JP2775852B2 - Positive resist composition - Google Patents
Positive resist compositionInfo
- Publication number
- JP2775852B2 JP2775852B2 JP1141768A JP14176889A JP2775852B2 JP 2775852 B2 JP2775852 B2 JP 2775852B2 JP 1141768 A JP1141768 A JP 1141768A JP 14176889 A JP14176889 A JP 14176889A JP 2775852 B2 JP2775852 B2 JP 2775852B2
- Authority
- JP
- Japan
- Prior art keywords
- radiation
- compound
- sensitive component
- reaction
- positive 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.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、特定構造の多核フェノール化合物のキノン
ジアジドスルホン酸エステルを感放射線性成分として用
いたポジ型レジスト組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a positive resist composition using a quinonediazidesulfonic acid ester of a polynuclear phenol compound having a specific structure as a radiation-sensitive component.
〈従来の技術〉 従来より、ノボラック樹脂をバインダーとするポジ型
レジストの感放射線性成分として、フェノール化合物の
キノンジアジドスルホン酸エステルが用いられている。
この場合のフェノール化合物としては、トリヒドロキシ
ベンゾフェノンやテトラヒドロキシベンゾフェノンなど
のポリヒドロキシベンゾフェノン系化合物が多く用いら
れている。<Prior Art> Hitherto, a quinonediazidesulfonic acid ester of a phenol compound has been used as a radiation-sensitive component of a positive resist using a novolak resin as a binder.
As the phenol compound in this case, polyhydroxybenzophenone-based compounds such as trihydroxybenzophenone and tetrahydroxybenzophenone are often used.
〈発明が解決しようとする課題〉 しかしながら、これらベンゾフェノン系化合物から合
成された感放射線性成分を含むレジストは、解像力やパ
ターン形状(プロファイル)に難があった。<Problems to be Solved by the Invention> However, resists containing a radiation-sensitive component synthesized from these benzophenone-based compounds have difficulty in resolution and pattern shape (profile).
本発明の目的は、解像力やパターン形状の良好なポジ
型レジスト組成物を提供することにある。かかる目的の
ために鋭意検討を行った結果、特定構造を有するフェノ
ール化合物のキノンジアジドスルホン酸エステルを感放
射線性成分として用いれば、これらの性能が向上するこ
とを見出し、本発明を完成するに至った。An object of the present invention is to provide a positive resist composition having good resolution and pattern shape. As a result of intensive studies for this purpose, they have found that the use of quinonediazidesulfonic acid ester of a phenolic compound having a specific structure as a radiation-sensitive component improves their performance, and completed the present invention. .
〈課題を解決するための手段〉 本発明は、下記式(I) 〔式中、X1及びX2の一方は水素を、他方は水酸基を表わ
し、Y1及びY2の一方は水素を、他方は水酸基を表わす〕 で示される多核フェノール化合物、すなわち2−(3−
又は4−ヒドロキシフェニル)−2−(2,3,4−又は2,
4,5−トリヒドロキシフェニル)プロパンの、キノンジ
アジドスルホン酸エステルを感放射線性成分として含有
するポジ型レジスト組成物を提供するものである。<Means for Solving the Problems> The present invention provides the following formula (I) [Wherein one of X 1 and X 2 represents hydrogen, the other represents a hydroxyl group, one of Y 1 and Y 2 represents hydrogen, and the other represents a hydroxyl group], ie, 2- (3 −
Or 4-hydroxyphenyl) -2- (2,3,4- or 2,
An object of the present invention is to provide a positive resist composition containing a quinonediazidesulfonic acid ester of (4,5-trihydroxyphenyl) propane as a radiation-sensitive component.
式(I)のフェノール化合物は、酸性触媒の存在下、
ピロガロール又はヒドロキシヒドロキノンと、2−(3
−ヒドロキシフェニル)プロペン又は2−(4−ヒドロ
キシフェニル)プロペンとの反応により、合成すること
ができる。この反応における溶媒としては、触媒との組
合せにより、ジオキサン、酢酸、ニドロベンゼン、モノ
クロロベンゼン、水などが使用可能であるが、なかでも
ジオキサンが好ましい。また、反応の触媒としては、溶
媒との組合せにより、塩化アルミニウム、三フッ化ホウ
素の各種錯体、塩化第二スズ、塩化亜鉛、硫酸などが使
用可能であるが、なかでも塩化アルミニウムが好まし
い。ジオキサン溶媒中、塩化アルミニウム触媒の存在下
で反応を行う場合、反応温度は、触媒の量に応じて10℃
からジオキサンの沸点までの範囲で選ぶことができる。The phenolic compound of formula (I) is prepared in the presence of an acidic catalyst.
Pyrogallol or hydroxyhydroquinone and 2- (3
-Hydroxyphenyl) propene or 2- (4-hydroxyphenyl) propene can be synthesized. As a solvent in this reaction, dioxane, acetic acid, nitrobenzene, monochlorobenzene, water and the like can be used depending on a combination with a catalyst, and among them, dioxane is preferable. As the catalyst for the reaction, aluminum chloride, various complexes of boron trifluoride, stannic chloride, zinc chloride, sulfuric acid, and the like can be used depending on the combination with the solvent. Among them, aluminum chloride is preferable. When the reaction is carried out in a dioxane solvent in the presence of an aluminum chloride catalyst, the reaction temperature is 10 ° C. according to the amount of the catalyst.
