JPH07209861A - Positive type radiation sensitive resin composition - Google Patents
Positive type radiation sensitive resin compositionInfo
- Publication number
- JPH07209861A JPH07209861A JP1694194A JP1694194A JPH07209861A JP H07209861 A JPH07209861 A JP H07209861A JP 1694194 A JP1694194 A JP 1694194A JP 1694194 A JP1694194 A JP 1694194A JP H07209861 A JPH07209861 A JP H07209861A
- Authority
- JP
- Japan
- Prior art keywords
- radiation
- alkali
- compound
- resin
- pattern
- 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.)
- Pending
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、紫外線、遠紫外線、電
子線、イオン線及びＸ線等の放射線に感応し、特にＩＣ
等の半導体回路及びフォトマスク作製用として好適なポ
ジ型感放射線性樹脂組成物に関するものである。BACKGROUND OF THE INVENTION The present invention is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron rays, ion rays and X-rays, and particularly IC
The present invention relates to a positive radiation-sensitive resin composition suitable for producing semiconductor circuits such as the above and photomasks.
【０００２】[0002]
【従来の技術】従来、半導体集積回路の製造において
は、シリコンウェハー、クロム蒸着板等の基板上にレジ
ストを塗布し、放射線を照射し、さらに現像することで
微細パターンを形成、ついでパターン部以外の基板部分
をエッチングする操作が行われている。近年、集積回路
の高性能化及び信頼性向上を図るため、素子の高密度化
の要請が高まってきている。2. Description of the Related Art Conventionally, in the manufacture of semiconductor integrated circuits, a resist is coated on a substrate such as a silicon wafer or a chromium vapor deposition plate, irradiated with radiation, and further developed to form a fine pattern, and then a portion other than the pattern portion is formed. The operation of etching the substrate portion of the. In recent years, in order to improve the performance and reliability of integrated circuits, there is an increasing demand for higher density of elements.
【０００３】一般にポジ型感放射線性樹脂組成物は、ア
ルカリ可溶性樹脂と樹脂のアルカリ溶解性を抑制するナ
フトキノンジアジド化合物とからなる組成物が広く用い
られている。この組成物に放射線を照射すると感放射線
性を示すナフトキノンジアジド化合物が分解し、系中の
水分と反応してインデンカルボン酸を生成する。このイ
ンデンカルボン酸は抑制力を持たず、逆にアルカリ可溶
性を示すため、照射部はアルカリ現像液に溶解するよう
になる。一方未照射部は、抑制力を有するナフトキノン
ジアジド化合物がそのまま存在する為に、アルカリ現像
液に殆ど溶解せず膨潤もしない。その結果、高解像性の
樹脂パターンを得ることができる。この様な高解像力を
有する、アルカリ可溶性樹脂とナフトキノンジアジド化
合物からなる樹脂組成物が以前より種々開発され、１μ
ｍ前後での半導体製造技術において多く使用されてい
る。しかしながら、半導体回路の高集積化は益々進み、
要求される解像性も０．５μｍ以下となるに至り、光源
もｇ線（４３６ｎｍ）から光学的に解像性の優れたｉ線
（３６５ｎｍ）や遠紫外線（３００ｎｍ以下）へと短波
長化しており、それぞれの光源に適合した、エッチング
耐性を有する高感度、高解像性のポジ型感放射線性樹脂
組成物の開発が強く望まれている。In general, a positive-type radiation-sensitive resin composition is widely used which is composed of an alkali-soluble resin and a naphthoquinonediazide compound which suppresses the alkali solubility of the resin. When this composition is irradiated with radiation, the naphthoquinonediazide compound exhibiting radiation sensitivity is decomposed and reacts with water in the system to form indenecarboxylic acid. Since this indenecarboxylic acid has no inhibitory effect and is alkali-soluble on the contrary, the irradiated part is dissolved in the alkali developing solution. On the other hand, in the non-irradiated portion, the naphthoquinonediazide compound having the inhibitory force is present as it is, so that it is hardly dissolved in the alkaline developer and does not swell. As a result, a resin pattern with high resolution can be obtained. Various resin compositions comprising an alkali-soluble resin and a naphthoquinonediazide compound having such a high resolution have been developed from before, and 1 μm has been developed.
It is widely used in semiconductor manufacturing technology around m. However, the higher integration of semiconductor circuits is progressing,
The required resolution is 0.5 μm or less, and the light source is shortened from g-line (436 nm) to i-line (365 nm) and far-ultraviolet (300 nm or less), which have excellent optical resolution. Therefore, it has been strongly desired to develop a high-sensitivity, high-resolution positive-type radiation-sensitive resin composition having etching resistance, which is suitable for each light source.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、紫外線、遠
紫外線、電子線、イオン線及びＸ線等の放射線に感応
し、感度、残膜率、解像性のバランスのよいエッチング
耐性の優れた、微細加工用ポジ型感放射線性樹脂組成物
を提供することにある。The present invention is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, ion beams and X-rays, and is excellent in etching resistance with a good balance of sensitivity, residual film ratio and resolution. Another object is to provide a positive-working radiation-sensitive resin composition for microfabrication.
【０００５】[0005]
【課題を解決するための手段】本発明者等は前記課題を
解決すべく鋭意研究を重ねた結果、本発明に至ったもの
である。すなわち本発明は、アルカリ可溶性樹脂及び式
（１）Means for Solving the Problems The inventors of the present invention have achieved the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to an alkali-soluble resin and the formula (1)
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】（式中、Ｄは水素原子あるいは、１，２−
ナフトキノンジアジド−５−（及び／又は−４−）スル
ホニル基を示す。ただし、少なくともどちらか１つは
１，２−ナフトキノンジアジド−５−（及び／又は−４
−）スルホニル基を示す。Ｒは−Ｈ、−ＯＨ、アルキル
基、アルコキシ基、アリール基、アリールアルキル基、
アシル基、アシルオキシ基を示す。ｌ，ｍは１〜３の整
数。）で示される感放射線性化合物を含有するポジ型感
放射線性樹脂組成物、に関する。(In the formula, D is a hydrogen atom or 1,2-
A naphthoquinonediazide-5- (and / or -4-) sulfonyl group is shown. However, at least one of them is 1,2-naphthoquinonediazide-5- (and / or -4
-) Represents a sulfonyl group. R is —H, —OH, alkyl group, alkoxy group, aryl group, arylalkyl group,
An acyl group and an acyloxy group are shown. l and m are integers of 1 to 3. And a positive-type radiation-sensitive resin composition containing the radiation-sensitive compound represented by the formula (1).
