resist material will be explained with reference to the drawings. The resist material 2 was spin-coated onto a substrate 1 such as a semiconductor, and after soft baking on a hot plate at 90° C. for 90 seconds, a resist material film with a thickness of 1.0 μm was obtained (FIG. 1(a)). Next, KrF excimer laser light 3 of 248.4 na was selectively exposed through a mask 4 (
Figure 1(b)). After baking on a hot plate at 130°C for 90 seconds, developing with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds dissolves and removes only the exposed areas of resist material 2, forming a positive pattern. 2a was obtained (Fig. 1(C)). FIG. 2 shows the ultraviolet ray spectral curves of this resist material film (1 μm) before and after exposure. The transmittance was approximately 65% before exposure, and the transmittance was as high as approximately 80% after exposure. In addition, the aspect ratio of the continuous pattern was a 0.25 μm line-and-space pattern with a shadow shape of about 88 degrees. Furthermore, the γ characteristics of this resist material film (1 μl) are shown in FIG. This material has a minimum exposure dose of 2011 IJ/a
It had a high sensitivity of 112.

実施例 2゜ 実施例1に於て樹脂を下記に示すスチレン系樹脂に変更
し、それ以外は実施例1と同様にしてレジスト材料を調
製し、実施例1と同様の実験を行った。
Example 2 A resist material was prepared in the same manner as in Example 1 except that the resin in Example 1 was changed to the styrene resin shown below, and the same experiment as in Example 1 was conducted.

p−tert−ブトキシスチレン− p−ヒドロキシスチレン共重合体(F+約13,000
)その結果、実施例1と同様の良好な結果が得られた。
p-tert-butoxystyrene-p-hydroxystyrene copolymer (F+ approx. 13,000
) As a result, the same good results as in Example 1 were obtained.

このレジスト材料を用いて得たポジ型パターンは約25
mJ/cm”の露光エネルギー量でパターン形成が可能
であった。
The positive pattern obtained using this resist material was approximately 25
Pattern formation was possible with an exposure energy amount of "mJ/cm".

実施例 3゜ 実施例1に於て感光性化合物を下記に示す化合物に変更
し、それ以外は実施例1と同様にしてレジスト材料を調
製し、実施例1と同様の実験を行った・ その結果、実施例1と同様の良好な結果が得られた。こ
のレジスト材料を用いて得たポジ型パターンは約18c
+J/c口2の露光エネルギー量でパターン形成が可能
であった。
Example 3゜A resist material was prepared in the same manner as in Example 1 except that the photosensitive compound in Example 1 was changed to the compound shown below, and the same experiment as in Example 1 was conducted. As a result, good results similar to those in Example 1 were obtained. The positive pattern obtained using this resist material is approximately 18cm
Pattern formation was possible with the exposure energy amount of +J/c port 2.

実施例 4゜ 実施例2に於て感光性化合物を下記に示す化合物に変更
し、それ以外は実施例2と同様にしてレジスト材料を調
製し、実施例2と同様の実験を行った。
Example 4 A resist material was prepared in the same manner as in Example 2 except that the photosensitive compound in Example 2 was changed to the compound shown below, and the same experiment as in Example 2 was conducted.

その結果、実施例2と同様の良好な結果が得られた。こ
のレジスト材料を用いて得たポジ型パターンは約12m
J/cm2の露光エネルギー量でパターン形成が可能で
あった。
As a result, good results similar to those of Example 2 were obtained. The positive pattern obtained using this resist material is approximately 12 m long.
Pattern formation was possible with an exposure energy amount of J/cm2.

実施例 5゜ p−メトキシメトキシスチレン− マレイン酸系共重合体(l約15,000)(k/1/
p=2/1/1) 6.0g ジエチレングリコールジメチルエーテル15.0g 実施例1と同様の実験を行った。
Example 5 p-methoxymethoxystyrene-maleic acid copolymer (about 15,000 l) (k/1/
p=2/1/1) 6.0 g Diethylene glycol dimethyl ether 15.0 g An experiment similar to Example 1 was conducted.

その結果、実施例1と同様の良好な結果が得られた。こ
のレジスト材料を用いて得たポジ型パターンは約22m
J/am2の露光エネルギー量でパターン形成が可能で
あった。
As a result, good results similar to those of Example 1 were obtained. The positive pattern obtained using this resist material is approximately 22 m long.
Pattern formation was possible with an exposure energy amount of J/am2.

