JP3854689B2 - Novel photoacid generator - Google Patents
Novel photoacid generator Download PDFInfo
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- JP3854689B2 JP3854689B2 JP19895397A JP19895397A JP3854689B2 JP 3854689 B2 JP3854689 B2 JP 3854689B2 JP 19895397 A JP19895397 A JP 19895397A JP 19895397 A JP19895397 A JP 19895397A JP 3854689 B2 JP3854689 B2 JP 3854689B2
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Description
【0001】
【発明の属する技術分野】
本発明は新規スルホニルジアゾメタン化合物からなる、特に化学増幅型レジスト用として好適な光酸発生剤に関するものである。
【0002】
【従来の技術】
近年、半導体素子や液晶素子などの製造においては、化学増幅型レジスト組成物が使用されるようになってきた。この化学増幅型レジスト組成物は、放射線の照射により生成した酸の触媒作用を利用したレジストであって、高い感度と解像性を有し、放射線の照射により酸を発生する化合物すなわち光酸発生剤の使用量が少なくてよいという利点を有している。
【0003】
この化学増幅型レジストにはポジ型とネガ型の2つのタイプがあり、これらは、一般に、酸発生剤と、発生する酸の作用によりアルカリ水溶液に対する溶解性が変化する被膜形成成分とを基本成分としている。
【0004】
前記ポジ型レジストにおいては、被膜形成成分として、通常tert‐ブトキシカルボニル基、テトラヒドロピラニル基などの溶解抑制基で水酸基の一部を保護したポリヒドロキシスチレンなどが用いられており、一方、ネガ型レジストにおいては、被膜形成成分として、通常上記溶解抑制基で水酸基の一部を保護したポリヒドロキシスチレン、あるいはポリヒドロキシスチレンやノボラック樹脂などの樹脂成分に、メラミン樹脂や尿素樹脂などの酸架橋性物質を組み合わせたものが用いられている。
【0005】
ところで、このような光酸発生剤として、ある種のジアゾメタン化合物が用いられているが(特開平3−103854号公報、特開平4−210960号公報、特開平4−217249号公報)、これらを用いたレジスト組成物は、露光部と未露光部のコントラストに劣り、また満足すべき感度が得られにくいという欠点がある。
【0006】
【発明が解決しようとする課題】
本発明は、従来のジアゾメタン化合物がもつ欠点を克服し、化学増幅型レジストの光酸発生剤として用いた場合、露光部と未露光部のコントラストに優れ、十分な感度を示す新規なスルホニルジアゾメタン化合物を提供することを目的としてなされたものである。
【0007】
【課題を解決するための手段】
本発明者らは、化学増幅型レジストの光酸発生剤として用いたときに、露光部と未露光部のコントラストに優れ、十分な感度を示す新規なジアゾメタン化合物を開発するために鋭意研究を重ねた結果、ビスフェニルスルホニルジアゾメタンの2個のフェニル基に、酸解離性基として第三アルコキシカルボニルアルコキシ基を導入した化合物とすることにより、その目的を達成しうることを見出し、この知見に基づいて本発明をなすに至った。
【0008】
すなわち、本発明は、一般式
【化2】
(式中のR1は炭素数1〜4の低級アルキレン基、R2は炭素数4〜8の第三アルキル基である)
で表わされる新規なスルホニルジアゾメタン化合物からなる光酸発生剤を提供するものである。
【0009】
この一般式(I)におけるR1の低級アルキレン基は、炭素数1〜4のアルキレン基であり、これは直鎖状又は枝分れ状のいずれでもよい。このような低級アルキレン基の例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、イソプロピレン基、イソブチレン基などを挙げることができる。
また、一般式(I)におけるR2の第三アルキル基は、炭素数4〜8の第三アルキル基、例えば第三ブチル基、第三ペンチル基、1,1‐ジメチルブチル基などを挙げることができる。
【0010】
【発明の実施の形態】