【０００８】本発明において用いられる式（１）の感放
射線性化合物は、１，２−ナフトキノンジアジド−５−
（及び／又は−４−）スルホニルクロライドと下記式
（２）The radiation-sensitive compound of the formula (1) used in the present invention is 1,2-naphthoquinonediazide-5-
(And / or -4-) sulfonyl chloride and the following formula (2)
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】式中 Ｒは −Ｈ、−ＯＨ、アルキル基、
アルコキシ基、アリール基、アリールアルキル基、アシ
ル基、アシルオキシ基を示す。ｌ，ｍは １〜３の整
数。）で示される公知のテルペンフエノール系化合物を
縮合反応させることにより得ることができる。In the formula, R is --H, --OH, an alkyl group,
An alkoxy group, an aryl group, an arylalkyl group, an acyl group, and an acyloxy group are shown. l and m are integers of 1 to 3. ) It can be obtained by subjecting a known terpene phenol compound represented by
【００１１】反応は一般に、アセトン、メチルエチルケ
トン、テトラヒドロフラン、ジオキサン、エーテル、酢
酸エチル等のアルコール性ＯＨ基やフェノール性ＯＨ基
を持たない溶媒が用いられ、また反応中に生成する塩化
水素を取り除くため、トリメチルアミン、トリエチルア
ミン、ピリジン等のアミン類、水酸化ナトリウム水溶
液、水酸化カリウム水溶液等の無機アルカリ水溶液が同
時に加えられる。In the reaction, a solvent having no alcoholic OH group or phenolic OH group such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ether, ethyl acetate is generally used, and hydrogen chloride produced during the reaction is removed. Amine such as trimethylamine, triethylamine and pyridine, and an aqueous solution of inorganic alkali such as aqueous solution of sodium hydroxide and aqueous solution of potassium hydroxide are added at the same time.
【００１２】これらの化合物の仕込割合は式（２）の化
合物１当量に対し、１，２−ナフトキノンジアジド−５
−（及び／又は−４−）スルホニルクロライドを０．５
〜２．０当量である。その量が０．５当量以下では、生
成した式（１）の化合物を使用したレジスト組成物のア
ルカリ現像液に対する抑制力が低下するため未露光部の
許容出来ない膜減りや転写パターン形状の劣化を招く。The charging ratio of these compounds is 1,2-naphthoquinonediazide-5 with respect to 1 equivalent of the compound of the formula (2).
0.5- (and / or -4-) sulfonyl chloride
~ 2.0 equivalents. If the amount is 0.5 equivalent or less, the inhibitory power of the resist composition containing the compound of formula (1) thus produced against an alkali developing solution is lowered, and thus unacceptable film loss in the unexposed area and deterioration of the transfer pattern shape. Invite.
【００１３】本発明のポジ型感放射線性樹脂組成物にお
いて用いるアルカリ可溶性樹脂としては、ノボラック樹
脂、レゾール樹脂、ポリビニルフェノール、（メタ）ア
クリル酸、（メタ）アクリル酸エステル、スチレン−マ
レイン酸共重合体、スチレン−（メタ）アクリル酸共重
合体等が挙げられるが、特にノボラック樹脂が本発明に
おいて好適に使用される。ノボラック樹脂としては、フ
ェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレ
ゾール、ビスフェノール−Ａ、ビスフェノール−Ｆ、レ
ゾルシノール、ピロガロール、２，６−キシレノール、
２，４−キシレノール、２，５−キシレノール、３，５
−キシレノール、２，４，６−トリメチルフェノール、
２，３，５−トリメチルフェノール等のフェノール類を
単独又は２種以上組み合わせて、ホルムアルデヒド、パ
ラホルムアルデヒド、トリオキサン、ベンズアルデヒ
ド、ｏ−ニトロベンズアルデヒド、ｐ−ニトロベンズア
ルデヒド、ｏ−メチルベンズアルデヒド、ｐ−メチルベ
ンズアルデヒド等のアルデヒド類と酸性触媒下、重縮合
させることによって得ることができる。該酸性触媒とし
ては、塩酸、硫酸、燐酸、硝酸、ギ酸、シュウ酸、酢酸
等が挙げられる。Examples of the alkali-soluble resin used in the positive-type radiation-sensitive resin composition of the present invention include novolak resin, resole resin, polyvinylphenol, (meth) acrylic acid, (meth) acrylic acid ester, and styrene-maleic acid copolymer. Examples thereof include coalesce products and styrene- (meth) acrylic acid copolymers, and novolak resins are particularly preferably used in the present invention. Examples of novolak resins include phenol, o-cresol, m-cresol, p-cresol, bisphenol-A, bisphenol-F, resorcinol, pyrogallol, 2,6-xylenol,
2,4-xylenol, 2,5-xylenol, 3,5
-Xylenol, 2,4,6-trimethylphenol,
Formaldehyde, paraformaldehyde, trioxane, benzaldehyde, o-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, p-methylbenzaldehyde, etc., such as 2,3,5-trimethylphenol and the like, alone or in combination of two or more. It can be obtained by polycondensation with the aldehydes of 1. under acidic catalyst. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, oxalic acid, acetic acid and the like.
【００１４】本発明において用いられるアルカリ可溶性
樹脂の重量平均分子量は、１，０００〜２０，０００、
好ましくは２，０００〜１５，０００である。分子量が
１，０００未満では耐熱性が著しく低下したり、アルカ
リ現像液に対する溶解性が高くなり過ぎる傾向がある。
また２０，０００を超えると感度低下や現像性低下等の
傾向がみられる。The weight average molecular weight of the alkali-soluble resin used in the present invention is 1,000 to 20,000,
It is preferably 2,000 to 15,000. When the molecular weight is less than 1,000, the heat resistance tends to be remarkably lowered, and the solubility in an alkali developing solution tends to be too high.
On the other hand, if it exceeds 20,000, the sensitivity and the developing property tend to decrease.
【００１５】本発明におけるアルカリ可溶性樹脂及び式
（１）で示される感放射線性化合物の組成比率は、全固
形分を１００重量部としたとき、アルカリ可溶性樹脂は
５０〜９５重量部、好ましくは６０〜９０重量部、感放
射線性化合物は５〜５０重量部であり、好ましくは１０
〜４０重量部である。感放射線性化合物の比率が５重量
部未満では、アルカリ現像液に対する溶解抑制効果が著
しく低下し、転写パターン形状に影響する。また５０重
量部を超えると、感度低下及び転写後のパターンの耐熱
性が低くなる。The composition ratio of the alkali-soluble resin and the radiation-sensitive compound represented by the formula (1) in the present invention is 50 to 95 parts by weight, preferably 60 when the total solid content is 100 parts by weight. To 90 parts by weight, and the radiation-sensitive compound is 5 to 50 parts by weight, preferably 10
~ 40 parts by weight. When the ratio of the radiation-sensitive compound is less than 5 parts by weight, the effect of suppressing dissolution in an alkali developing solution is remarkably reduced, which affects the transfer pattern shape. On the other hand, when it exceeds 50 parts by weight, the sensitivity is lowered and the heat resistance of the pattern after transfer is lowered.