[発明の効果] 本開明に係るレジスト材料を400nm以下の光源例え
ば365nmの1線光、300nm以下の遠紫外光(D
eepUV)−例えばKrFIキシマレーザ光(248
゜4nn+)等の露光用レジスト材料として用いた場合
には、サブミクロンオーダーの形状の良い微細なパター
ンが容易に得られる。従つ−C本発明は、半導体産業等
に於ける超微細パターンの形成にとって大きな価値を有
するものである。
[Effects of the Invention] The resist material according to the present invention can be used with a light source of 400 nm or less, for example, 365 nm or less single-line light, 300 nm or less deep ultraviolet light (D
eepUV) - for example, KrFI ximer laser light (248
When used as a resist material for exposure such as 4nn+), fine patterns with good shapes on the order of submicrons can be easily obtained. Accordingly, the present invention has great value for the formation of ultra-fine patterns in the semiconductor industry and the like.

尚、本レジスト材料はi線光や遠紫外光、KrFエキシ
マレーザ光で特に効果を発揮するが、電子線やX線でも
充分使用が可能である。
This resist material is particularly effective with i-line light, far ultraviolet light, and KrF excimer laser light, but it can also be used satisfactorily with electron beams and X-rays.

【図面の簡単な説明】[Brief explanation of drawings]

第1図〜第3図は実施例1で得られた結果を示し、第1
図は本発明のレジスト材料を用いたパターン形成方法の
工程断面図、第2図は本発明のレジスト材料の紫外線分
光曲線図(但し、実線は露光前、破線は露光後)、第3
図は本発明のレジスト材料のγ特性図を夫々示す。また
第4図は従来のレジスト材料を用いたパターン形成方法
の工程断面図、第5図は従来のレジスト材料の紫外線分
光曲線図(但し、実線は露光前、破線は露光後)、第6
図は従来のレジスト材料のγ特性図である。 1・・・基板、2・・・本発明のレジスト材料膜、3・
・・KrFエキシマレーザ光、4・・・マスク、5・・
・従来のレジスト材料膜、2a・・・樹脂パターン。
Figures 1 to 3 show the results obtained in Example 1;
The figure is a process cross-sectional view of a pattern forming method using the resist material of the present invention.
The figures show γ characteristic diagrams of the resist materials of the present invention. Fig. 4 is a process cross-sectional view of a pattern forming method using a conventional resist material, Fig. 5 is an ultraviolet ray spectral curve diagram of a conventional resist material (the solid line is before exposure, the broken line is after exposure), and Fig.
The figure is a γ characteristic diagram of a conventional resist material. DESCRIPTION OF SYMBOLS 1...Substrate, 2...Resist material film of the present invention, 3.
...KrF excimer laser light, 4...mask, 5...
- Conventional resist material film, 2a...resin pattern.

Claims (3)