本発明で用いる新規なスルホニルジアゾメタン化合物は、例えば次に示す反応式に従い、チオフェノール(II)に、メチレンハライド(III)を縮合させてビス(ヒドロキシフェニルチオ)メタン(IV)を生成させ、次いでこれを酸化してビス(ヒドロキシフェニルスルホニル)メタン(V)を生成させ、これにω‐ハロゲノアルカン酸第三アルキル(VI)を反応させたのち、ジアゾ化するか、あるいはビス(ヒドロキシフェニルスルホニル)メタンをジアゾ化したのち、ω‐ハロゲノアルカン酸第三アルキルを反応させることにより製造することができる。
【0011】
【化3】
(ただし、R 1 及びR 2 は前記と同じ意味をもち、X、X′はハロゲン原子である)
【0012】
この反応において用いるメチレンハライド(III)の例としては、メチレンクロリド、メチレンブロミド、メチレンヨージドを挙げることができる。また、ω‐ハロゲノアルカン酸第三アルキル(VI)の例としては、クロロ酢酸、ブロモ酢酸、3‐クロロプロピオン酸、3‐ブロモプロピオン酸、4‐クロロ酪酸又は4‐ブロモ酪酸の第三ブチルエステル、第三ペンチルエステル又は1,1‐ジメチルブチルエステルなどを挙げることができる。
【0013】
前記反応式におけるチオフェノール(II)とメチレンハライド(III)との縮合は、不活性溶媒例えばアセトン中において、第四アンモニウム塩例えばテトラブチルアンモニウムハライドと炭酸アルカリとの組み合せのような脱ハロゲン化水素剤を用いて行われる。
【0014】
次に、このようにして得たビス(ヒドロキシフェニルチオ)メタン(IV)を酸化して対応するビス(ヒドロキシフェニルスルホニル)メタン(V)を生成する反応は、例えばエタノールのような不活性溶媒中、タングステン酸アルカリを触媒として過酸化水素によって行うことができる。
【0015】
また、ビス(ヒドロキシフェニルスルホニル)メタン(V)又はそのジアゾ化物(VIII)に第三アルコキシカルボニルアルコキシ基を導入する反応は、ジメチルホルムアミドのような不活性溶媒中で炭酸アルカリのようなアルカリの存在下、ω‐ハロゲノアルカン酸第三アルキル(VI)を反応させることにより行うことができる。
【0016】
さらに、ビス(ヒドロキシフェニルスルホニル)メタン(V)又はその第三アルコキシカルボニルアルコキシ化物(VII)のジアゾ化は、エタノールのような不活性溶媒中、第三アミン例えばトリエチルアミンの存在下でトシルアジドを反応させることによって行われる。
このようにして得た生成物は、常法に従い再結晶などの手段により精製することができる。
【0017】
このようにして得られる前記一般式(I)のスルホニルジアゾメタン化合物は、文献未載の新規化合物であって、光の照射により酸を発生する性質を有している。
【0018】
【実施例】
次に実施例により本発明をさらに詳細に説明する。
【0019】
参考例1
4‐ヒドロキシベンゼンチオール50g(0.40モル)とテトラブチルアンモニウムブロミド1.5g(0.006モル)をアセトン250g中に溶かし、これに炭酸カリウム43g(0.31モル)を加えた。次いでメチレンブロミド40g(0.23モル)を45℃において30分間にわたって滴下した。この混合物をさらに45℃で8時間かき混ぜたのち、析出した臭化カリウムをろ別し、溶媒を真空下40℃で留去し、次いで得られた生成物に水500gを加え、酢酸エチル600gで抽出後、溶媒を留去しビス(4‐ヒドロキシフェニルチオ)メタンを黄色油状物として得た。
【0020】
次に、このビス(4‐ヒドロキシフェニルチオ)メタン50g(0.19モル)をエタノール275gに溶かし、タングステン酸ナトリウム5g(0.02g)を加えた。これに35%過酸化水素水162g(1.67モル)を50℃において、1時間にわたって滴下した。この反応混合物をさらに50℃で5時間かき混ぜた。次いで、30%水酸化ナトリウム水溶液で中和し、析出した結晶をろ取した。このようにしてビス(4‐ヒドロキシフェニルスルホニル)メタンを白色結晶として得た。
【0021】
次に、このビス(4‐ヒドロキシフェニルスルホニル)メタン30g(0.09モル)をジメチルホルムアミド160gに溶かし、炭酸カリウム28g(0.20モル)を加えた。これにクロロ酢酸tert‐ブチル30g(0.20モル)を室温において30分にわたって滴下した。この混合物をさらに80℃で3時間かき混ぜたのち、室温まで冷却し、炭酸カリウムをろ別し、次いで希塩酸1200gで洗浄し、ビス(4‐tert‐ブトキシカルボニルメチルオキシフェニルスルホニル)メタン42.0gを黄色油状物として得た。
【0022】
最後に、このビス(4‐tert‐ブトキシカルボニルメチルオキシフェニルスルホニル)メタン30g(0.054モル)とトシルアジド15g(0.076モル)をエタノール300gに溶かし、これにトリエチルアミン12.5g(0.12モル)を室温で30分間にわたって滴下した。この混合物をさらに室温で1.5時間かき混ぜたのち、析出した結晶をろ取し、得られた最終生成物をアセトニトリルから繰り返し再結晶し、目的物であるビス(4‐tert‐ブトキシカルボニルメチルオキシフェニルスルホニル)ジアゾメタン13.0gを得た。その化合物の融点は98℃、分解点は114℃であった。