To the boiling point of dioxane.
ピロガロール又はヒドロキシヒドロキノンを、2−
(3−ヒドロキシフェニル)プロペンと反応させる場
合、反応温度は45〜65℃が好ましい。この際の仕込みモ
ル比については、2−(3−ヒドロキシフェニル)プロ
ペン1モルに対し、ピロガロール又はヒドロキシヒドロ
キノンは通常1.2モル以上、好ましくは2.5〜4モルの範
囲で用いられ、そして塩化アルミニウムは通常0.05〜2
モル、好ましくは0.2〜0.4モルの範囲で用いられる。Pyrogallol or hydroxyhydroquinone, 2-
When reacting with (3-hydroxyphenyl) propene, the reaction temperature is preferably 45 to 65 ° C. In this case, the mole ratio of pyrogallol or hydroxyhydroquinone is usually 1.2 mol or more, preferably 2.5 to 4 mol per mol of 2- (3-hydroxyphenyl) propene, and aluminum chloride is usually used in the range of 2.5 to 4 mol. 0.05-2
Mole, preferably in the range of 0.2 to 0.4 mole.
ピロガロール又はヒドロキシヒドロキノンを、2−
(4−ヒドロキシフェニル)プロペンと反応させる場
合、反応温度は20〜40℃が好ましい。この際の仕込みモ
ル比については、2−(4−ヒドロキシフェニル)プロ
ペン1モルに対し、ピロガロール又はヒドロキシヒドロ
キノンは通常1.2モル以上、好ましくは2.5〜4モルの範
囲で用いられ、そして塩化アルミニウムは通常0.05〜2
モル、好ましくは0.3〜0.5モルの範囲で用いられる。Pyrogallol or hydroxyhydroquinone, 2-
When reacting with (4-hydroxyphenyl) propene, the reaction temperature is preferably from 20 to 40C. In this case, the molar ratio of pyrogallol or hydroxyhydroquinone is usually 1.2 mol or more, preferably 2.5 to 4 mol per mol of 2- (4-hydroxyphenyl) propene, and aluminum chloride is usually used in the range of 2.5 to 4 mol. 0.05-2
Mole, preferably in the range of 0.3 to 0.5 mole.
式(I)のフェノール化合物は、水酸基の少なくとも
一部をキノンジアジドスルホン酸エステルの形にし、ポ
ジ型レジスト用の感放射線性成分として用いられる。ポ
ジ型レジスト用の感放射線性成分の合成は、公知のエス
テル化反応に準じて行うことができる。すなわち、式
(I)のフェノール化合物とキノンジアジドスルホン酸
ハライドとを、ジオキサン等を溶媒として、塩基性触
媒、例えばトリエチルアミンを滴下することにより縮合
させ、その後水中にチャージして結晶を析出させ、濾過
及び乾燥を経て、感放射線性成分を得ることができる。
感放射線性成分の合成に用いるキノンジアジドスルホン
酸ハライドとしては、ナフトキノン−(1,2)−ジアジ
ド−(2)−5−スルホン酸クロリド、ナフトキノン−
(1,2)−ジアジド−(2)−4−スルホン酸クロリ
ド、ベンゾキノン−(1,2)−ジアジド−(2)−4−
スルホン酸クロリドが挙げられる。The phenol compound of the formula (I) has at least a part of the hydroxyl group in the form of a quinonediazidesulfonic acid ester and is used as a radiation-sensitive component for a positive resist. The synthesis of the radiation-sensitive component for a positive resist can be performed according to a known esterification reaction. That is, a phenol compound of the formula (I) and a quinonediazidesulfonic acid halide are condensed by adding a basic catalyst, for example, triethylamine, dropwise using dioxane or the like as a solvent, and then charged in water to precipitate crystals. After drying, a radiation-sensitive component can be obtained.
The quinonediazidesulfonic acid halide used in the synthesis of the radiation-sensitive component includes naphthoquinone- (1,2) -diazide- (2) -5-sulfonic chloride, naphthoquinone-
(1,2) -diazide- (2) -4-sulfonic acid chloride, benzoquinone- (1,2) -diazide- (2) -4-
Sulfonic acid chloride.
