JP3854689B2 - The novel photo-acid-generating agent - Google Patents

The novel photo-acid-generating agent Download PDF

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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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acid
group
bis
tert
methane
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JPH1135551A (en
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和史 佐藤
利治 島巻
伸哉 庫本
和行 新田
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ダイトーケミックス株式会社
東京応化工業株式会社
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【0001】 [0001]
【発明の属する技術分野】 BACKGROUND OF THE INVENTION
本発明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。 The present invention consists of novel sulfonyl diazomethane compounds, and more particularly to a suitable photoacid generator used for a chemically amplified resist.
【0002】 [0002]
【従来の技術】 BACKGROUND OF THE INVENTION
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。 In recent years, in the production of semiconductor devices and liquid crystal devices, a chemically amplified resist composition has come to be used. 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。 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 has the advantage that with a small amount of the agent.
【0003】 [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。 This chemically amplified resist has two types of positive and negative, they are generally the acid generator, the basic component and a film-forming component that exhibits a changed solubility in an alkali aqueous solution by the action of the acid generated It is set to.
【0004】 [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。 In the above positive resist, as a film forming component, usually tert- butoxycarbonyl group, such as polyhydroxystyrene with a protected portion of the hydroxyl groups have been used in the dissolution inhibiting groups such as tetrahydropyranyl group, whereas, negative in the resist, as a film forming component, polyhydroxystyrene normally protecting the portion of the hydroxyl groups in the dissolution inhibiting group or a resin component such as polyhydroxystyrene or novolak resins, acid-crosslinkable materials such as melamine resins or urea resins a combination of is used.
【0005】 [0005]
ところで、このような酸発生剤として、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。 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 were inferior in contrast between exposed and unexposed areas, the sensitivity satisfactory there is a disadvantage that is difficult to obtain.
【0006】 [0006]
【発明が解決しようとする課題】 [Problems that the Invention is to Solve
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。 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 has been made for the purpose of providing a.
【0007】 [0007]
【課題を解決するための手段】 In order to solve the problems]
本発明者らは、化学増幅型レジストの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。 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, the two phenyl groups of bisphenyl diazomethane, by a compound obtained by introducing a third alkoxycarbonylalkoxy group as the acid dissociable group, found that can achieve the purpose, based on this finding It has led to the completion of the present invention.
【0008】 [0008]
すなわち、本発明は、一般式【化2】 That is, the present invention has the general formula ## STR2 ##
(式中のR 1炭素数1〜4の低級アルキレン基、R 2炭素数4〜8の第三アルキル基である) (R 1 in the formula is a lower alkylene group having 1 to 4 carbon atoms, R 2 is tertiary alkyl group having 4 to 8 carbon atoms)
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。 In which it is provided a photoacid generator comprising a novel sulfonyl diazomethane compounds represented.
【0009】 [0009]
この一般式(I)におけるR 1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。 Lower alkylene group R 1 in the general formula (I) is an alkylene group having 1 to 4 carbon atoms, which may be either linear or branched C. 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。 Examples of such lower alkylene group include methylene group, ethylene group, trimethylene group, tetramethylene group, isopropylene group, an isobutylene group.
また、一般式(I)におけるR 2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。 Further, tertiary alkyl groups of R 2 in general formula (I), tertiary alkyl groups of 4 to 8 carbon atoms, for example tert-butyl group, tert-pentyl, 1,1-dimethylbutyl group, and the like can.
【0010】 [0010]
【発明の実施の形態】 DETAILED DESCRIPTION OF THE INVENTION
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。 Novel sulfonyl diazomethane compounds used in the present invention, for example according to the reaction formula shown below, thiophenol (II), methylene halide (III) is condensed to produce a bis (hydroxyphenyl thio) methane (IV), then and oxidized to bis to produce a (hydroxyphenyl) methane (V), by reacting a thereto ω- halogeno-alkanoic acid tertiary alkyl (VI), or diazotized, or bis (hydroxyphenyl sulfonyl) After diazotization methane, it can be prepared by reacting the ω- halogeno-alkanoic acid tertiary alkyl.
【0011】 [0011]
【化3】 [Formula 3]
(ただし、 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 (Wherein, R 1 and R 2 have the same meanings as defined above, X, X 'is a halogen atom)
【0012】 [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。 Examples of methylene halides (III) used in this reaction include methylene chloride, methylene bromide, methylene iodide. 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。 Further, examples of ω- halogeno-alkanoic acid tertiary alkyl (VI), chloroacetic acid, bromoacetic acid, 3-chloropropionic acid, 3-bromopropionic acid, 4-tert-butyl ester of chloroacetic acid or 4-bromobutyrate , etc. can be mentioned tertiary pentyl ester or 1,1-dimethyl-butyl ester.
