JPH01188852A - Resist using photosensitive compound - Google Patents
Resist using photosensitive compoundInfo
- Publication number
- JPH01188852A JPH01188852A JP1293788A JP1293788A JPH01188852A JP H01188852 A JPH01188852 A JP H01188852A JP 1293788 A JP1293788 A JP 1293788A JP 1293788 A JP1293788 A JP 1293788A JP H01188852 A JPH01188852 A JP H01188852A
- Authority
- JP
- Japan
- Prior art keywords
- examples
- resist
- photosensitive
- forming material
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 150000003839 salts Chemical group 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- -1 organic base salt Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 10
- 150000007530 organic bases Chemical class 0.000 claims 4
- 125000000962 organic group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 56
- 229920005989 resin Polymers 0.000 abstract description 28
- 239000011347 resin Substances 0.000 abstract description 28
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 229910005948 SO2Cl Inorganic materials 0.000 abstract 2
- 229910006069 SO3H Inorganic materials 0.000 abstract 2
- 230000027455 binding Effects 0.000 abstract 1
- 238000009739 binding Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 230000002250 progressing effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 39
- 239000003153 chemical reaction reagent Substances 0.000 description 37
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 37
- 238000002474 experimental method Methods 0.000 description 36
- 229920003986 novolac Polymers 0.000 description 35
- 239000010408 film Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 230000007261 regionalization Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZQXDUKMRLYGEHT-UHFFFAOYSA-N ethene hydrochloride Chemical compound Cl.C=C.C=C ZQXDUKMRLYGEHT-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/0163—Non ionic diazonium compounds, e.g. diazosulphonates; Precursors thereof, e.g. triazenes
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は半導体素子等を製造するときに用いられるレジ
ストに係り、露光エネルギー源として例えば２４８．４
１ｍのすなわちＫｒＦエキシマレーザ、遠紫外光等を用
いてポジ型のパターンを形成する際のレジストに関する
。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a resist used when manufacturing semiconductor devices, etc.
The present invention relates to a resist for forming a positive pattern using a 1 m long KrF excimer laser, deep ultraviolet light, or the like.
従来の技術
近年、半導体デバイスの高密度集積化に伴い、微細加工
、中でもフォトリングラフィに用いる露光装置の使用波
長は益々短波長化し、今では、ＫｒＦ ｘキシマレーザ
（２４８，４ｎｍ ）光が検討されるまでになってきて
いる。しかしながら、この波長に適した感光性材料は未
だ適当なものがなかった。Background of the Invention In recent years, as semiconductor devices have become more densely integrated, the wavelengths used by exposure equipment used for microfabrication, particularly photolithography, have become increasingly shorter, and KrF x ximer laser (248.4 nm) light is now being considered. It is getting to the point where However, there has not yet been a photosensitive material suitable for this wavelength.
例えば現在広く知られているレジストで、ＫｒＦエキシ
マレーザ光に対してかなり感光性が高く、光透過率もよ
いと言われているＭＰ２４００（シブレイ社）を用いた
場合でも、現像後のパターン形状は非常に悪く、使用で
きそうにもない１、発明が解決しようとする課題
このようにパターン形状が悪い原因は、ＭＰ２４ｏＯレ
ジストの露光光に対する表面吸収が大きいことに起因し
ていると考えられる。For example, even when using the currently widely known resist MP2400 (Sibley), which is said to have high sensitivity to KrF excimer laser light and good light transmittance, the pattern shape after development is It is very poor and unlikely to be usable. 1. Problems to be Solved by the Invention The reason for the poor pattern shape as described above is thought to be due to the large surface absorption of the exposure light of the MP24oO resist.