フェノール化合物のキノンジアジドスルホン酸エステ
ルからなる感放射線性成分は通常、アルカリ可溶性のノ
ボラック樹脂と組み合わせて、ポジ型レジスト組成物に
なる。ノボラック樹脂は、キノンジアジド系ポジ型レジ
ストのバインダー樹脂として一般に用いられるものでよ
く、フェノール類、例えばクレゾールなどを、ホルムア
ルデヒドと縮合させることにより得られる。このような
ノボラック樹脂と前述の感放射線性成分、また必要に応
じて他の添加物を、適当な溶剤に混合溶解することによ
り、レジスト液が調製される。これをシリコンウェハー
などの基板上に塗布し、溶剤を蒸発乾燥させて、レジス
ト膜が得られる。このレジスト膜に、所定パターンのマ
スクを介して、紫外線などの放射線を照射し、現像する
ことにより、ポジ型パターンが得られる。そして、式
(I)のフェノール化合物をキノンジアジドスルホン酸
エステル化し、これを感放射線性成分として用いた本発
明のポジ型レジスト組成物は、優れた解像力及びパター
ン形状(プロファイル)を与える。A radiation-sensitive component comprising a quinonediazide sulfonic acid ester of a phenol compound is usually combined with an alkali-soluble novolak resin to form a positive resist composition. The novolak resin may be a resin generally used as a binder resin for a quinonediazide-based positive resist, and is obtained by condensing phenols such as cresol with formaldehyde. A resist solution is prepared by mixing and dissolving such a novolak resin, the above-mentioned radiation-sensitive component, and if necessary, other additives in an appropriate solvent. This is applied on a substrate such as a silicon wafer, and the solvent is evaporated and dried to obtain a resist film. By irradiating the resist film with radiation such as ultraviolet rays through a mask having a predetermined pattern and developing the resist, a positive pattern is obtained. The positive resist composition of the present invention using the phenolic compound of the formula (I) as a quinonediazide sulfonic acid ester and using this as a radiation-sensitive component gives excellent resolution and pattern shape (profile).
〈実施例〉 次に実施例をあげて、本発明をさらに具体的に説明す
るが、本発明はこれらの実施例によって何ら限定される
ものではない。例中にある部は重量基準である。<Examples> Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Parts in the examples are by weight.
合成例1 ジオキサン60gに塩化アルミニウム2.1gを加え、撹拌
下、50〜55℃に昇温して均一溶液とした後、ピロガロー
ル19.7gを加えた。そこへ、2−(3−ヒドロキシフェ
ニル)プロペン7.0gをジオキサン20gに溶かした溶液を
1時間かけて滴下し、さらに1時間撹拌した。反応中、
温度は50〜55℃に保った。Synthesis Example 1 2.1 g of aluminum chloride was added to 60 g of dioxane, and the mixture was heated to 50 to 55 ° C. with stirring to form a homogeneous solution, and 19.7 g of pyrogallol was added. A solution of 7.0 g of 2- (3-hydroxyphenyl) propene in 20 g of dioxane was added dropwise thereto over 1 hour, and the mixture was further stirred for 1 hour. During the reaction,
The temperature was kept at 50-55 ° C.
反応終了後室温まで冷却し、反応溶液に酢酸エチル35
0g及び水600gを加えて抽出し、次に酢酸エチル層を300g
の水で5回洗浄した。これを濃縮して得られたオイル状
物質7.04gに、酢酸エチル5g及びクロロホルム220gを加
えて氷冷すると、結晶が析出した。濾過、乾燥して得ら
れた結晶は4.21gであり、これが下式(II)の構造を有
する化合物であることを、1H核磁気共鳴スペクトル、マ
ススペクトル、赤外吸収スペクトル及び融点により確認
した。After completion of the reaction, the reaction solution is cooled to room temperature, and ethyl acetate 35
0 g and water 600 g were added and extracted, and then the ethyl acetate layer was 300 g.
Of water 5 times. This was concentrated, and to 7.04 g of an oily substance obtained, 5 g of ethyl acetate and 220 g of chloroform were added, and the mixture was ice-cooled to precipitate crystals. The crystals obtained by filtration and drying were 4.21 g, and it was confirmed by 1 H nuclear magnetic resonance spectrum, mass spectrum, infrared absorption spectrum and melting point that this was a compound having the structure of the following formula (II). .
この化合物の1H核磁気共鳴スペクトルを第1図に、ま
た赤外吸収スペクトルを第2図に示す。1 H−NMRスペクトル(溶媒:アセトンd6、TMS) 化学シフト値δ(ppm): 1.62(s.6H),6,32(broad,1H),6.39(d,1H), 6.58(m,1H),6.66(t,1H),6.72(d,1H), 6.74(m,1H),7.03(t,1H),7,23(broad,1H), 7,95(broad,2H). マススペクトル:m/e 260(M+) 赤外吸収スペクトル:ν=3,000〜3,700cm-1(OH) 融点:162〜163℃ 合成例2 ジオキサン90gに塩化アルミニウム4.97gを加え、20〜
25℃で撹拌して均一溶液とした後、ピロガロール28.19g
を加えた。そこへ、2−(4−ヒドロキシフェニル)プ
ロペン10.0gをジオキサン30gに溶かした溶液を1時間か
けて滴下し、さらに1時間撹拌した。反応中、温度は20
〜25℃に保った。 FIG. 1 shows the 1 H nuclear magnetic resonance spectrum of this compound, and FIG. 2 shows its infrared absorption spectrum. 1 H-NMR spectrum (solvent: acetone d 6 , TMS) Chemical shift value δ (ppm): 1.62 (s.6H), 6,32 (broad, 1H), 6.39 (d, 1H), 6.58 (m, 1H) ), 6.66 (t, 1H), 6.72 (d, 1H), 6.74 (m, 1H), 7.03 (t, 1H), 7, 23 (broad, 1H), 7,95 (broad, 2H). Mass spectrum: m / e 260 (M + ) Infrared absorption spectrum: ν = 3,000-3,700 cm −1 (OH) Melting point: 162-163 ° C. Synthesis example 2 To 90 g of dioxane, add 4.97 g of aluminum chloride,
After stirring at 25 ° C. to make a homogeneous solution, pyrogallol 28.19 g
Was added. A solution of 10.0 g of 2- (4-hydroxyphenyl) propene in 30 g of dioxane was added dropwise thereto over 1 hour, and the mixture was further stirred for 1 hour. During the reaction, the temperature is 20
Kept at 2525 ° C.