【特許請求の範囲】[Claims] (1)酸雰囲気下で加熱により化学変化を受けてアルカ
リ可溶性となる官能基を有する成分と樹脂に耐熱性を付
与する成分とから構成される耐熱性樹脂と、露光により
酸を発生する下記一般式[ I ]で示される感光性化合
物と、この両者を溶解可能な溶剤とを含んで成ることを
特徴とするレジスト材料。 ▲数式、化学式、表等があります▼[ I ] [式中、R_0^1、R_0^2、R_0^3、R_0
^4は夫々独立して水素原子ハロゲン原子、炭素数1〜
10の直鎖状、分枝状又は環状のアルキル基、炭素数1
〜10のハロアルキル基、炭素数1〜10の直鎖状又は
分枝状のアルコキシ基、炭素数2〜10のアルケニル基
、炭素数7〜10のアラルキル基、フェニル基、置換フ
ェニル基(置換基は、ハロゲン原子、炭素数1〜10の
直鎖状、分枝状又は環状のアルキル基、炭素数1〜10
のハロアルキル基、炭素数1〜10の直鎖状又は分枝状
のアルコキシ基、ニトロ基、ニトリル基又はアミド基。 )を表わす。また、R_0^1とR_0^2、R_0^
2とR_0^3及びR_0^3とR_0^4は夫々独立
して、互いに結合して脂環、]ヘテロ脂環、芳香環又は
ヘテロ芳香環を成していても良い。]
(1) A heat-resistant resin consisting of a component that has a functional group that undergoes a chemical change when heated in an acid atmosphere and becomes alkali-soluble, and a component that imparts heat resistance to the resin, and the following general resins that generate acid when exposed to light: A resist material comprising a photosensitive compound represented by formula [I] and a solvent capable of dissolving both. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_0^1, R_0^2, R_0^3, R_0
^4 each independently represents a hydrogen atom, a halogen atom, and a carbon number of 1 to
10 linear, branched or cyclic alkyl groups, 1 carbon number
-10 haloalkyl group, linear or branched alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, phenyl group, substituted phenyl group (substituent is a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms.
a haloalkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms, a nitro group, a nitrile group, or an amide group. ). Also, R_0^1, R_0^2, R_0^
2 and R_0^3 and R_0^3 and R_0^4 may each independently be bonded to each other to form an alicyclic ring, a heteroalicyclic ring, an aromatic ring, or a heteroaromatic ring. ]
(2)酸雰囲気下で加熱により化学変化を受けてアルカ
リ可溶性となる官能基を有する成分と樹脂に耐熱性を付
与する成分とから構成される耐熱性樹脂が下記一般式[
II] ▲数式、化学式、表等があります▼[II] [式中、R^1はメチル基、イソプロピル基、tert
−ブチル基、メトキシメチル基、イソプロポキシメチル
基、テトラヒドロピラニル基、テトラヒドロプラニル基
、トリメチルシリル基、tert−ブトキシカルボニル
基又はイソプロポキシカルボニル基を表わし、R^2は
水素原子、ハロゲン原子又はメチル基を表わし、R^3
は水素原子、p−ヒドロキシフェニル基、p−クロルフ
ェニル基、フェニル基、シアノ基又は−COOR^7(
但し、R^7は炭素数3〜10の分岐状又は環状のアル
キル基、又は水素原子を表わす。 )を表わし、R^4及びR^6は夫々独立して水素原子
、メチル基又はハロゲン原子を表わし、R^5は水素原
子、シアノ基又は−COOR^8(但し、R^8は炭素
数3〜10の分岐状又は環状のアルキル基、又は水素原
子を表わす。)を表わし、R^9は水素原子又は−CO
OR^1^0(但し、R^1^0は炭素数3〜10の分
岐状又は環状のアルキル基、又は水素原子を表わす。)
を表わし、k及びlは夫々独立して自然数を表わす。]
で示される樹脂である請求項(1)に記載のレジスト材
料。
(2) A heat-resistant resin composed of a component having a functional group that undergoes a chemical change upon heating in an acid atmosphere and becomes alkali-soluble, and a component that imparts heat resistance to the resin has the following general formula [
II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] [In the formula, R^1 is a methyl group, isopropyl group, tert
- represents a butyl group, methoxymethyl group, isopropoxymethyl group, tetrahydropyranyl group, tetrahydropranyl group, trimethylsilyl group, tert-butoxycarbonyl group, or isopropoxycarbonyl group, and R^2 is a hydrogen atom, a halogen atom, or a methyl group. Represents a group, R^3
is a hydrogen atom, p-hydroxyphenyl group, p-chlorophenyl group, phenyl group, cyano group or -COOR^7(
However, R^7 represents a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a hydrogen atom. ), R^4 and R^6 each independently represent a hydrogen atom, a methyl group, or a halogen atom, and R^5 is a hydrogen atom, a cyano group, or -COOR^8 (however, R^8 is the number of carbon atoms 3 to 10 branched or cyclic alkyl groups, or a hydrogen atom), and R^9 is a hydrogen atom or -CO
OR^1^0 (However, R^1^0 represents a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a hydrogen atom.)
, and k and l each independently represent a natural number. ]
The resist material according to claim 1, which is a resin represented by:
(3)酸雰囲気下で加熱により化学変化を受けてアルカ
リ可溶性となる官能基を有する成分と樹脂に耐熱性を付
与する成分とから構成される耐熱性樹脂が下記一般式[
III] ▲数式、化学式、表等があります▼[III] [式中、Xは酸素原子又は▲数式、化学式、表等があり
ます▼(但し、 R^1^1は炭素数1〜10の直鎖状、分岐状又は環状
のアルキル基又は置換基を有していても良いフェニル基
を表わし、qは0又は自然数を表わす。)を表わし、l
’及びpは夫々独立して0又は自然数を表わし、R^1
、R^2、R^3、R^4、R^5、R^6、R^9及
びkは前記と同じ。]で示される樹脂である請求項(1
)に記載のレジスト材料。
(3) A heat-resistant resin composed of a component having a functional group that undergoes a chemical change upon heating in an acid atmosphere and becomes alkali-soluble and a component that imparts heat resistance to the resin has the following general formula [
III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] [In the formula, represents a chain, branched or cyclic alkyl group or a phenyl group which may have a substituent, q represents 0 or a natural number);
' and p each independently represent 0 or a natural number, R^1
, R^2, R^3, R^4, R^5, R^6, R^9 and k are the same as above. ] Claim (1)
) Resist materials listed in ).
JP2019616A 1990-01-30 1990-01-30 Resist material Expired - Lifetime JP2747735B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019616A JP2747735B2 (en) 1990-01-30 1990-01-30 Resist material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2019616A JP2747735B2 (en) 1990-01-30 1990-01-30 Resist material