このことは、レジストに用いられているメインポリマー
（樹脂）自身が露光光に対して大きな吸収性を持ってい
るか、レジスト中の感光剤の光反応性が良くないためで
ある。即ち、従来のレジストに使用されているナフトキ
ノンジアゾ系の感光剤は、一般に２４８．４ｎｍ付近の
光に対して吸収が大きく、また露光後の透過率も殆どよ
くならない。例えば膜厚１．０７１ｍのＭＰ２４００で
は、 １ＫｒＦ ｘキシマレーザ（２４８，４ｎｍ）
を用いた露光前後の光透過小変化は第９図に示すように
２４Ｂ、４ｎｍにおいてわずか３係程度であり、反応性
の悪いことが理解される。This is because the main polymer (resin) used in the resist itself has a large absorbency for exposure light, or the photoreactivity of the photosensitizer in the resist is poor. That is, naphthoquinone diazo photosensitizers used in conventional resists generally have a large absorption of light around 248.4 nm, and the transmittance after exposure is hardly improved. For example, in MP2400 with a film thickness of 1.071 m, 1 KrF x ximer laser (248,4 nm)
As shown in FIG. 9, the small change in light transmission before and after exposure using 24B and 4 nm is only about a factor of 3, which indicates that the reactivity is poor.
従って、２４８．４ｎｍのエキシマレーザ光に対してよ
り反応性の高い感光材料の出現が、言い換えれば、同レ
ーザ光に対してより光反応性の高い感光剤の出現が待ち
望まれている現状にある。Therefore, the appearance of photosensitive materials that are more reactive to 248.4 nm excimer laser light, or in other words, the emergence of photosensitive agents that are more photoreactive to the same laser light, is currently being awaited. .
課題を解決するための手段
一３ｏ３Ｈ、−３ｏ３ＣＨ，を表しく但し、−５ｏ２ｃ
４はその第４級塩を含み、−３ｏ、Ｈはそのアンモニウ
ム塩、有機塩基の塩及び第４級塩を含む）、Ｙは夫々独
立で置換基を示す。ｎは夫々独立で整数を表す二１なる
感光基を少くとも１つ以上有する感光性化合物と樹脂よ
りなるレジストである。Means to solve the problem -3o3H, -3o3CH, where -5o2c
4 includes its quaternary salt, -3o and H include its ammonium salt, organic base salt and quaternary salt), and Y each independently represents a substituent. The resist is made of a resin and a photosensitive compound having at least one photosensitive group, 21, where n is an integer.
作用
本発明に用いられる感光性化合物の内、Ｎ２０
ＩＩ ＩＩ ＩＩ
−Ｃ−Ｃ−Ｃ−基は２４ ａ ｎｍ付近に吸収ピークを
持ち、エキシマレーザ光等の遠紫外光（ｄｅｅｐ ＵＶ
） によりＣ−Ｃ結合が切断され、その吸収ピーク
が小さくなる。これがアルカリ水溶解することになる。Function Among the photosensitive compounds used in the present invention, the N20 II II II -C-C-C- group has an absorption peak near 24 nm, and is sensitive to deep UV light such as excimer laser light.
), the C-C bond is broken and its absorption peak becomes smaller. This will dissolve in alkaline water.
従って本発明のレジストは光照射部分のみがアルカリ可
溶性となり、結果としてポジ型のパターンが得られる。Therefore, in the resist of the present invention, only the light-irradiated portion becomes alkali-soluble, resulting in a positive pattern.
ところが一般にレジストのメインポリマーはアルカリ可
溶性のノボラック樹脂などが主に用いられる。従って樹
脂のアルカリ可溶性を抑制できる事が望ましい。However, the main polymer of the resist is generally an alkali-soluble novolak resin. Therefore, it is desirable to be able to suppress the alkali solubility of the resin.
本発明のレジストにおいて感光性化合物の末端Ｋ −３
Ｏ２Ｇ６ 、−８ＯｓＨ＋−８ＯｓＣＨ３等ノ官能基を
有するものは、樹脂のアルカリ可溶部である一結合等を
おこし、樹脂のアルカリ可溶性を抑えることができる。In the resist of the present invention, the terminal K-3 of the photosensitive compound
Those having functional groups such as O2G6, -8OsH+-8OsCH3, etc. can form a bond, which is an alkali-soluble part of the resin, and can suppress the alkali solubility of the resin.