反応終了後、反応溶液に酢酸エチル490g及び水840gを
加えて抽出し、次に酢酸エチル層を420gの水で5回洗浄
した。これを濃縮して得られたオイル状物質9.58gに、
酢酸エチル7g及びクロロホルム290gを加えて氷冷する
と、結晶が析出した。濾過後、乾燥して得られた結晶は
4.57gであり、これが下式(III)の構造を有する化合物
であることを、1H核磁気共鳴スペクトル、マススペクト
ル、赤外吸収スペクトル及び融点により確認した。After completion of the reaction, 490 g of ethyl acetate and 840 g of water were added to the reaction solution for extraction, and then the ethyl acetate layer was washed five times with 420 g of water. To 9.58 g of an oily substance obtained by concentrating this,
After adding 7 g of ethyl acetate and 290 g of chloroform and cooling with ice, crystals were precipitated. After filtration, the crystals obtained by drying are
4.57 g, which was confirmed to be a compound having the structure of the following formula (III) by 1 H nuclear magnetic resonance spectrum, mass spectrum, infrared absorption spectrum and melting point.
この化合物の1H核磁気共鳴スペクトルを第3図に、ま
た赤外吸収スペクトルを第4図に示す。1 H−NMRスペクトル(溶媒:アセトンd6、TMS) 化学シフト値δ(ppm): 1.63(s.6H),6,19(broad,1H),6.36(d,1H), 6.67(d,1H),6.68(d,2H),7.06(d,2H), 7,20(broad,1H),7.90(broad,1H), 7.99(broad,1H). マススペクトル:m/e 260(M+) 赤外吸収スペクトル:ν=3,000〜3,600cm-1(OH) 融点:176〜177℃ 合成例3 ジオキサン60gに塩化アルミニウム2.1gを加え、撹拌
下、50〜55℃に昇温して均一溶液とした後、ヒドロキシ
ヒドロキノン19.75gを加えた。そこへ、2−(3−ヒド
ロキシフェニル)プロペン7.0gをジオキサン20gに溶か
した溶液を1時間かけて滴下し、さらに1時間撹拌し
た。反応中、温度は50〜55℃に保った。 FIG. 3 shows the 1 H nuclear magnetic resonance spectrum of this compound, and FIG. 4 shows its infrared absorption spectrum. 1 H-NMR spectrum (solvent: acetone d 6 , TMS) Chemical shift value δ (ppm): 1.63 (s.6H), 6,19 (broad, 1H), 6.36 (d, 1H), 6.67 (d, 1H) ), 6.68 (d, 2H), 7.06 (d, 2H), 7,20 (broad, 1H), 7.90 (broad, 1H), 7.99 (broad, 1H). Mass spectrum: m / e 260 (M + ) Infrared absorption spectrum: ν = 3,000 to 3,600 cm −1 (OH) Melting point: 176 to 177 ° C. Synthesis Example 3 2.1 g of aluminum chloride was added to 60 g of dioxane, and 50 After raising the temperature to 55 ° C. to form a homogeneous solution, 19.75 g of hydroxyhydroquinone was added. A solution of 7.0 g of 2- (3-hydroxyphenyl) propene in 20 g of dioxane was added dropwise thereto over 1 hour, and the mixture was further stirred for 1 hour. During the reaction, the temperature was kept at 50-55 ° C.
反応終了後、室温まで冷却し、反応溶液に酢酸エチル
350g及び水600gを加えて抽出し、次に、酢酸エチル層を
300gの水で3回洗浄した。これを濃縮して得られたオイ
ル状物質18.25gに、酢酸エチル10g及びクロロホルム190
gを加えて氷冷すると、粗結晶が析出した。濾過して得
られた粗結晶は12.92gであり、これを酢酸エチル23gに
溶かし、クロロホルム75gを加えて氷冷すると、結晶が
析出した。濾過後、乾燥して得られた結晶は4.69gであ
り、これが下式(IV)の構造を有する化合物であること
を、1H核磁気共鳴スペクトル、マススペクトル、赤外吸
収スペクトル及び融点により確認した。After completion of the reaction, the reaction solution is cooled to room temperature, and ethyl acetate is added to the reaction solution.
350 g and 600 g of water were added for extraction, and then the ethyl acetate layer was separated.