Publications (2)

Publication Number Publication Date
JPH03223865A true JPH03223865A (en) 1991-10-02
JP2747735B2 JP2747735B2 (en) 1998-05-06

Family

ID=12004120

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2019616A Expired - Lifetime JP2747735B2 (en) 1990-01-30 1990-01-30 Resist material

Country Status (1)

Country Link
JP (1) JP2747735B2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0488348A (en) * 1990-08-01 1992-03-23 Wako Pure Chem Ind Ltd Novel resist material
EP0588544A2 (en) * 1992-09-14 1994-03-23 Wako Pure Chemical Industries Ltd Fine pattern forming material and pattern formation process
US5468589A (en) * 1991-06-18 1995-11-21 Wako Pure Chemical Industries, Ltd. Resist material and pattern formation process
US5563022A (en) * 1991-11-02 1996-10-08 Basf Aktiengesellschaft Positive-working radiation-sensitive mixture and the production of relief patterns
US6586152B1 (en) 1999-06-10 2003-07-01 Wako Pure Chemical Industries, Ltd. Agent for reducing substrate dependence
US6790589B2 (en) 1993-12-28 2004-09-14 Fujitsu Limited Radiation sensitive material and method for forming pattern

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0488348A (en) * 1990-08-01 1992-03-23 Wako Pure Chem Ind Ltd Novel resist material
US5468589A (en) * 1991-06-18 1995-11-21 Wako Pure Chemical Industries, Ltd. Resist material and pattern formation process
US5670299A (en) * 1991-06-18 1997-09-23 Wako Pure Chemical Industries, Ltd. Pattern formation process
US5563022A (en) * 1991-11-02 1996-10-08 Basf Aktiengesellschaft Positive-working radiation-sensitive mixture and the production of relief patterns
EP0588544A2 (en) * 1992-09-14 1994-03-23 Wako Pure Chemical Industries Ltd Fine pattern forming material and pattern formation process
EP0588544A3 (en) * 1992-09-14 1994-09-28 Wako Pure Chem Ind Ltd Fine pattern forming material and pattern formation process
US6790589B2 (en) 1993-12-28 2004-09-14 Fujitsu Limited Radiation sensitive material and method for forming pattern
US7179580B2 (en) 1993-12-28 2007-02-20 Fujitsu Limited Radiation sensitive material and method for forming pattern
US7465529B2 (en) 1993-12-28 2008-12-16 Fujitsu Limited Radiation sensitive material and method for forming pattern
US6586152B1 (en) 1999-06-10 2003-07-01 Wako Pure Chemical Industries, Ltd. Agent for reducing substrate dependence

Also Published As

Publication number Publication date
JP2747735B2 (en) 1998-05-06

Similar Documents

Publication Publication Date Title
JPH03223860A (en) Novel resist material
KR101661803B1 (en) Chemically amplified negative resist composition
JPH07199467A (en) Photosensitive resin composition and method for forming pattern
JPH03289658A (en) Photosensitive composition
JP3228193B2 (en) Negative photoresist composition and pattern forming method using the same
KR19990044758A (en) Negative resist material, pattern formation method using same, and semiconductor device manufacturing method
KR100711542B1 (en) Method of forming resist pattern, positive resist composition, and layered product
JPH0215270A (en) Photoresist composition
JPH04199152A (en) Photosensitive composition
JP2861253B2 (en) Photosensitive resin composition
JPH03223865A (en) Resist material
JP2847414B2 (en) Resist material
JP2847413B2 (en) Resist material
JPH03223863A (en) Resist material
JP3510502B2 (en) Dissolution inhibitor for chemically amplified photoresist and chemically amplified photoresist composition containing the same
JPH10133380A (en) Novel copolymer for photoresist
JPH08240911A (en) Radiation sensitive resin composition
JPH03223866A (en) Resist material
JP2849666B2 (en) New resist material
JPH04104251A (en) Novel resist material
US6083659A (en) Polymer mixture for photoresist and photoresist composition containing the same
JP2861992B2 (en) New resist material
JPH03223861A (en) Novel resist material
JP4023867B2 (en) Photosensitive resin composition for resist
WO2012014576A1 (en) Negative radiation-sensitive resin composition