【0013】 [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。 The condensation of thiophenol (II) and methylene halide (III) in the reaction formula, in an inert solvent such as acetone, dehydrohalogenation such as combinations of a quaternary ammonium salt such as tetrabutyl ammonium halide and alkali carbonate It is carried out using the agent.
【0014】 [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。 The reaction is, for example an inert solvent such as ethanol to produce the thus obtained bis (hydroxyphenyl thio) bis corresponding to oxidize methane (IV) (hydroxyphenyl) methane (V) it can be carried out by hydrogen peroxide tungsten alkali as catalyst.
【0015】 [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。 Also, the reaction of introducing a third alkoxycarbonylalkoxy group bis (hydroxyphenyl) methane (V) or its diazo compound (VIII), the presence of an alkali such as an alkali carbonate in an inert solvent such as dimethylformamide below it can be carried out by reacting the ω- halogeno-alkanoic acid tertiary alkyl (VI).
【0016】 [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。 Furthermore, diazotization of bis (hydroxyphenyl) methane (V) or a tertiary alkoxycarbonylalkoxy compound (VII) in an inert solvent such as ethanol, are reacted tosyl azide in the presence of a tertiary amine such as triethylamine It is carried out by.
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。 The product thus obtained in the can be purified by means such as recrystallization in a conventional manner.
【0017】 [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。 Thus the general formula obtained sulfonyl diazomethane compounds of (I) is a novel compound of the mounting un document has a property of generating an acid through irradiation with light.
【0018】 [0018]
【実施例】 【Example】
次に実施例により本発明をさらに詳細に説明する。 Next a more detailed description of the present invention through examples.
【0019】 [0019]
参考例 Reference Example 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。 4-hydroxy-benzenethiol 50g and (0.40 moles) of tetrabutylammonium bromide 1.5 g (0.006 mol) was dissolved in acetone 250 g, which was added potassium carbonate 43 g (0.31 mol). 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。 It was added dropwise over 30 minutes at 45 ° C. The methylene bromide 40 g (0.23 mol). 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。 After stirring 8 h the mixture further 45 ° C., the precipitated potassium bromide was filtered off, the solvent was distilled off under 40 ° C. vacuum, then the resulting water 500g was added to the product, with ethyl acetate 600g after extraction, the distillation was bis (4-hydroxyphenyl thio) methane and the solvent as a yellow oil.
【0020】 [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。 Next, the bis (4-hydroxyphenyl-thio) methane 50 g (0.19 mol) in ethanol 275 g, was added sodium tungstate 5 g (0.02 g). 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。 35% aqueous hydrogen peroxide 162g of (1.67 mol) at 50 ° C. To this was added dropwise over 1 hour. この反応混合物をさらに50℃で5時間かき混ぜた。 The reaction mixture was further stirred for 5 hours at 50 ° C.. 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。 Then neutralized with 30% sodium hydroxide solution, and the precipitated crystals were collected by filtration. 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。 The thus-bis (4-hydroxyphenyl) methane as white crystals.
【0021】 [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。 Then dissolved the bis (4-hydroxyphenyl) methane 30 g (0.09 mol) in dimethyl formamide 160 g, was added potassium carbonate 28 g (0.20 mol). 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。 Chloroacetate tert- butyl 30g (0.20 mol) was added dropwise over 30 minutes at room temperature thereto. 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。 After stirring 3 hours the mixture further 80 ° C., cooled to room temperature, potassium carbonate is filtered off, then washed with dilute hydrochloric acid 1200 g, the bis (4-tert- butoxycarbonyl- methyl oxyphenyl) methane 42.0g It was obtained as a yellow oil.
【0022】 [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。 Finally, dissolving the bis (4-tert- butoxycarbonyl- methyl oxyphenyl) methane 30 g (0.054 mol) and tosyl azide 15 g (0.076 mol) in ethanol 300 g, which triethylamine 12.5 g (0.12 mol) was added dropwise over 30 minutes at room temperature. 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。 After stirring the mixture at room temperature for a further 1.5 hours, the precipitated crystals were collected by filtration and the resulting final product was repeatedly recrystallized from acetonitrile, the desired product bis (4-tert- butoxycarbonyl- methyloxy phenyl) diazomethane 13.0 g. その化合物の融点は98℃、分解点は114℃であった。 Its melting point compounds 98 ° C., decomposition point was 114 ° C..
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。 1 and 2 show the infrared absorption spectrum and proton nuclear magnetic resonance spectrum of this compound.
【0023】 [0023]
参考例 Reference Example 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。 Bis By in the same manner as in Reference Example 1 to produce a bis (4-hydroxyphenyl) methane, which in using 3-chloropropionic acid tert- butyl 33g instead of chloroacetic acid tert- butyl 30g, operating as (4-tert- butoxycarbonyl- ethyl oxy phenylsulfonyl) was obtained diazomethane 13.5 g.