【００１６】本発明のポジ型感放射線性樹脂組成物は、
通常前記各成分を有機溶剤に溶解して感光液の形で用い
られる。この際用いられる有機溶剤としては、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、プ
ロピレングリコールメチルエーテルアセテート、メトキ
シプロピルアセテート、プロピレングリコールプロピル
エーテルアセテート、ジエチレングリコールモノメチル
エーテル、ジエチレングリコールモノエチルエーテル、
メチルセロソルブ、エチルセロソルブ、ブチルアセテー
ト、アミルアセテート、メチルエチルケトン、メチルイ
ソブチルケトン、シクロヘキサノン、メチルラクテー
ト、エチルラクテート、ブチルラクテート等を挙げるこ
とができる。特に感放射線性化合物及びアルカリ可溶性
樹脂に対する溶解力が強く、また毒性の極めて低いラク
テート類、及びメトキシプロピルアセテートは有用であ
る。これらは、単独で用いてもよいし、２種以上混合し
て使用することができる。The positive type radiation sensitive resin composition of the present invention comprises
Usually, the above components are dissolved in an organic solvent and used in the form of a photosensitive solution. As the organic solvent used at this time, ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol methyl ether acetate, methoxypropyl acetate, propylene glycol propyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Examples thereof include methyl cellosolve, ethyl cellosolve, butyl acetate, amyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl lactate, ethyl lactate, and butyl lactate. Particularly, lactate and methoxypropylacetate, which have strong solubility in a radiation-sensitive compound and an alkali-soluble resin and have extremely low toxicity, are useful. These may be used alone or in combination of two or more.
【００１７】本発明のポジ型感放射線性樹脂組成物は、
さらに用途に応じて、増感剤、可塑剤、光変色剤、染
料、密着向上剤、界面活性剤、保存安定剤等の添加剤を
添加することができる。The positive type radiation sensitive resin composition of the present invention comprises
Further, additives such as a sensitizer, a plasticizer, a photochromic agent, a dye, an adhesion improver, a surfactant and a storage stabilizer can be added depending on the application.
【００１８】本発明のポジ型感放射線性樹脂組成物を固
形分が１０〜５０重量％となるように前記溶剤に溶解
し、孔径０．５μｍ以下のフィルターで濾過後スピンコ
ーター、バーコーター等によりクロム蒸着板、ウェハー
等の基板に塗布し乾燥することにより感光層が形成され
る。ついで所定のフォトマスク、ステンシルマスク等の
マスクを通して放射線を照射、又は放射線を走査し直接
選択的に放射線を照射した後、必要に応じて７０〜１４
０℃で加熱処理を施し、アルカリ水溶液により現像する
ことにより良好な樹脂パターンを転写することができ
る。この際使用される現像液としては、水酸化ナトリウ
ム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、
メタケイ酸ナトリウム等の無機アルカリ水溶液、又はテ
トラメチルアンモニウムハイドロオキサイド、テトラエ
チルアンモニウムハイドロオキサイド、コリン、トリメ
タノールアミン、トリエタノールアミン、トリエチルア
ミン等の有機アルカリ水溶液等が使用できる。これらア
ルカリ水溶液中の溶質の濃度は好ましくは０．５〜５％
であるがこの範囲に限定されるものではない。また該現
像液には、メタノール、エタノール、プロパノール等の
水溶性有機溶媒や界面活性剤を適量添加することができ
る。現像時間としては通常３０秒乃至５分である。The positive-type radiation-sensitive resin composition of the present invention is dissolved in the above solvent so that the solid content is 10 to 50% by weight, filtered through a filter having a pore size of 0.5 μm or less, and then spin coater, bar coater or the like. A photosensitive layer is formed by applying it to a substrate such as a chromium vapor deposition plate or a wafer and drying it. Then, after irradiating the radiation through a mask such as a predetermined photomask or stencil mask, or directly scanning the radiation and selectively irradiating the radiation, 70 to 14 as required.
A good resin pattern can be transferred by performing heat treatment at 0 ° C. and developing with an alkaline aqueous solution. As the developer used at this time, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
An inorganic alkaline aqueous solution such as sodium metasilicate or an organic alkaline aqueous solution such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, trimethanolamine, triethanolamine or triethylamine can be used. The concentration of solute in these alkaline aqueous solutions is preferably 0.5 to 5%
However, it is not limited to this range. Further, a water-soluble organic solvent such as methanol, ethanol, propanol or the like or a surfactant can be added to the developer in an appropriate amount. The developing time is usually 30 seconds to 5 minutes.
【００１９】[0019]
【実施例】以下実施例により本発明を更に詳細に説明す
るが、本発明はこれらに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００２０】合成例１ 下記式（３）で表される化合物５．０ｇ（０．０１５４
モル）及び１，２−ナフトキノンジアジド−５−スルホ
ニルクロライド８．３ｇ（０．０３０９モル）をテトラ
ヒドロフラン３０ｍｌに溶解させた。ついで、トリエチ
ルアミン３．７ｇ（０．０３７１モル）の３０％テトラ
ヒドロフラン溶液を３０度以下の温度で滴下した。滴下
後、さらに室温で３時間撹拌を続け、反応を完結させ
た。反応後、溶液を純水１０００ｍｌに滴下し、析出し
た結晶を濾取、水洗し乾燥させて感放射線性化合物を得
た。得られた化合物（以下化合物Ａとする）を高速液体
クロマトグラフにより分析したところ、ジエステル体
１００％であった。ＵＶ吸収スペクトルの測定結果、λ
max は２２５ｎｍであった。Synthesis Example 1 5.0 g (0.0154) of a compound represented by the following formula (3)
Mol) and 8.3 g (0.0309 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride were dissolved in 30 ml of tetrahydrofuran. Then, a 30% tetrahydrofuran solution of 3.7 g (0.0371 mol) of triethylamine was added dropwise at a temperature of 30 degrees or lower. After the dropping, stirring was further continued at room temperature for 3 hours to complete the reaction. After the reaction, the solution was dropped into 1000 ml of pure water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain a radiation-sensitive compound. The obtained compound (hereinafter referred to as compound A) was analyzed by high performance liquid chromatography to find that the diester compound was obtained.
It was 100%. UV absorption spectrum measurement result, λ
The max was 225 nm.