図1及び図2にこの化合物の赤外吸収スペクトル及びプロトン核磁気共鳴スペクトルを示す。
【0023】
参考例2
参考例1と同様にしてビス(4‐ヒドロキシフェニルスルホニル)メタンを製造し、これにクロロ酢酸tert‐ブチル30gの代りに3‐クロロプロピオン酸tert‐ブチル33gを用い、同様に操作することによりビス(4‐tert‐ブトキシカルボニルエチルオキシフェニルスルホニル)ジアゾメタン13.5gを得た。
【0024】
実施例
水酸基の水素原子の39モル%がtert‐ブチルオキシカルボニル基で置換された重量平均分子量10,000のポリヒドロキシスチレンと水酸基の水素原子の39モル%がエトキシエチル基で置換された重量平均分子量10,000のポリヒドロキシスチレンとを重量比3:7の割合で含む樹脂混合物100重量部に、光酸発生剤として参考例1で得たビス(4‐tert‐ブトキシカルボニルメチルオキシフェニルスルホニル)ジアゾメタン5重量部とトリエチルアミン0.3重量部とサリチル酸0.2重量部を配合し、プロピレングリコールモノメチルエーテルアセテート490重量部に溶解し、この溶液を孔径0.2μmのメンブランフィルターを通してろ過し、ポジ型レジスト組成物を調製した。
次に、このポジ型レジスト組成物について以下に示す方法で物性を求め、その結果を表1に示す。
なお、比較のために、公知の光酸発生剤であるビス(シクロヘキシルスルホニル)ジアゾメタン5重量部を用いたポジ型レジスト組成物についての物性を求め、その結果を表1に併記した。
【0025】
(1)感度:
試料をスピンナーを用いてシリコンウエーハ上に塗布し、これをホットプレート上で90℃、90秒間乾燥して膜厚0.7μmのレジスト膜を得た。この膜に縮小投影露光装置NSR−2005EX8A(ニコン社製)を用いて、1mJ/cm2ずつドーズ量を加え露光したのち、110℃、90秒間のPEB(POST EXPOSURE BAKE)を行い、2.38重量%テトラメチルアンモニウムヒドロキシド水溶液で23℃にて60秒間現像し、30秒間水洗して乾燥したとき、現像後の露光部の膜厚が0となる最小露光時間を感度としてmJ/cm2(エネルギー量)単位で測定した。
【0026】
(2)解像性:
上記(1)と同様な操作を行い、0.25μmのマスクパターンを再現する露光量における限界解像度で示した。
【0027】
(3)レジストパターン形状:
上記(1)と同様な操作を行い、0.25μmの矩形のレジストパターンが得られた場合を○、レジストパターントップがやや細いパターンとなったり、波打ったレジストパターンとなった場合を×として評価した。
【0028】
(4)引き置き経時安定性:
上記(1)において、露光までの操作を行ったのち、60分間放置したあと、同様にPEB処理、現像を行い、0.25μmのレジストパターンの断面形状をSEM(走査型電子顕微鏡)写真により観察し、0.25μmのラインアンドスペースが1:1に形成されたものを5、ライン幅(レジストパターン幅)が0.25μmより広くなり、スペース幅が0.25μmより狭くなったものを3、解像しないものを1とし、それぞれの中間を4,2として評価した。
【0029】
(5)残膜率:
上記(1)と同様な操作を行い、未露光部の残膜率を現像前膜厚に対する現像後膜厚の割合として示した。
【0030】
【表1】
【0031】
【発明の効果】
本発明の光酸発生剤は新規化合物を活性成分とするものであって、これを化学増幅型レジストの光酸発生剤として用いると、露光部と未露光部のコントラストがよいため、残膜率が高く、プロファイル形状の優れたパターンを与える。また、本発明の活性成分として用いる化合物は、第三アルキル基が酸により切断され、残基からはカルボン酸が生成するので高感度を示すという利点もある。
【図面の簡単な説明】
【図1】 参考例1で得た化合物の赤外吸収スペクトル図。
【図2】 参考例1で得た化合物の+H核磁気共鳴スペクトル図。[0001]
BACKGROUND OF THE INVENTION
The present invention consists of novel sulfonyl diazomethane compounds, and more particularly to a suitable photoacid generator used for a chemically amplified resist.