【0024】 [0024]
実施例 Example
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、 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。 The weight average molecular weight 10 to 39 mol% of a polyhydroxy styrene and hydroxyl hydrogen atoms of a weight average molecular weight of 10,000 to 39 mole% of the hydrogen atoms of the hydroxyl groups is substituted with tert- butyloxycarbonyl group is substituted with ethoxyethyl group , 000 polyhydroxystyrene and a weight 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) diazomethane 5 blended parts by weight of triethylamine, 0.3 parts by weight and 0.2 parts by weight of salicylic acid were dissolved in 490 parts by weight of propylene glycol monomethyl ether acetate, the solution was filtered through a membrane filter having a pore size of 0.2 [mu] m, the positive resist composition things were prepared.
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。 Next, the positive resist composition sought physical properties by the following methods, and the results are shown in Table 1.
なお、比較のために、公知の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。 For comparison, determine the physical properties of the known photoacid generators bis (cyclohexyl sulfonyl) diazomethane 5 parts by weight positive resist composition using, shown together with the results in Table 1.
【0025】 [0025]
(1)感度: (1) Sensitivity:
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。 Sample using a spinner was applied onto a silicon wafer, which 90 ° C. on a hot plate to obtain a resist film having a thickness 0.7μm was dried for 90 seconds. この膜に縮小投影露光装置NSR−2005EX8A(ニコン社製)を用いて、1mJ/cm 2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/cm 2 (エネルギー量)単位で測定した。 This film using a reduction projection exposure apparatus NSR-2005EX8A (manufactured by Nikon Corporation), after exposure added dose by 1 mJ / cm 2, 110 ° C., carried out for 90 seconds PEB (POST EXPOSURE BAKE), 2.38 wt% tetramethylammonium hydroxide was developed for 60 seconds at 23 ° C. in an aqueous solution, when washed with water and dried for 30 seconds, mJ / cm 2 the minimum exposure time the film thickness of the exposed portions after development becomes 0 as sensitivity ( was measured by the amount of energy) units.
【0026】 [0026]
(2)解像性: (2) Resolution:
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。 Then the procedure of the above (1), shown at the limit resolution in the exposure amount necessary for reproducing a 0.25μm mask pattern.
【0027】 [0027]
(3)レジストパターン形状: (3) the resist pattern shape:
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。 Then the procedure of the above (1), the case where rectangular resist pattern 0.25μm was obtained ○, or become resist pattern top slightly narrower pattern, as × a case where a wavy resist pattern evaluated.
【0028】 [0028]
(4)引き置き経時安定性: (4) the post exposure stability of the latent image:
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。 In the above (1), after performing the operations up to exposure, after standing for 60 minutes, likewise PEB treatment and developed, observing the cross-sectional shape of 0.25μm of the resist pattern by SEM (scanning electron microscope) photograph and, 0.25 [mu] m line-and-space 1: 1 those formed in 5, line width (resist pattern width) becomes wider than 0.25 [mu] m, what space width becomes narrower than 0.25 [mu] m 3, those not resolved and 1 to evaluate each of the intermediate as 4,2.
【0029】 [0029]
(5)残膜率: (5) Residual Film Ratio:
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。 Then the procedure of the above (1), showed a film remaining ratio at the unexposed portion as a proportion of the film thickness after development to the film thickness before development.
【0030】 [0030]
【表1】 [Table 1]
【0031】 [0031]
【発明の効果】 【Effect of the invention】
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。 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 It is high, give an excellent pattern of the profile shape. 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。 The compound used as an active ingredient of the present invention, tertiary alkyl groups are cleaved by acid, the residues also has the advantage of exhibiting high sensitivity because it produces a carboxylic acid.
【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS
【図1】 参考例 1で得た化合物の赤外吸収スペクトル図。 [1] Infrared absorption spectrum of the compound obtained in Reference Example 1.
【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。 [Figure 2] + H nuclear magnetic resonance spectrum of the compound obtained in Reference Example 1.

Claims (3)

  1. 一般式 The general formula
    (式中のR 1炭素数1〜4の低級アルキレン基、R 2炭素数4〜8の第三アルキル基である) (R 1 in the formula is a lower alkylene group having 1 to 4 carbon atoms, R 2 is tertiary alkyl group having 4 to 8 carbon atoms)
    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 Photoacid generator comprising a sulfonyl diazomethane compounds represented in.
  2. 1がメチレン基である請求項1記載の光酸発生剤 The photoacid generator according to claim 1 R 1 is a methylene group.
  3. 2が第三ブチル基である請求項1又は2記載の光酸発生剤 Photoacid generator according to claim 1 or 2 wherein R 2 is a tert-butyl group.
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