【００２１】[0021]
【化４】 [Chemical 4]
【００２２】合成例２ 下記式（４）で表される化合物５．０ｇ（０．０１４２
モル）及び１，２−ナフトキノンジアジド−５−スルホ
ニルクロライド７．６ｇ（０．０２８４モル）をテトラ
ヒドロフラン ３０ｍｌに溶解させた。ついで、トリエ
チルアミン３．５ｇ（０．０３４７モル）の３０％テト
ラヒドロフラン溶液を３０度以下の温度で滴下した。滴
下後、さらに室温で３時間撹拌を続け、反応を完結させ
た。反応後、溶液を純水１０００ｍｌに滴下し、析出し
た結晶を濾取、水洗し乾燥させて感放射線性化合物を得
た。得られた化合物（以下化合物Ｂとする）は、ジエス
テル体１００％であった。ＵＶ吸収スペクトルの測定結
果、λmax は２２５ｎｍであった。Synthesis Example 2 5.0 g (0.0142) of a compound represented by the following formula (4)
Mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (7.6 g, 0.0284 mol) were dissolved in 30 ml of tetrahydrofuran. Then, a 30% tetrahydrofuran solution of 3.5 g (0.0347 mol) of triethylamine was added dropwise at a temperature of 30 ° C. or lower. After the dropping, stirring was further continued at room temperature for 3 hours to complete the reaction. After the reaction, the solution was dropped into 1000 ml of pure water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain a radiation-sensitive compound. The obtained compound (hereinafter referred to as compound B) was 100% diester. As a result of measuring the UV absorption spectrum, λmax was 225 nm.
【００２３】[0023]
【化５】 [Chemical 5]
【００２４】合成例３ 下記式（５）で表される化合物５．０ｇ（０．０１３モ
ル）及び１，２−ナフトキノンジアジド−５−スルホニ
ルクロライド７．０ｇ（０．０２６モル）をテトラヒド
ロフラン３０ｍｌに溶解させた。ついで、トリエチルア
ミン３．２ｇ（０．０３１７モル）の３０％テトラヒド
ロフラン溶液を３０度以下の温度で滴下た。滴下後、さ
らに室温で３時間撹拌を続け、反応を完結させた。反応
後、溶液を純水１０００ｍｌに滴下し、析出した結晶を
濾取、水洗し乾燥させて感放射線性化合物を得た。得ら
れた化合物（以下化合物Ｃとする）は、モノエステル体
１４％、ジエステル体８６％であった。ＵＶ吸収スペク
トルの測定結果、いずれもλmax は２２５ｎｍであっ
た。Synthesis Example 3 5.0 g (0.013 mol) of the compound represented by the following formula (5) and 7.0 g (0.026 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride were added to 30 ml of tetrahydrofuran. Dissolved. Then, a 30% tetrahydrofuran solution containing 3.2 g (0.0317 mol) of triethylamine was added dropwise at a temperature of 30 ° C. or lower. After the dropping, stirring was further continued at room temperature for 3 hours to complete the reaction. After the reaction, the solution was dropped into 1000 ml of pure water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain a radiation-sensitive compound. The obtained compound (hereinafter referred to as compound C) was 14% monoester and 86% diester. As a result of measuring the UV absorption spectrum, λmax was 225 nm in all cases.
【００２５】[0025]
【化６】 [Chemical 6]
【００２６】合成例４ 上記式（４）で表される化合物５．０ｇ（０．０１４２
モル）及び１，２−ナフトキノンジアジド−５−スルホ
ニルクロライド５．７２ｇ（０．０２１３モル）をテト
ラヒドロフラン３０ｍｌに溶解させた。ついで、トリエ
チルアミン２．６ｇ（０．０２５７モル）の３０％テト
ラヒドロフラン溶液を３０度以下の温度で滴下した。滴
下後、さらに室温で３時間撹拌を続け、反応を完結させ
た。反応後、溶液を純水１０００ｍｌに滴下し、析出し
た結晶を濾取、水洗し乾燥させて感放射線性化合物を得
た。得られた化合物（以下化合物Ｄとする）は、モノエ
ステル体２４％、ジエステル体７６％であった。ＵＶ吸
収スペクトルの測定結果、いずれもλmax は２２５ｎｍ
であった。Synthesis Example 4 5.0 g (0.0142) of the compound represented by the above formula (4)
Mol) and 5.72 g (0.0213 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride were dissolved in 30 ml of tetrahydrofuran. Then, a 30% tetrahydrofuran solution of 2.6 g (0.0257 mol) of triethylamine was added dropwise at a temperature of 30 degrees or lower. After the dropping, stirring was further continued at room temperature for 3 hours to complete the reaction. After the reaction, the solution was dropped into 1000 ml of pure water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain a radiation-sensitive compound. The obtained compound (hereinafter referred to as compound D) was 24% in monoester form and 76% in diester form. UV absorption spectrum measurement results, λmax is 225 nm for both
Met.
【００２７】合成例５ 上記式（５）で表される化合物５．０ｇ（０．０１３モ
ル）及びナフトキノンジアジド−４−スルホニルクロラ
イド５．２３ｇ（０．０１９５モル）をテトラヒドロフ
ラン３０ｍｌに溶解させた。ついで、トリエチルアミン
２．４ｇ（０．０２３８モル）の３０％テトラヒドロフ
ラン溶液を３０度以下の温度で滴下した。滴下後、さら
に室温で３時間撹拌を続け反応を完結させた。反応後、
溶液を純水１０００ｍｌに滴下し、析出した結晶を濾
取、水洗し乾燥させて感放射線性化合物を得た。得られ
た化合物（以下化合物Ｅとする）は、モノエステル体３
５％、ジエステル体６５％であった。ＵＶ吸収スペクト
ルの測定結果、いずれもλmax は２２５ｎｍであった。Synthesis Example 5 5.0 g (0.013 mol) of the compound represented by the above formula (5) and 5.23 g (0.0195 mol) of naphthoquinonediazide-4-sulfonyl chloride were dissolved in 30 ml of tetrahydrofuran. Then, a 30% tetrahydrofuran solution containing 2.4 g (0.0238 mol) of triethylamine was added dropwise at a temperature of 30 degrees or lower. After the dropping, stirring was further continued at room temperature for 3 hours to complete the reaction. After the reaction
The solution was added dropwise to 1000 ml of pure water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain a radiation-sensitive compound. The obtained compound (hereinafter referred to as compound E) is a monoester body 3
It was 5% and diester 65%. As a result of measuring the UV absorption spectrum, λmax was 225 nm in all cases.