[0002]
[Prior art]
In recent years, chemically amplified resist compositions have been used in the manufacture of semiconductor devices, liquid crystal devices, and the like. The chemically amplified resist composition is a resist utilizing a catalytic action of the generated acid by irradiation of radiation, it has high sensitivity and resolution, of generating an acid upon irradiation with radioactive compound i.e. photoacid generator There is an advantage that the amount of the agent used may be small.
[0003]
There are two types of chemically amplified resists, positive type and negative type, which are generally composed of an acid generator and a film forming component whose solubility in an alkaline aqueous solution is changed by the action of the generated acid. It is said.
[0004]
In the positive resist, polyhydroxystyrene or the like in which a part of the hydroxyl group is protected with a dissolution inhibiting group such as a tert-butoxycarbonyl group or a tetrahydropyranyl group is usually used as a film forming component. In resist, as a film-forming component, polyhydroxystyrene in which a part of the hydroxyl group is usually protected with the above-described dissolution inhibiting group, or a resin component such as polyhydroxystyrene or novolac resin, and an acid-crosslinking substance such as melamine resin or urea resin A combination of these is used.
[0005]
Incidentally, as such a photo-acid generating agent, although certain diazomethane compounds are used (JP-A 3-103854, JP-A No. 4-210960 and JP-Hei 4-217249), these The resist composition used has the disadvantages that the contrast between the exposed and unexposed areas is inferior and that satisfactory sensitivity is difficult to obtain.
[0006]
[Problems to be solved by the invention]
The present invention overcomes the disadvantages conventional diazomethane compounds have, when used as a photoacid generator of the chemically amplified resist, excellent in contrast between exposed and unexposed areas, novel sulfonyl diazomethane compounds exhibit sufficient sensitivity It was made for the purpose of providing.
[0007]
[Means for Solving the Problems]
The present inventors have found that when used as a photoacid generator of the chemically amplified resist, excellent in contrast between exposed and unexposed areas, intensive studies to develop a novel diazomethane compounds exhibit sufficient sensitivity As a result, it was found that the purpose can be achieved by using a compound obtained by introducing a tertiary alkoxycarbonylalkoxy group as an acid dissociable group into the two phenyl groups of bisphenylsulfonyldiazomethane. It came to make this invention.
[0008]
That is, the present invention has the general formula:
(Wherein R 1 is a lower alkylene group having 1 to 4 carbon atoms , and R 2 is a tertiary alkyl group having 4 to 8 carbon atoms )
A photoacid generator comprising a novel sulfonyldiazomethane compound represented by the formula:
[0009]
The lower alkylene group represented by R 1 in the general formula (I) is an alkylene group having 1 to 4 carbon atoms, which may be linear or branched. Examples of such a lower alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, an isopropylene group, and an isobutylene group.
The tertiary alkyl group represented by R 2 in the general formula (I) includes tertiary alkyl groups having 4 to 8 carbon atoms, such as tertiary butyl group, tertiary pentyl group, and 1,1-dimethylbutyl group. Can do.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The novel sulfonyldiazomethane compound used in the present invention is produced by, for example, condensing thiophenol (II) with methylene halide (III) to produce bis (hydroxyphenylthio) methane (IV) according to the following reaction formula. This is oxidized to produce bis (hydroxyphenylsulfonyl) methane (V), which is reacted with a tertiary alkyl (VI) ω-halogenoalkanoate and then diazotized, or bis (hydroxyphenylsulfonyl) After diazotizing methane, it can be produced by reacting a tertiary alkyl ω-halogenoalkanoate.
[0011]
[Chemical 3]
(However, R 1 and R 2 have the same meaning as described above, and X and X ′ are halogen atoms . )
[0012]
Examples of methylene halide (III) used in this reaction include methylene chloride, methylene bromide, and methylene iodide. Examples of tertiary alkyl (VI) ω-halogenoalkanoates include chloroacetic acid, bromoacetic acid, 3-chloropropionic acid, 3-bromopropionic acid, 4-chlorobutyric acid or tert-butyl ester of 4-bromobutyric acid. And tertiary pentyl ester or 1,1-dimethylbutyl ester.