特に分子内に上記官能基を２個以上有するものは、上記
エステル結合が１分子中２か所以上で発生し、架橋反応
が進行し分子量増大をもたらすため、樹脂の溶解性をさ
らに一層抑制させる事ができる。In particular, when the molecule has two or more of the above-mentioned functional groups, the above-mentioned ester bonds occur at two or more places in one molecule, and the crosslinking reaction progresses, resulting in an increase in molecular weight, which further suppresses the solubility of the resin. I can do things.
なお本発明に用いられる感光性化合物において、−５ｏ
２Ｃ１、−３ｏ５Ｉ（、−８ｏ５ＣＨ，等の官能基はベ
ンゼン環、ナフタレン環のいずれの位置にあってもよく
、いずれの場合も感光剤としての効果に相違はない。In addition, in the photosensitive compound used in the present invention, -5o
The functional groups such as 2C1, -3o5I(, -8o5CH, etc.) may be located at either the benzene ring or the naphthalene ring, and there is no difference in the effect as a photosensitizer in either case.
また良好なパターン形状を得るには、２４ Ｅ１４ｎｍ
における吸収強度がｄｅｅｐ Ｕ Ｖ 露光により大き
な差を生じる事が必要不可欠である。In addition, to obtain a good pattern shape, 24E14nm
It is essential that the absorption intensities at 100 to 200 nm vary greatly with deep UV exposure.
本発明のレジストに用いる感光性化合物において、−Ｃ
Ｈ５，−ＣＨ２Ｃ）１３ 等の水素原子以外の置換基
をベンゼン環に付加したものや、これに代えてナフタレ
ン基を使用したものは、通常２５０ｎＸＩｌ付近にピー
クを持つベンゼン環の吸収を２０〜ｓｏｎｍ高波長側に
シフトさせ、結果として２４８．４ｎｌＨにおける透過
率を露光前後ともに６〜１６チ向上させた。In the photosensitive compound used in the resist of the present invention, -C
Those with substituents other than hydrogen atoms such as H5, -CH2C)13 added to the benzene ring, or those using a naphthalene group in place of this, usually reduce the absorption of the benzene ring, which has a peak around 250nXIl, from 20 to As a result, the transmittance at 248.4 nlH was improved by 6 to 16 inches both before and after exposure.
なお−〇Ｈ，、−０Ｈ２Ｃ３Ｈ，等の置換基は、ベンゼ
ン環中のいずれの位置でもよく、いずれの場合も透過率
が北昇する事を発明者らは確認している。The substituents such as -0H, -0H2C3H, etc. may be placed at any position on the benzene ring, and the inventors have confirmed that the transmittance increases northward in either case.
実施例
以下に実施例を用いて本発明を更に詳細に説明するが、
本発明は、これらの実施例に何ら限定されるものではな
い。EXAMPLES The present invention will be explained in more detail using examples below.
The present invention is not limited to these examples in any way.