【００２８】実施例１ 化合物Ａ２ｇ及びクレゾールノボラック（メタ／パラ比
＝５／５；分子量３，４００）８ｇをフッ素系界面活性
剤を添加した乳酸エチル３５ｇに溶解させ、孔径０．１
μｍのメンブランフィルターで濾過し本発明の組成物の
溶液を得た。得られた溶液を、低反射膜を有するクロム
蒸着板上に回転数１，５００ｒｐｍで回転塗布した後、
表面温度９０℃のホットプレート上で５分間ソフトベー
クして膜厚１．０μｍの感放射線層を得た。ついで超高
圧水銀灯に東芝硝子製Ｖ−４２，ＵＶＤ−３５フィルタ
ーを装着し、透過してきた３６５ｎｍの紫外線を用い
て、マスクを介し照射を行った。照射後、表面温度１１
０℃のホットプレート上で５分間ポストエクスポージャ
ーベークし、ついでテトラメチルアンモニウムハイドロ
オキサイド２．３８重量％水溶液で温度２３℃にて６０
秒間現像、純水でリンスし、クロム基板上に転写パター
ンを得、感度、解像性、パターン形状、残膜率、耐熱性
の評価を行った。その結果、感度は２００ｍＪ／ｃ
ｍ2 、０．５μｍラインアンドスペースを解像し、パタ
ーンは剥離もなく矩形を示し、残膜率は９９％以上あ
り、１３０℃までパターンの変形を起こさず高い耐熱性
を示した。Example 1 2 g of compound A and 8 g of cresol novolac (meta / para ratio = 5/5; molecular weight 3,400) were dissolved in 35 g of ethyl lactate containing a fluorine-containing surfactant to give a pore size of 0.1.
The solution of the composition of the present invention was obtained by filtration with a membrane filter of μm. After the obtained solution was spin-coated at a rotation speed of 1,500 rpm on a chromium vapor deposition plate having a low reflection film,
Soft-baking was performed on a hot plate having a surface temperature of 90 ° C. for 5 minutes to obtain a radiation-sensitive layer having a film thickness of 1.0 μm. Next, a V-42, UVD-35 filter manufactured by Toshiba Glass was attached to the ultra-high pressure mercury lamp, and irradiation was performed through a mask using the transmitted 365-nm ultraviolet rays. Surface temperature after irradiation 11
Post-exposure bake was performed on a hot plate at 0 ° C. for 5 minutes, and then with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at a temperature of 23 ° C. for 60 minutes.
After development for 2 seconds and rinsing with pure water, a transfer pattern was obtained on a chromium substrate, and the sensitivity, resolution, pattern shape, residual film rate, and heat resistance were evaluated. As a result, the sensitivity is 200 mJ / c
m 2 and 0.5 μm line and space were resolved, the pattern was rectangular without peeling, the residual film ratio was 99% or more, and the pattern did not deform up to 130 ° C. and showed high heat resistance.
【００２９】実施例２ 化合物Ａ２ｇ及びクレゾールノボラック（メタ／パラ比
＝４／６；分子量２，４００）１０ｇをフッ素系界面活
性剤を添加したエチルラクテート１０ｇに溶解させ、孔
径０．５μｍのメンブランフィルターで濾過し本発明の
組成物の溶液を調製した。得られた溶液を、銅張り積層
板上にバーコーターで塗布した後、温度９０℃のオーブ
ン中で１５分間ソフトベークして膜厚５μｍの感放射線
層を得た。ついで超高圧水銀灯の紫外線を用いてマスク
を介し照射を行い、２％メタケイ酸ナトリウム水溶液で
現像、水洗を行った。その結果、感度は９５０ｍＪ／ｃ
ｍ2 、１．５μｍラインアンドスペースを解像し、剥離
は観察されなかった。Example 2 2 g of Compound A and 10 g of cresol novolak (meta / para ratio = 4/6; molecular weight 2,400) were dissolved in 10 g of ethyl lactate containing a fluorine-containing surfactant, and a membrane filter having a pore size of 0.5 μm was dissolved. And filtered to prepare a solution of the composition of the present invention. The obtained solution was applied on a copper-clad laminate with a bar coater and then soft-baked in an oven at a temperature of 90 ° C. for 15 minutes to obtain a radiation-sensitive layer having a film thickness of 5 μm. Then, irradiation with ultraviolet rays from an ultra-high pressure mercury lamp was performed through a mask, followed by development with a 2% sodium metasilicate aqueous solution and washing with water. As a result, the sensitivity is 950 mJ / c
m 2 and 1.5 μm line and space were resolved, and no peeling was observed.
【００３０】実施例３ 化合物Ｂ１．２ｇ及びクレゾールノボラック（メタ／パ
ラ比＝４／６；分子量２，４００）８ｇをフッ素系界面
活性剤を添加したエチルラクテート２５ｇに溶解させ、
孔径０．１μｍのメンブランフィルターで濾過し本発明
の組成物の溶液を調製した。得られた溶液を、酸化膜を
有するシリコンウェハー上に回転数４，０００ｒｐｍで
回転塗布した後、表面温度９０℃のホットプレート上で
９０秒間ソフトベークして膜厚１．２μｍの感放射線層
を得た。ついで超高圧水銀灯に東芝硝子製Ｖ−４２，Ｕ
ＶＤ−３５フィルターを装着し、透過してきた３６５ｎ
ｍの紫外線を用いて、マスクを介し照射を行った。照射
後表面温度１１０℃のホットプレート上で６０秒間ポス
トエクスポージャーベークし、ついでテトラメチルアン
モニウムハイドロオキサイド２．３８重量％水溶液で温
度２３℃にて６０秒間現像、純水でリンスし、シリコン
ウェハー上に転写パターンを得、感度、解像性、パター
ン形状、残膜率、耐熱性の評価を行った。その結果、感
度は２２０ｍＪ／ｃｍ2 、０．５μｍラインアンドスペ
ースを解像し、パターンは剥離もなく矩形を示し、残膜
率は９９％以上あり、１２５℃までパターンの変形を起
こさず高い耐熱性を示した。Example 3 1.2 g of compound B and 8 g of cresol novolac (meta / para ratio = 4/6; molecular weight 2,400) were dissolved in 25 g of ethyl lactate containing a fluorosurfactant,
The solution of the composition of the present invention was prepared by filtering with a membrane filter having a pore size of 0.1 μm. The obtained solution was spin-coated at a rotation speed of 4,000 rpm on a silicon wafer having an oxide film, and then soft-baked for 90 seconds on a hot plate having a surface temperature of 90 ° C. to form a radiation-sensitive layer having a thickness of 1.2 μm. Obtained. Next, the ultra-high pressure mercury lamp is used with Toshiba Glass V-42, U
365n with VD-35 filter attached and transmitted
Irradiation was carried out through a mask using ultraviolet rays of m. After irradiation, post-exposure bake is performed on a hot plate having a surface temperature of 110 ° C. for 60 seconds, then development is performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at a temperature of 23 ° C. for 60 seconds, rinsed with pure water, and then on a silicon wafer. A transfer pattern was obtained, and the sensitivity, resolution, pattern shape, residual film rate, and heat resistance were evaluated. As a result, the sensitivity was 220 mJ / cm 2 , 0.5 μm line and space was resolved, the pattern was rectangular without peeling, the residual film rate was 99% or more, and the pattern did not deform up to 125 ° C. and had high heat resistance. Showed sex.