[0013]
The condensation of thiophenol (II) and methylene halide (III) in the above reaction formula is performed by dehydrohalogenation such as a combination of a quaternary ammonium salt such as tetrabutylammonium halide and an alkali carbonate in an inert solvent such as acetone. It is performed using an agent.
[0014]
Next, the reaction of oxidizing the bis (hydroxyphenylthio) methane (IV) thus obtained to produce the corresponding bis (hydroxyphenylsulfonyl) methane (V) is carried out in an inert solvent such as ethanol. It can be carried out with hydrogen peroxide using an alkali tungstate as a catalyst.
[0015]
In addition, the reaction of introducing a tertiary alkoxycarbonylalkoxy group into bis (hydroxyphenylsulfonyl) methane (V) or a diazotized product thereof (VIII) is carried out in the presence of an alkali such as an alkali carbonate in an inert solvent such as dimethylformamide. Below, it can carry out by making omega-haloalkanoic acid tertiary alkyl (VI) react.
[0016]
Furthermore, diazotization of bis (hydroxyphenylsulfonyl) methane (V) or its tertiary alkoxycarbonylalkoxylate (VII) reacts tosyl azide in the presence of a tertiary amine such as triethylamine in an inert solvent such as ethanol. Is done by.
The product thus obtained can be purified by means such as recrystallization according to a conventional method.
[0017]
The sulfonyldiazomethane compound of the general formula (I) thus obtained is a novel compound not described in any literature, and has a property of generating an acid upon irradiation with light.
[0018]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0019]
Reference example 1
4-hydroxybenzenethiol 50 g (0.40 mol) and tetrabutylammonium bromide 1.5 g (0.006 mol) were dissolved in 250 g of acetone, and 43 g (0.31 mol) of potassium carbonate was added thereto. Subsequently, 40 g (0.23 mol) of methylene bromide was added dropwise at 45 ° C. over 30 minutes. The mixture was further stirred at 45 ° C. for 8 hours, the precipitated potassium bromide was filtered off, the solvent was distilled off under vacuum at 40 ° C., and then 500 g of water was added to the resulting product, and 600 g of ethyl acetate was added. After extraction, the solvent was distilled off to obtain bis (4-hydroxyphenylthio) methane as a yellow oil.
[0020]
Next, 50 g (0.19 mol) of this bis (4-hydroxyphenylthio) methane was dissolved in 275 g of ethanol, and 5 g (0.02 g) of sodium tungstate was added. To this, 162 g (1.67 mol) of 35% aqueous hydrogen peroxide was added dropwise at 50 ° C. over 1 hour. The reaction mixture was further stirred at 50 ° C. for 5 hours. Next, the solution was neutralized with a 30% aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration. Thus, bis (4-hydroxyphenylsulfonyl) methane was obtained as white crystals.
[0021]
Next, 30 g (0.09 mol) of bis (4-hydroxyphenylsulfonyl) methane was dissolved in 160 g of dimethylformamide, and 28 g (0.20 mol) of potassium carbonate was added. To this, 30 g (0.20 mol) of tert-butyl chloroacetate was added dropwise at room temperature over 30 minutes. The mixture is further stirred at 80 ° C. for 3 hours, then cooled to room temperature, potassium carbonate is filtered off, washed with 1200 g of diluted hydrochloric acid, and 42.0 g of bis (4-tert-butoxycarbonylmethyloxyphenylsulfonyl) methane is added. Obtained as a yellow oil.
[0022]
Finally, 30 g (0.054 mol) of bis (4-tert-butoxycarbonylmethyloxyphenylsulfonyl) methane and 15 g (0.076 mol) of tosyl azide were dissolved in 300 g of ethanol, and 12.5 g (0.12 g) of triethylamine was dissolved therein. Mol) was added dropwise at room temperature over 30 minutes. The mixture is further stirred at room temperature for 1.5 hours, and the precipitated crystals are collected by filtration. The obtained final product is recrystallized repeatedly from acetonitrile, and the target product bis (4-tert-butoxycarbonylmethyloxy) is obtained. 13.0 g of phenylsulfonyl) diazomethane was obtained. The melting point of the compound was 98 ° C. and the decomposition point was 114 ° C.