（実施例１） 下記の組成で試薬を調整し、パターン形成材料とした。(Example 1) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレンクリコールジメチルエーテル・・・・・・３
ｏｙ
第１図を用いて本発明に係る感光性材料（パターン形成
材料）を用いたパターン形成方法を説明する。半導体等
の基板１上に上記組成で溶解されたパターン形成材′科
２を回転塗布し、１．０μｍのレジスト膜を得る（第１
図ａ）。なお、基板１上には酸化膜、絶縁膜、導電膜等
が形成されている場合が多い。次に２４８．４ｎｔ１１
のエキシマレーザ光３をマスク４を介して選択的にパル
ス露光を行う（第１図ｂ）。そして最後に通常のアルカ
リ現像液を用いて現像を行う事により、パターン形成材
料２の光露光部のみを溶解除去してレジストパターン２
ａを得た（第１図Ｃ）。なおこのときレジストパターン
２ａはアスペクト比が９０度の好形状で、第２図の感度
曲線に示す様、約６０ｍＪという少い露光漬でパターン
形成が可能で、膜減りも約１０係以下のサブミクロンパ
ターンであった。このパターン形成材料の露光前後の紫
外線分光曲線図を第３図に示すが、２４８，４ｎｍにお
ける露光前後の透過率はそれぞれ１０％と８５％となり
、その変化量は約７５係と大きなものであった。すなわ
ちこの感光材料及び本発明の感光性化合物がＫｒＦエキ
シマレーザ光に対して好反応性を示したことがわかる。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
oy A pattern forming method using a photosensitive material (pattern forming material) according to the present invention will be explained using FIG. The pattern forming material 2 dissolved in the above composition is spin-coated onto a substrate 1 such as a semiconductor to obtain a 1.0 μm resist film (first
Diagram a). Note that an oxide film, an insulating film, a conductive film, etc. are often formed on the substrate 1. Next 248.4nt11
Selective pulse exposure is performed using excimer laser light 3 through a mask 4 (FIG. 1b). Finally, by performing development using a normal alkaline developer, only the light-exposed areas of the pattern forming material 2 are dissolved and removed, resulting in a resist pattern 2.
a was obtained (Fig. 1C). At this time, the resist pattern 2a has a good shape with an aspect ratio of 90 degrees, and as shown in the sensitivity curve in Figure 2, it is possible to form a pattern with a small exposure dip of about 60 mJ, and the film reduction is about 10 factors or less. It was a micron pattern. Figure 3 shows the ultraviolet spectral curves of this pattern-forming material before and after exposure, and the transmittance before and after exposure at 248 and 4 nm was 10% and 85%, respectively, and the amount of change was as large as about 75 factors. Ta. That is, it can be seen that this photosensitive material and the photosensitive compound of the present invention showed good reactivity to KrF excimer laser light.
（実施例２） 下記の組成で試薬を調整し、パターン形成材料とした。(Example 2) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・ １９
ノボラック位１月旨 ・−・・・・
９ｇジエチレングリコールジメチルエーテル・・・・
・・３０ｇ
これを用いて実施例１と同様の実験を行った。・・・・・・ 19 Novolak rank January ・・・・・・・・・
9g diethylene glycol dimethyl ether...
...30g Using this, the same experiment as in Example 1 was conducted.
その結果レジストパターンは実施例１と同様の高アスペ
クト比のサブミクロンパターンであった。As a result, the resist pattern was a submicron pattern with a high aspect ratio similar to that in Example 1.
第４図にその感度曲線を示すが、膜減り１０φ以内で感
度も約６０ｍＪと実施例１と同様の結果を得だ。また第
６図にこのパターン形成材料の露光前後の紫外線分光曲
線図を示すが、２４８．４ｎｌ１１における露光前後の
透過率変化も実施例１とほぼ同じ約７５係となった。The sensitivity curve is shown in FIG. 4, and the sensitivity was about 60 mJ when the film was reduced within 10φ, which is the same result as in Example 1. Further, FIG. 6 shows ultraviolet ray spectral curves of this pattern forming material before and after exposure, and the change in transmittance before and after exposure at 248.4nl11 was about 75 factors, which is almost the same as in Example 1.
（実施例３） 下記の組成で試薬を調整し、パターン形成材料とした。(Example 3) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレンクリコールジメチルエーテル・・・・・・３
０．９
これを用いて実施例１〜２と同様の実験を行った。その
結果、実施例１．２と同様の高アスペクト比なサブミク
ロンパターンが得られた。第６図に感度曲線を示すが、
膜減りはまったく観察されず、実施例１．２より高い感
度（約４８＋１１Ｊ）が得られた。第７図にこのパター
ン形成材料の露光前後の紫外線分光曲線を示すが、２４
Ｂ、４ｎｍにおける露光前後の透過率変化は約８６％で
あった。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0.9 Using this, experiments similar to those in Examples 1 and 2 were conducted. As a result, a high aspect ratio submicron pattern similar to Example 1.2 was obtained. Figure 6 shows the sensitivity curve.