【００３１】実施例４ 化合物Ｂ１．６ｇ及びクレゾールノボラック（メタ／パ
ラ比＝５／５；分子量５，０００）８ｇをフッ素系界面
活性剤を添加したエチルラクテート３０ｇに溶解させ孔
径０．１μｍのメンブランフィルターで濾過し本発明の
組成物の溶液を調製した。得られた溶液を、ベアーシリ
コンウェハー上に回転数４，０００ｒｐｍで回転塗布し
た後、表面温度９０℃のホットプレート上で９０秒間ソ
フトベークして膜厚１．２μｍの感放射線層を得た。つ
いで超高圧水銀灯に東芝硝子製ＫＬ−２５フィルターを
装着し、透過してきた遠紫外線を用い、マスクを介し照
射を行った。照射後、表面温度１１０℃のホットプレー
ト上で６０秒間ポストエクスポージャーベークし、つい
でテトラメチルアンモニウムハイドロオキサイド２．３
８重量％水溶液で温度２３℃にて６０秒間現像、純水に
てリンスし、シリコンウェハー上に転写パターンを得、
感度、解像性、パターン形状、残膜率、耐熱性の評価を
行った。その結果、感度は２５０ｍＪ／ｃｍ2 、０．５
μｍラインアンドスペースを解像、パターンは剥離もな
く矩形を示し、残膜率は９９％以上あり、１３０℃まで
パターンの変形を起こさず高い耐熱性を示した。Example 4 1.6 g of the compound B and 8 g of cresol novolac (meta / para ratio = 5/5; molecular weight 5,000) were dissolved in 30 g of ethyl lactate containing a fluorine-containing surfactant to obtain a membrane having a pore diameter of 0.1 μm. It filtered with the filter and prepared the solution of the composition of this invention. The obtained solution was spin-coated on a bare silicon wafer at a rotation speed of 4,000 rpm, and then soft-baked for 90 seconds on a hot plate having a surface temperature of 90 ° C. to obtain a radiation-sensitive layer having a film thickness of 1.2 μm. Then, a KL-25 filter manufactured by Toshiba Glass was attached to the ultra-high pressure mercury lamp, and irradiation was performed through a mask using far ultraviolet rays that had passed through. After irradiation, post-exposure bake was performed on a hot plate having a surface temperature of 110 ° C. for 60 seconds, and then tetramethylammonium hydroxide 2.3 was used.
Develop with an 8 wt% aqueous solution at a temperature of 23 ° C. for 60 seconds, rinse with pure water to obtain a transfer pattern on a silicon wafer,
The sensitivity, resolution, pattern shape, residual film rate, and heat resistance were evaluated. As a result, the sensitivity was 250 mJ / cm 2 , 0.5.
The μm line and space was resolved, the pattern was rectangular without peeling, the residual film rate was 99% or more, and the pattern did not deform up to 130 ° C. and showed high heat resistance.
【００３２】実施例５ 化合物Ｂ２．２ｇ及びクレゾールノボラック（メタ／パ
ラ比＝６／４；分子量７，０００）８ｇをジメチルフォ
ルムアミド及びフッ素系界面活性剤を添加したエチルラ
クテート６０ｇに溶解させ、孔径０．１μｍのメンブラ
ンフィルターで濾過し本発明の組成物の溶液を得た。得
られた溶液を、低反射膜層を有するクロム蒸着板上に回
転数１，５００ｒｐｍで回転塗布した後、表面温度９０
℃のホットプレート上で５分間ソフトベークして膜厚
０．４μｍの感放射線層を得た。ついで超高圧水銀灯に
東芝硝子製Ｖ−４２，ＵＶＤ−３５フィルターを装着
し、透過してきた３６５ｎｍの紫外線を用いて、マスク
を介し照射を行った。照射後、表面温度１１０℃のホッ
トプレート上で５分間ポストエクスポージャーベーク
し、ついでテトラメチルアンモニウムハイドロオキサイ
ド２．３８重量％水溶液で温度２３℃にて６０秒間現
像、純水でリンスし、クロム基板上に転写パターンを
得、感度、解像性、パターン形状、残膜率、耐熱性の評
価を行った。その結果、感度は１００ｍＪ／ｃｍ2 、
０．５μｍラインアンドスペースを解像し、パターンは
剥離もなく矩形を示し、残膜率は９９％以上あり、１３
０℃までパターンの変形を起こさず高い耐熱性を示し
た。Example 5 2.2 g of compound B and 8 g of cresol novolac (meta / para ratio = 6/4; molecular weight 7,000) were dissolved in 60 g of ethyl lactate to which dimethylformamide and a fluorosurfactant were added to obtain a pore size. It was filtered with a 0.1 μm membrane filter to obtain a solution of the composition of the present invention. The obtained solution was spin-coated at a rotation speed of 1,500 rpm on a chromium vapor deposition plate having a low reflection film layer, and then the surface temperature was 90.
Soft-baking was performed on a hot plate at 0 ° C. for 5 minutes to obtain a radiation-sensitive layer having a film thickness of 0.4 μm. Next, a V-42, UVD-35 filter manufactured by Toshiba Glass was attached to the ultra-high pressure mercury lamp, and irradiation was performed through a mask using the transmitted 365-nm ultraviolet rays. After the irradiation, post-exposure bake was performed on a hot plate having a surface temperature of 110 ° C. for 5 minutes, followed by development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at a temperature of 23 ° C. for 60 seconds, rinsing with pure water, and chrome substrate. A transfer pattern was obtained, and the sensitivity, resolution, pattern shape, residual film rate, and heat resistance were evaluated. As a result, the sensitivity is 100 mJ / cm 2 ,
0.5 μm line and space was resolved, the pattern was rectangular without peeling, and the residual film rate was 99% or more.
It showed high heat resistance without pattern deformation up to 0 ° C.