1 and 2 show the infrared absorption spectrum and proton nuclear magnetic resonance spectrum of this compound.
[0023]
Reference example 2
Bis (4-hydroxyphenylsulfonyl) methane was produced in the same manner as in Reference Example 1 and bis-tert-butyl 3-chloropropionate (33 g) was used instead of tert-butyl chloroacetate (30 g). 13.5 g of (4-tert-butoxycarbonylethyloxyphenylsulfonyl) diazomethane was obtained.
[0024]
EXAMPLE Weight average molecular weight of polyhydroxystyrene having a weight average molecular weight of 10,000 in which 39 mol% of the hydrogen atoms of the hydroxyl group are substituted with tert-butyloxycarbonyl groups and 39 mol% of the hydrogen atoms of the hydroxyl groups are substituted with ethoxyethyl groups weight and polyhydroxystyrene having a molecular weight of 10,000 ratio of 3: 100 parts by weight of the resin mixture containing 7 ratio of bis obtained in reference example 1 as a photoacid generator (4-tert- butoxycarbonyl- methyloxy phenylsulfonyl) 5 parts by weight of diazomethane, 0.3 part by weight of triethylamine and 0.2 part by weight of salicylic acid are mixed and dissolved in 490 parts by weight of propylene glycol monomethyl ether acetate, and this solution is filtered through a membrane filter having a pore size of 0.2 μm. A resist composition was prepared.
Next, the physical properties of this positive resist composition were determined by the following method, and the results are shown in Table 1.
For comparison, determine the physical properties of the known photoacid generators bis (cyclohexyl sulfonyl)
[0025]
(1) Sensitivity:
The sample was applied onto a silicon wafer using a spinner and dried on a hot plate at 90 ° C. for 90 seconds to obtain a resist film having a thickness of 0.7 μm. The film was exposed using a reduced projection exposure apparatus NSR-2005EX8A (Nikon Corp.) with a dose of 1 mJ / cm 2 , and then subjected to PEB (POST EXPOSURE BAKE) at 110 ° C. for 90 seconds, 2.38. When developed with a weight% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washed with water for 30 seconds and dried, the sensitivity is defined as the minimum exposure time at which the film thickness of the exposed area after development becomes 0 mJ / cm 2 ( Measured in units of energy.
[0026]
(2) Resolution:
The same operation as the above (1) was performed, and the limit resolution at the exposure amount for reproducing the 0.25 μm mask pattern is shown.
[0027]
(3) Resist pattern shape:
When the same operation as in (1) above is performed and a rectangular resist pattern of 0.25 μm is obtained, ○, and when the resist pattern top becomes a slightly thin pattern or a wavy resist pattern, × evaluated.
[0028]
(4) Stability over time:
In the above (1), after performing the operations up to exposure, after leaving for 60 minutes, PEB treatment and development were performed in the same manner, and the cross-sectional shape of the 0.25 μm resist pattern was observed with a SEM (scanning electron microscope) photograph. 5 in which the line and space of 0.25 μm is formed at 1: 1, 3 in which the line width (resist pattern width) is wider than 0.25 μm, and the space width is narrower than 0.25 μm, Evaluation was made with 1 as the non-resolved one and 4 and 2 between the two.
[0029]
(5) Residual film rate:
The same operation as the above (1) was performed, and the remaining film ratio in the unexposed area was shown as a ratio of the film thickness after development to the film thickness before development.
[0030]
[Table 1]
[0031]
【The invention's effect】
The photoacid generator of the present invention has been made to a novel compound and active ingredient, when used as a photoacid generator for a chemically amplified resist, for good contrast between exposed and unexposed portions, residual film ratio Is high and gives an excellent profile profile pattern. In addition, the compound used as the active ingredient of the present invention also has an advantage of high sensitivity since the tertiary alkyl group is cleaved by an acid and a carboxylic acid is generated from the residue.
[Brief description of the drawings]
1 is an infrared absorption spectrum of the compound obtained in Reference Example 1. FIG.
2 is a + H nuclear magnetic resonance spectrum of the compound obtained in Reference Example 1. FIG.
Claims (3)
で表わされるスルホニルジアゾメタン化合物からなる光酸発生剤。General formula
A photoacid generator comprising a sulfonyldiazomethane compound represented by the formula:
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US09/119,640 US5945517A (en) | 1996-07-24 | 1998-07-21 | Chemical-sensitization photoresist composition |
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