Washed three times with 300 g of water. To 18.25 g of an oily substance obtained by concentrating this, 10 g of ethyl acetate and 190
When g was added and the mixture was cooled with ice, crude crystals were precipitated. The crude crystal obtained by filtration was 12.92 g. This was dissolved in 23 g of ethyl acetate, 75 g of chloroform was added, and the mixture was ice-cooled to precipitate crystals. After filtration, the crystals obtained by drying were 4.69 g, and it was confirmed by 1 H nuclear magnetic resonance spectrum, mass spectrum, infrared absorption spectrum and melting point that this was a compound having the structure of the following formula (IV). did.
この化合物の1H核磁気共鳴スペクトルを第5図に、ま
た赤外吸収スペクトルを第6図に示す。1 H−NMRスペクトル(溶媒:アセトンd6、TMS) 化学シフト値δ(ppm): 1.60(s.6H),6,31(s,1H),6.58(m,1H), 6.66(t,1H),6.67(s,1H),6.74(m,1H), 6,85(s,1H),7.03(t,1H),7.15(s,1H), 7.50(s,1H),7.97(s,1H). マススペクトル:m/e 260(M+) 赤外吸収スペクトル:ν=3,100〜3,700cm-1(OH) 融点:166〜167℃ 合成例4 ジオキサン90gに塩化アルミニウム4.97gを加え、20〜
25℃で撹拌して均一溶液とした後、ヒドロキシヒドロキ
ノン28.19gを加えた。そこへ、2−(4−ヒドロキシフ
ェニル)プロペン10.0gをジオキサン30gに溶かした溶液
を1時間かけて滴下し、さらに1時間撹拌した。反応
中、温度は20〜25℃に保った。 FIG. 5 shows the 1 H nuclear magnetic resonance spectrum of this compound, and FIG. 6 shows its infrared absorption spectrum. 1 H-NMR spectrum (solvent: acetone d 6 , TMS) Chemical shift value δ (ppm): 1.60 (s.6H), 6,31 (s, 1H), 6.58 (m, 1H), 6.66 (t, 1H) ), 6.67 (s, 1H), 6.74 (m, 1H), 6,85 (s, 1H), 7.03 (t, 1H), 7.15 (s, 1H), 7.50 (s, 1H), 7.97 (s, 1H). Mass spectrum: m / e 260 (M + ) Infrared absorption spectrum: ν = 3,100-3,700 cm −1 (OH) Melting point: 166-167 ° C. Synthesis Example 4 Add 4.97 g of aluminum chloride to 90 g of dioxane,
After stirring at 25 ° C. to make a homogeneous solution, 28.19 g of hydroxyhydroquinone was added. A solution of 10.0 g of 2- (4-hydroxyphenyl) propene in 30 g of dioxane was added dropwise thereto over 1 hour, and the mixture was further stirred for 1 hour. During the reaction, the temperature was kept at 20-25 ° C.
反応終了後、反応溶液に酢酸エチル350g及び水1,200g
を加えて抽出し、次に酢酸エチル層を500gの水で3回洗
浄した。これを濃縮して得られたオイル状物質22.2g
に、酢酸エチル10g及びクロロホルム150gを加えて氷冷
すると、粗結晶が析出した。濾過して得られた粗結晶は
11.84gであり、これを45gの酢酸エチルに溶かし、1.0g
の活性炭を加えて撹拌後、自然濾過を2回行った。この
溶液を濃縮して得たオイル状物質に、酢酸エチル10g及
びクロロホルム400gを加えて氷冷すると、結晶が析出し
た。濾過後、乾燥して得られた結晶は7.90gであり、こ
れが下式(V)の構造を有する化合物であることを、1H
核磁気共鳴スペクトル、マススペクトル、赤外吸収スペ
クトル及び融点により確認した。After the reaction, 350 g of ethyl acetate and 1,200 g of water were added to the reaction solution.
Was added and extracted, and then the ethyl acetate layer was washed three times with 500 g of water. 22.2 g of oily substance obtained by concentrating this
Then, 10 g of ethyl acetate and 150 g of chloroform were added thereto, and the mixture was cooled with ice, whereby crude crystals were precipitated. The crude crystals obtained by filtration are
11.84 g, dissolved in 45 g of ethyl acetate, 1.0 g
After activated carbon was added and stirred, natural filtration was performed twice. The solution was concentrated, and 10 g of ethyl acetate and 400 g of chloroform were added to an oily substance obtained by cooling with ice, whereby crystals were precipitated. After filtration, the crystals obtained by drying were 7.90 g. It was confirmed that this was a compound having the structure of the following formula (V) by 1 H
It was confirmed by nuclear magnetic resonance spectrum, mass spectrum, infrared absorption spectrum and melting point.