【００３３】実施例６ 化合物Ｃ２ｇ及びクレゾールノボラック（メタ／パラ比
＝４／６；分子量１０，０００）８ｇをフッ素系界面活
性剤を添加したメトキシプロピルアセテート２５ｇに溶
解させ、孔径０．１μｍのメンブランフィルターで濾過
し本発明の組成物の溶液を調製した。得られた溶液を、
酸化膜を有するシリコンウェハー上に回転数４，０００
ｒｐｍで回転塗布した後、表面温度９０℃のホットプレ
ート上で３分間ソフトベークして膜厚１．２μｍの感放
射線層を得た。ついで超高圧水銀灯に東芝硝子製Ｖ−４
２，ＵＶＤ−３５フィルターを装着し、透過してきた３
６５ｎｍの紫外線を用いて、マスクを介し照射を行っ
た。照射後、表面温度１１０℃のホットプレート上で１
分間ポストエクスポージャーベークし、ついでテトラメ
チルアンモニウムハイドロオキサイド２．３８重量％水
溶液で温度２３℃にて６０秒間現像、純水でリンスを行
いシリコンウェハー上に転写パターンを得、感度、解像
性、パターン形状、残膜率、耐熱性の評価を行った。そ
の結果、感度は２２０ｍＪ／ｃｍ2 、０．５μｍライン
アンドスペースを解像、パターンは剥離もなく矩形を示
し、残膜率は９９％以上あり、１３５℃までパターンの
変形を起こさず高い耐熱性を示した。Example 6 2 g of compound C and 8 g of cresol novolac (meta / para ratio = 4/6; molecular weight 10,000) were dissolved in 25 g of methoxypropyl acetate containing a fluorine-containing surfactant, and a membrane having a pore size of 0.1 μm was dissolved. It filtered with the filter and prepared the solution of the composition of this invention. The obtained solution is
Rotation speed of 4,000 on a silicon wafer with an oxide film
After spin coating at rpm, a radiation sensitive layer having a thickness of 1.2 μm was obtained by soft baking for 3 minutes on a hot plate having a surface temperature of 90 ° C. Next, the V-4 made by Toshiba Glass for the ultra-high pressure mercury lamp
2, with UVD-35 filter attached and transmitted 3
Irradiation was performed through a mask using 65 nm UV light. After irradiation, 1 on a hot plate with a surface temperature of 110 ° C
Post-exposure bake for minutes, then develop with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds at a temperature of 23 ° C., rinse with pure water to obtain a transfer pattern on a silicon wafer, and obtain sensitivity, resolution and pattern. The shape, residual film rate, and heat resistance were evaluated. As a result, the sensitivity was 220 mJ / cm 2 , 0.5 μm line and space was resolved, the pattern was rectangular without peeling, the residual film ratio was 99% or more, and the pattern did not deform up to 135 ° C. and had high heat resistance. showed that.
【００３４】実施例７ 化合物Ｄ２ｇ及びクレゾールノボラック（メタ／パラ比
＝４／６；分子量５，０００）８ｇをフッ素系界面活性
剤を添加したメトキシプロピルアセテート３０ｇに溶解
させ、孔径０．１μｍのメンブランフィルターで濾過し
本発明の組成物の溶液を調製した。得られた溶液を、酸
化膜を有するシリコンウェハー上に回転数４，０００ｒ
ｐｍで回転塗布した後、表面温度９０℃のホットプレー
ト上で２分間ソフトベークして膜厚１．２μｍの感放射
線層を得た。ついで超高圧水銀灯に東芝硝子製Ｖ−４
２，ＵＶＤ−３５フィルターを装着し、透過してきた３
６５ｎｍの紫外線を用いて、マスクを介し照射を行っ
た。照射後、表面温度１１０℃のホットプレート上で１
分間ポストエクスポージャーベークし、ついでテトラメ
チルアンモニウムハイドロオキサイド２．３８重量％水
溶液で温度２３℃にて６０秒間現像、純水にてリンス
し、シリコンウェハー上に転写パターンを得、感度、解
像性、パターン形状、残膜率、耐熱性の評価を行った。
その結果、感度は２８０ｍＪ／ｃｍ2 、０．５μｍライ
ンアンドスペースを解像し、パターンは剥離もなく矩形
を示し、残膜率は９９％以上あり、１２０℃までパター
ンの変形を起こさず高い耐熱性を示した。Example 7 2 g of compound D and 8 g of cresol novolak (meta / para ratio = 4/6; molecular weight 5,000) were dissolved in 30 g of methoxypropyl acetate containing a fluorine-containing surfactant, and a membrane having a pore size of 0.1 μm was dissolved. It filtered with the filter and prepared the solution of the composition of this invention. The obtained solution is spun on a silicon wafer having an oxide film at a rotation speed of 4,000 r.
After spin coating at pm, it was soft-baked for 2 minutes on a hot plate having a surface temperature of 90 ° C. to obtain a radiation-sensitive layer having a film thickness of 1.2 μm. Next, the V-4 made by Toshiba Glass for the ultra-high pressure mercury lamp
2, with UVD-35 filter attached and transmitted 3
Irradiation was performed through a mask using 65 nm UV light. After irradiation, 1 on a hot plate with a surface temperature of 110 ° C
Post exposure bake for minutes, then develop with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds at a temperature of 23 ° C., rinse with pure water, obtain a transfer pattern on a silicon wafer, and obtain sensitivity, resolution, The pattern shape, residual film rate, and heat resistance were evaluated.
As a result, the sensitivity was 280 mJ / cm 2 , 0.5 μm line and space was resolved, the pattern was rectangular without peeling, the residual film rate was 99% or more, and the pattern did not deform up to 120 ° C. Showed sex.
【００３５】実施例８ 化合物Ｅ２．５ｇ及びクレゾールノボラック（メタ／パ
ラ比＝６／４；分子量１０，０００）８ｇをフッ素系界
面活性剤を添加したエチルセロソルブアセテート乳酸エ
チル７０ｇに溶解させ、孔径０．１μｍのメンブランフ
ィルターで濾過し本発明の組成物の溶液を得た。得られ
た溶液を、低反射膜層を有するクロム蒸着板上に回転数
１，５００ｒｐｍで回転塗布した後、表面温度９０℃の
ホットプレート上で３分間ソフトベークして膜厚０．４
５μｍの感放射線層を得た。ついで超高圧水銀灯に東芝
硝子製Ｖ−４２，ＵＶＤ−３５フィルターを装着し、透
過してきた３６５ｎｍの紫外線を用いて、マスクを介し
照射を行った。照射後表面温度１００℃のホットプレー
ト上で５分間ポストエクスポージャーベークし、ついで
テトラメチルアンモニウムハイドロオキサイド２．３８
重量％水溶液で温度２３℃にて６０秒間現像、純水でリ
ンスし、クロム基板上に転写パターンを得、感度、解像
性、パターン形状、残膜率、耐熱性の評価を行った。そ
の結果、感度は１２０ｍＪ／ｃｍ2 、０．５μｍライン
アンドスペースを解像し、パターンは剥離もなく矩形を
示し、残膜率は９９％以上あり、１３０℃までパターン
の変形を起こさず高い耐熱性を示した。Example 8 2.5 g of compound E and 8 g of cresol novolac (meta / para ratio = 6/4; molecular weight 10,000) were dissolved in 70 g of ethyl cellosolve acetate ethyl lactate containing a fluorine-containing surfactant to give a pore size of 0. The solution of the composition of the present invention was obtained by filtration with a membrane filter of 1 μm. The obtained solution was spin-coated at a rotation speed of 1,500 rpm on a chromium vapor deposition plate having a low reflection film layer, and then soft-baked on a hot plate having a surface temperature of 90 ° C. for 3 minutes to give a film thickness of 0.4.