No film thinning was observed at all, and higher sensitivity (approximately 48+11 J) than in Example 1.2 was obtained. Figure 7 shows the ultraviolet ray spectral curves of this pattern forming material before and after exposure.
B, the transmittance change before and after exposure at 4 nm was about 86%.
（実施例４） 下記の組成で試薬を調整しパターン形成材料とした。(Example 4) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １９
ノボラック樹脂 ・・・・・・ ９！
ｉジエチレングリコールジメチルエーテル・・・・・・
３０ｇ
これを用いて実施例１〜３と同様の実験を行った。その
結果は、実施例３と同様の良好なものが得られた。・・・・・・ 19 Novolac resin ・・・・・・ 9!
i Diethylene glycol dimethyl ether...
30g Using this, experiments similar to Examples 1 to 3 were conducted. The results were as good as in Example 3.
（実施例６） 下記の組成で試薬を調整しパターン形成材料としだ。(Example 6) Prepare a reagent with the following composition and use it as a pattern forming material.
・・・・・・ １９
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
ｏ９
これを用いて実施例１〜４と同様の実験を行った。その
結果は、実施例３〜４と同様の良好な結果が得られた。・・・・・・ 19 Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
o9 Using this, experiments similar to Examples 1 to 4 were conducted. As for the results, good results similar to those of Examples 3 and 4 were obtained.
（実施例６） 下記の組成で試薬を調整しパターン形成材料とした。(Example 6) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボ２ツク樹脂 ・・・・・・ ９９
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜５と同様の実験を行った。その
結果は、実施例３〜６と同様の良好な結果が得られた。・・・・・・ 1g Novo 2 Tsuku Resin ・・・・・・ 99
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 5 were conducted. As for the results, good results similar to those of Examples 3 to 6 were obtained.
（実施例７） 以下の組成で試薬を調整しパターン形成材料とした。(Example 7) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １１
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜６と同様の実験を行った。その
結果、実施例３〜６と同様の良好な結果が得られた。・・・・・・ 11 Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 6 were conducted. As a result, good results similar to Examples 3 to 6 were obtained.
（実施例８） 以下の組成で試薬を調整しパターン形成材料とした。(Example 8) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １１
ノボラ、７り樹脂 ・町・・ ９ｇジ
エチレンクｌ） −ｔ−ルジメチルエーテル・・・・・
・３０．５１’
これを用いて実施例１〜７と同様の実験を行った。その
結果、実施例３〜７と同様の良好な結果が得られた。...... 11 Novola, 7 resin ・Machi... 9g diethylene chloride) -t-dimethyl ether...
-30.51' Experiments similar to Examples 1 to 7 were conducted using this. As a result, good results similar to Examples 3 to 7 were obtained.
（実施例９）
以下の組成で試薬を調整しパターン形成材料と・・・・
・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
ｏｙ
これを用いて実施例１〜８と同様の実験を行った。その
結果は実施例３〜８と同様の良好なものが得られた。(Example 9) Prepare a reagent with the following composition and use it as a pattern forming material...
・・・ 1g Novolak resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
oy Using this, experiments similar to Examples 1 to 8 were conducted. The results were as good as those in Examples 3-8.
（実施例１０） 以下の組成で試薬を調整しパターン形成材料としだ。(Example 10) Prepare the reagent with the following composition and use it as a pattern forming material.
（以下余 白）
・・・・・・ １ ｇ
ノボラ・ツク樹脂 ・・・・・・ ９
ｇジエチレングリコールジメチルエーテル・・・・・・
３０ｇ
これを用いて実施例１〜９と同様の実験を行った。その
結果は実施例３〜９と同様の良好なものであった。(Left below) ・・・・・・ 1 g Novola Tsuku Resin ・・・・・・ 9
g Diethylene glycol dimethyl ether...
30g Using this, experiments similar to Examples 1 to 9 were conducted. The results were as good as Examples 3-9.