この化合物の1H核磁気共鳴スペクトルを第7図に、ま
た赤外吸収スペクトルを第8図に示す。1 H−NMRスペクトル(溶媒:アセトンd6、TMS) 化学シフト値δ(ppm): 1.60(s.6H),6,30(s,1H),6.48(s,1H), 6.70(d,2H),6.82(s,1H),7.07(d,2H), 7,15(s,1H),7.49(s,1H),8.02(s,1H). マススペクトル:m/e 260(M+) 赤外吸収スペクトル:ν=3,100〜3,700cm-1(OH) 融点:180〜181℃ 合成例5 内容積300mlの三つ口フラスコに、合成例1で得られ
た式(II)の化合物を7.43g、ナフトキノン−(1,2)−
ジアジド−(2)−5−スルホン酸クロリドを23.04g
(反応モル比1:3)、及びジオキサンを305g仕込んだの
ち、撹拌を完溶させた。この後、撹拌しながらフラスコ
を水浴に浸して、反応温度を20〜25℃にコントロール
し、滴下ロートを用いてトリエチルアミン9.61gを30分
間で滴下した。さらに、反応温度を20〜25℃に保ちなが
ら4時間撹拌を続けた。反応後、イオン交換水にチャー
ジし、次いで濾過、乾燥することにより、感放射線性成
分を得た。これを感放射線性成分Aとする。 The 1 H nuclear magnetic resonance spectrum of this compound is shown in FIG. 7, and the infrared absorption spectrum is shown in FIG. 1 H-NMR spectrum (solvent: acetone d 6 , TMS) Chemical shift value δ (ppm): 1.60 (s.6H), 6,30 (s, 1H), 6.48 (s, 1H), 6.70 (d, 2H) ), 6.82 (s, 1H), 7.07 (d, 2H), 7,15 (s, 1H), 7.49 (s, 1H), 8.02 (s, 1H). Mass spectrum: m / e 260 (M + ) Infrared absorption spectrum: ν = 3,100-3,700 cm −1 (OH) Melting point: 180-181 ° C. Synthesis Example 5 In a three-necked flask with an internal volume of 300 ml, 7.43 g of the obtained compound of the formula (II), naphthoquinone- (1,2)-
23.04 g of diazide- (2) -5-sulfonic acid chloride
(Reaction molar ratio 1: 3) and 305 g of dioxane were charged, and then the mixture was completely dissolved. Thereafter, the flask was immersed in a water bath with stirring, the reaction temperature was controlled at 20 to 25 ° C., and 9.61 g of triethylamine was added dropwise using a dropping funnel over 30 minutes. Further, stirring was continued for 4 hours while maintaining the reaction temperature at 20 to 25 ° C. After the reaction, the mixture was charged into ion-exchanged water, then filtered and dried to obtain a radiation-sensitive component. This is designated as radiation-sensitive component A.
合成例6 式(II)の化合物の代わりに、合成例2で得られた式
(III)の化合物を用いた以外は、合成例5と同様に操
作して、感放射線性成分を得た。これを感放射線性成分
Bとする。Synthesis Example 6 A radiation-sensitive component was obtained in the same manner as in Synthesis Example 5, except that the compound of Formula (III) obtained in Synthesis Example 2 was used instead of the compound of Formula (II). This is designated as radiation-sensitive component B.
合成例7 式(II)の化合物の代わりに、合成例3で得られた式
(IV)の化合物を用いた以外は、合成例5と同様に操作
して、感放射線性成分を得た。これを感放射線性成分C
とする。Synthesis Example 7 A radiation-sensitive component was obtained in the same manner as in Synthesis Example 5, except that the compound of Formula (IV) obtained in Synthesis Example 3 was used instead of the compound of Formula (II). This is called radiation-sensitive component C
And
合成例8 式(II)の化合物の代わりに、合成例4で得られた式
(V)の化合物を用いた以外は、合成例5と同様に操作
して、感放射線性成分を得た。これを感放射線性成分D
とする。Synthesis Example 8 A radiation-sensitive component was obtained in the same manner as in Synthesis Example 5, except that the compound of Formula (V) obtained in Synthesis Example 4 was used instead of the compound of Formula (II). This is called radiation-sensitive component D
And
参考例9 式(II)の化合物の代わりに、2,3,4−トリヒドロキ
シベンゾフェノンを用い、それとナフトキノン−(1,
2)−ジアジド−(2)−5−スルホン酸クロリドとの
反応モル比を1:2とした以外は、合成例5と同様に操作
して、感放射性成分を得た。これを感放射線性成分Eと
する。REFERENCE EXAMPLE 9 Instead of the compound of the formula (II), 2,3,4-trihydroxybenzophenone was used, and the naphthoquinone- (1,
2) -Diazide- (2) -5-sulfonic acid chloride was operated in the same manner as in Synthesis Example 5 except that the reaction molar ratio was set to 1: 2 to obtain a radiosensitive component. This is designated as radiation-sensitive component E.
参考例10 式(II)の化合物の代わりに、2,3,4,4′−テトラヒ
ドロキシベンゾフェノンを同じ反応モル比で用いた以外
は、合成例5と同様に操作して、感放射線性成分を得
た。これを感放射線性成分Fとする。Reference Example 10 A radiation-sensitive component was prepared in the same manner as in Synthesis Example 5 except that 2,3,4,4'-tetrahydroxybenzophenone was used in the same reaction molar ratio instead of the compound of the formula (II). I got This is designated as radiation-sensitive component F.