A radiation-sensitive layer of 5 μm was obtained. Next, a V-42, UVD-35 filter manufactured by Toshiba Glass was attached to the ultra-high pressure mercury lamp, and irradiation was performed through a mask using the transmitted 365-nm ultraviolet rays. After irradiation, post-exposure bake was performed on a hot plate having a surface temperature of 100 ° C. for 5 minutes, and then tetramethylammonium hydroxide 2.38 was used.
It was developed with a weight% aqueous solution at a temperature of 23 ° C. for 60 seconds and rinsed with pure water to obtain a transfer pattern on a chromium substrate, and the sensitivity, resolution, pattern shape, residual film rate and heat resistance were evaluated. As a result, the sensitivity was 120 mJ / cm 2 , 0.5 μm line and space was resolved, the pattern was rectangular without peeling, the residual film rate was 99% or more, and the pattern did not deform up to 130 ° C. Showed sex.
【００３６】実施例９ 化合物Ｅ １．２ｇ及びクレゾールノボラック（メタ／
パラ比＝５／４；分子量 ３，４００） ８ｇをジメチ
ルフォルムアミド及びフッ素系界面活性剤を添加したプ
ロピレングリコールプロピルエーテルアセテート ６０
ｇに溶解させ、孔径０．１μｍのメンブランフィルター
で濾過し本発明の組成物の溶液を得た。得られた溶液
を、低反射膜層を有するクロム蒸着板上に回転数１，５
００ｒｐｍで回転塗布した後、表面温度９０℃のホット
プレート上で５分間ソフトベークして膜厚０．４μｍの
感放射線層を得た。ついで電子線照射装置を用いて電子
線照射を行った。ついでテトラメチルアンモニウムハイ
ドロオキサイド２．３８重量％水溶液で温度２３℃にて
６０秒間現像、純水にてリンスし、クロム基板上に転写
パターンを得、感度、解像性、パターン形状、残膜率、
耐熱性の評価を行った。その結果、感度は４５μＣ／ｃ
ｍ2 、０．５μｍラインアンドスペースを解像し、パタ
ーンは剥離もなく矩形を示し、残膜率は９９％以上あ
り、１３０℃までパターンの変形を起こさず高い耐熱性
を示した。Example 9 1.2 g of compound E and cresol novolac (meta /
Para ratio = 5/4; molecular weight 3,400) Propylene glycol propyl ether acetate 60 to which 8 g of dimethylformamide and a fluorosurfactant were added
g, and filtered through a membrane filter having a pore size of 0.1 μm to obtain a solution of the composition of the present invention. The obtained solution was spun on a chromium vapor deposition plate having a low reflection film layer at a rotation speed of 1,5.
After spin coating at 00 rpm, soft baking was performed on a hot plate having a surface temperature of 90 ° C. for 5 minutes to obtain a radiation-sensitive layer having a film thickness of 0.4 μm. Then, electron beam irradiation was performed using an electron beam irradiation device. Then, it is developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at a temperature of 23 ° C. for 60 seconds and rinsed with pure water to obtain a transfer pattern on a chromium substrate, and the sensitivity, resolution, pattern shape and residual film rate are obtained. ,
The heat resistance was evaluated. As a result, the sensitivity is 45 μC / c
m 2 and 0.5 μm line and space were resolved, the pattern was rectangular without peeling, the residual film ratio was 99% or more, and the pattern did not deform up to 130 ° C. and showed high heat resistance.
【００４０】[0040]
【発明の効果】本発明のポジ型感放射線樹脂組成物は、
放射線に対する感度が高く、基板に転写されたパターン
は、膨潤がなく感度、解像度が極めて優れ、さらに剥離
もなく耐熱性に極めて優れているので、半導体集積回路
の製造に極めて有用である。The positive type radiation sensitive resin composition of the present invention is
The pattern having high sensitivity to radiation and having no swelling and having excellent sensitivity and resolution, and having excellent heat resistance without peeling, is extremely useful for manufacturing a semiconductor integrated circuit.
Claims (2)
ジアジド−５−（及び／又は−４−）スルホニル基を示
す。ただし、少なくともどちらか１つは１，２−ナフト
キノンジアジド−５−（及び／又は−４−）スルホニル
基を示す。Ｒは−Ｈ、−ＯＨ、アルキル基、アルコキシ
基、アリール基、アリールアルキル基、アシル基、アシ
ルオキシ基を示す。ｌ，ｍは１〜３の整数。）で示され
る感放射線性化合物を含有することを特徴とするポジ型
感放射線性樹脂組成物。1. An alkali-soluble resin and a compound of formula (1): (In the formula, D represents a hydrogen atom or a 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl group, provided that at least one of them is 1,2-naphthoquinonediazide-5- ( And / or -4-) sulfonyl group, R represents -H, -OH, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, an acyl group, an acyloxy group, and l and m are integers of 1 to 3. The positive-type radiation-sensitive resin composition containing the radiation-sensitive compound shown by.
１，０００〜２０，０００である請求項１のポジ型感放
射線性樹脂組成物。2. The positive radiation-sensitive resin composition according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 1,000 to 20,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1694194A JPH07209861A (en) | 1994-01-18 | 1994-01-18 | Positive type radiation sensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1694194A JPH07209861A (en) | 1994-01-18 | 1994-01-18 | Positive type radiation sensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07209861A true JPH07209861A (en) | 1995-08-11 |
Family
ID=11930162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1694194A Pending JPH07209861A (en) | 1994-01-18 | 1994-01-18 | Positive type radiation sensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07209861A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998049601A1 (en) * | 1997-04-30 | 1998-11-05 | Nippon Zeon Co., Ltd. | Positive resist composition for photomask preparation |
| JP2008058548A (en) * | 2006-08-31 | 2008-03-13 | Sumitomo Bakelite Co Ltd | Positive photosensitive resin composition, protective film, interlayer insulation film, and semiconductor device and display element using the same |
| JP2015532649A (en) * | 2012-08-29 | 2015-11-12 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Bimesogenic compounds and mesogenic media |
-
1994
- 1994-01-18 JP JP1694194A patent/JPH07209861A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998049601A1 (en) * | 1997-04-30 | 1998-11-05 | Nippon Zeon Co., Ltd. | Positive resist composition for photomask preparation |
| JP2008058548A (en) * | 2006-08-31 | 2008-03-13 | Sumitomo Bakelite Co Ltd | Positive photosensitive resin composition, protective film, interlayer insulation film, and semiconductor device and display element using the same |
| JP2015532649A (en) * | 2012-08-29 | 2015-11-12 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Bimesogenic compounds and mesogenic media |
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