次に、感放射線性成分A、B、C又はDを配合したレ
ジストの性能と、感放射線性成分E又はFを配合したレ
ジストの性能とを、γ値及び解像度で比較した例を示
す。Next, an example is shown in which the performance of a resist containing the radiation-sensitive component A, B, C or D is compared with the performance of a resist containing the radiation-sensitive component E or F in terms of γ value and resolution.
実施例1〜4及び比較例1〜2 合成例5〜10で得られたそれぞれの感放射線性成分
を、ノボラック樹脂とともに表1に示す組成でエチルセ
ロソルブアセテート48部に溶かし、この液を孔径0.2μ
mのテフロン製フィルターで濾過してレジスト液を調製
した。これを、常方により洗浄したシリコンウェハー
に、回転塗布機を用いて1.3μm厚に塗布した。次に、
このシリコンウェハーを100℃のホットプレートで60秒
間ベークした。こうしてレジスト膜が形成されたウェハ
ーに、436nm(g線)の露光波長を有する縮小投影露光
機(GCA社製、DSW4800、NA=0.42)を用い、露光量を段
階的に変化させてパターニング露光した。これを、住友
化学工業(株)製の現像液SOPDで1分間現像することに
より、ポジ型パターンを得た。Examples 1 to 4 and Comparative Examples 1 to 2 Each of the radiation-sensitive components obtained in Synthesis Examples 5 to 10 was dissolved together with a novolak resin in 48 parts of ethyl cellosolve acetate with the composition shown in Table 1, and the liquid was subjected to a pore size of 0.2 μ
Then, the solution was filtered through a Teflon-made filter to prepare a resist solution. This was applied to a normally washed silicon wafer to a thickness of 1.3 μm using a spin coater. next,
This silicon wafer was baked on a hot plate at 100 ° C. for 60 seconds. The wafer on which the resist film was formed was subjected to patterning exposure using a reduction projection exposure machine (manufactured by GCA, DSW4800, NA = 0.42) having an exposure wavelength of 436 nm (g line) while changing the exposure stepwise. . This was developed with a developing solution SOPD manufactured by Sumitomo Chemical Co., Ltd. for 1 minute to obtain a positive pattern.
各々のレジスト液から得られたパターンにつき、露光
量の対数に対する規格化膜厚(=残膜厚/初期膜厚)を
プロットし、その傾きθを求め、tanθをγ値とした。
同時に求めた解像度とともに、結果を表1に示す。The normalized film thickness (= remaining film thickness / initial film thickness) with respect to the logarithm of the exposure amount was plotted for the pattern obtained from each resist solution, the slope θ was determined, and tan θ was defined as the γ value.
Table 1 shows the results together with the resolution obtained at the same time.
〈発明の効果〉 式(I)の多核フェノール化合物をキノンジアジドス
ルホン酸ハライドと縮合させて得られるエステルは、ポ
ジ型レジストの感放射線性成分として用いられ、この感
放射線性成分を含有するポジ型レジスト、具体的には、
この感放射線性成分とともにノボラック樹脂を含有する
ポジ型レジストは、優れた解像力(高いγ値)及び優れ
たパターン形状(プロファイル)を与える。 <Effect of the Invention> An ester obtained by condensing a polynuclear phenol compound of the formula (I) with a quinonediazidesulfonic acid halide is used as a radiation-sensitive component of a positive resist, and a positive resist containing this radiation-sensitive component is used. ,In particular,
A positive resist containing a novolak resin together with the radiation-sensitive component gives excellent resolution (high γ value) and excellent pattern shape (profile).
第1図は、合成例1で得られた2−(3−ヒドロキシフ
ェニル)−2−(2,3,4−トリヒドロキシフェニル)プ
ロパンの1H核磁気共鳴スペクトルであり、第2図は、こ
の化合物の赤外吸収スペクトルである。 第3図は、合成例2で得られた2−(4−ヒドロキシフ
ェニル)−2−(2,3,4−トリヒドロキシフェニル)プ
ロパンの1H核磁気共鳴スペクトルであり、第4図は、こ
の化合物の赤外吸収スペクトルである。 第5図は、合成例3で得られた2−(3−ヒドロキシフ
ェニル)−2−(2,4,5−トリヒドロキシフェニル)プ
ロパンの1H核磁気共鳴スペクトルであり、第6図は、こ
の化合物の赤外吸収スペクトルである。 第7図は、合成例4で得られた2−(4−ヒドロキシフ
ェニル)−2−(2,4,5−トリヒドロキシフェニル)プ
ロパンの1H核磁気共鳴スペクトルであり、第8図は、こ
の化合物の赤外吸収スペクトルである。FIG. 1 is a 1 H nuclear magnetic resonance spectrum of 2- (3-hydroxyphenyl) -2- (2,3,4-trihydroxyphenyl) propane obtained in Synthesis Example 1, and FIG. It is an infrared absorption spectrum of this compound. FIG. 3 is the 1 H nuclear magnetic resonance spectrum of 2- (4-hydroxyphenyl) -2- (2,3,4-trihydroxyphenyl) propane obtained in Synthesis Example 2, and FIG. It is an infrared absorption spectrum of this compound. FIG. 5 is the 1 H nuclear magnetic resonance spectrum of 2- (3-hydroxyphenyl) -2- (2,4,5-trihydroxyphenyl) propane obtained in Synthesis Example 3, and FIG. It is an infrared absorption spectrum of this compound. FIG. 7 is the 1 H nuclear magnetic resonance spectrum of 2- (4-hydroxyphenyl) -2- (2,4,5-trihydroxyphenyl) propane obtained in Synthesis Example 4, and FIG. It is an infrared absorption spectrum of this compound.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C07B 61/00 300 C07B 61/00 300 G03F 7/023 511 G03F 7/023 511 (72)発明者 上谷 保則 大阪府大阪市此花区春日出中3丁目1番 98号 住友化学工業株式会社内 (72)発明者 塙 良太郎 大阪府大阪市此花区春日出中3丁目1番 98号 住友化学工業株式会社内 (72)発明者 土居 靖宜 大阪府大阪市此花区春日出中3丁目1番 98号 住友化学工業株式会社内 (56)参考文献 特開 昭61−5037(JP,A) 特開 平2−269351(JP,A) (58)調査した分野(Int.Cl.6,DB名) C07C 39/15,37/14 C07C 309/71,309/74────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification code FI C07B 61/00 300 C07B 61/00 300 G03F 7/023 511 G03F 7/023 511 (72) Inventor Yasunori Uetani Konohana, Osaka City, Osaka 3-1-1 98 Kasuganaka-ku, Sumitomo Chemical Co., Ltd. (72) Inventor Ryotaro Hanawa 3-1-198 Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Doi Yasunori 3-1-98, Kasuganaka, Konohana-ku, Osaka-shi, Japan Sumitomo Chemical Co., Ltd. (56) References JP-A-61-5037 (JP, A) JP-A-2-269351 (JP, A) (58) Field surveyed (Int.Cl. 6 , DB name) C07C 39 / 15,37 / 14 C07C 309 / 71,309 / 74
Claims (2)
し、Y1及びY2の一方は水素を、他方は水酸基を表わす〕 で示されるフェノール化合物のキノンジアジドスルホン
酸エステルを含有することを特徴とするポジ型レジスト
組成物。(1) Formula (I) [Wherein, one of X 1 and X 2 represents hydrogen, the other represents a hydroxyl group, one of Y 1 and Y 2 represents hydrogen, and the other represents a hydroxyl group], which contains a quinonediazide sulfonic acid ester of a phenolic compound represented by the formula: A positive resist composition comprising:
記載の組成物。2. The composition according to claim 1, further comprising a novolak resin.
A composition as described.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP1141768A JP2775852B2 (en) | 1989-06-02 | 1989-06-02 | Positive resist composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1141768A JP2775852B2 (en) | 1989-06-02 | 1989-06-02 | Positive resist composition |
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Publication Number | Publication Date |
---|---|
JPH037240A JPH037240A (en) | 1991-01-14 |
JP2775852B2 true JP2775852B2 (en) | 1998-07-16 |
Family
ID=15299726
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Cited By (2)
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---|---|---|---|---|
CN113443969A (en) * | 2021-05-19 | 2021-09-28 | 辽宁靖帆新材料有限公司 | Method for preparing 4- [1- (4-hydroxyphenyl) -1-methyl-ethyl ] pyrogallol by resin method |
CN113620786A (en) * | 2021-05-19 | 2021-11-09 | 辽宁靖帆新材料有限公司 | Method for synthesizing polyhydroxy phenolic compound by acid method |
Families Citing this family (5)
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JP3364727B2 (en) * | 1993-10-22 | 2003-01-08 | イハラケミカル工業株式会社 | 2,2-bis (3,5-disubstituted-4-hydroxyphenyl) propane derivative, method for producing the same, and method for producing pyrogallol using the derivative |
JP2011144343A (en) | 2009-12-15 | 2011-07-28 | Kao Corp | Manufacturing method of refined oil and fat |
JP5717352B2 (en) | 2010-03-17 | 2015-05-13 | 花王株式会社 | Method for producing refined fats and oils |
JP5717351B2 (en) | 2010-03-17 | 2015-05-13 | 花王株式会社 | Method for producing refined fats and oils |
JP6008596B2 (en) | 2011-06-15 | 2016-10-19 | 花王株式会社 | Method for producing refined fats and oils |
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JPS615037A (en) * | 1984-06-18 | 1986-01-10 | Sumitomo Chem Co Ltd | Production of aralkyl monosubstituted polyhydric phenolic compound |
JPH0226931A (en) * | 1988-07-14 | 1990-01-29 | Towa Kogyo Kk | Device for removing remaining yarn on bobbin of spinning machine |
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1989
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CN113443969A (en) * | 2021-05-19 | 2021-09-28 | 辽宁靖帆新材料有限公司 | Method for preparing 4- [1- (4-hydroxyphenyl) -1-methyl-ethyl ] pyrogallol by resin method |
CN113620786A (en) * | 2021-05-19 | 2021-11-09 | 辽宁靖帆新材料有限公司 | Method for synthesizing polyhydroxy phenolic compound by acid method |
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