（実施例１１）
以下の組成で試薬を調整しパターン形成材料とノボラッ
ク樹脂 ・・・・・・ ９ｇジエチレ
ングリコールジメチルエーテル・・・・・・３０！！
これを用いて実施例１〜１ｏと同様の実験を行った。そ
の結果は実施例３〜１０と同様の良好なものが得られた
。(Example 11) Reagents were prepared with the following composition, pattern forming material and novolak resin...9g diethylene glycol dimethyl ether...30! ! Using this, experiments similar to Examples 1 to 1o were conducted. The results were as good as those of Examples 3 to 10.
（実施例１２） 以下の組成で試薬を調整しパターン形成材料とした。(Example 12) A reagent was prepared with the following composition and used as a pattern forming material.
ノボラ・ンク樹脂 ・・・・・・ ９
ｇジエチレングリコールジメチルエーテル・・・・・・
３０９
これを用いて実施例１〜１１と同様の実験を行った。そ
の結果は実施例３〜１１と同様の良好なものであった。Novola resin ・・・・・・9
g Diethylene glycol dimethyl ether...
309 Using this, experiments similar to Examples 1 to 11 were conducted. The results were as good as Examples 3-11.
（実施例１３） 以下の組成で試薬を調整しパターン形成材料とした。(Example 13) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０，９
これを用いて実施例１〜１２と同様の実験を行った。そ
の結果高アスペクト比なサブミクロンパターンが得られ
た。第８図に感度曲線を示すが、膜べりはまったく観察
されず、非常に高い感度（約４０ ｒｎＪ／ｃｙＡ
）である事がわかる。第９図にこのパターン形成材料の
露光前後の紫外線分光曲線を示すが、２４８．４１ｍに
おける透過率変化量は約８５憾であった。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0.9 Using this, experiments similar to Examples 1 to 12 were conducted. As a result, a submicron pattern with a high aspect ratio was obtained. The sensitivity curve is shown in Figure 8. No membrane loss was observed, and the sensitivity was very high (approximately 40 rnJ/cyA).
). FIG. 9 shows the ultraviolet ray spectral curves of this pattern-forming material before and after exposure, and the amount of change in transmittance at 248.41 m was about 85.
（実施例１４） 以下の組成で試薬を調整しパターン形成材料とした。(Example 14) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １１
ノボラック樹脂 ・−・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・ａ
ｏｇ
これを用いて実施例１〜１３と同様の実験を行った。そ
の結果は実施例１３と同様の良好なものが得られた。・・・・・・ 11 Novolac resin ・・・・・・・ 9g
Diethylene glycol dimethyl ether...a
og This was used to conduct experiments similar to Examples 1 to 13. The results were as good as in Example 13.
（実施例１５） 以下の組成で試薬を調整しパターン形成材料とした。(Example 15) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０．９
これを用いて実施例１〜１４と同様の実験を行った。そ
の結果は実施例１３〜１４と同様の良好なものであった
。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0.9 Using this, experiments similar to Examples 1 to 14 were conducted. The results were as good as Examples 13-14.
（実施例１６） 以下の組成で試薬を調整しパターン形成材料とした。(Example 16) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜１５と同様の実験を行った。そ
の結果は実施例１３〜１６と同様の良好なものが得られ
た。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 15 were conducted. The results were as good as those in Examples 13-16.
（実施例１７） 以下の組成で試薬を調整しパターン形成材料としだ。(Example 17) Prepare the reagent with the following composition and use it as a pattern forming material.
・・・・・・ １ ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレンクリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜１６と同様の実験を行った。そ
の結果は実施例１３〜１６と同様の良好なものであった
。・・・・・・ 1 g Novolak resin ・・・・・・ 9 g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 16 were conducted. The results were as good as Examples 13-16.
（実施例１８） 以下の組成で試薬を調整しパターン形成材料とした。(Example 18) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９Ｉ
ジエチレンクリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜１７と同様の実験を行った。そ
の結果は実施例１３〜１７と同様の良好なものが得られ
た。・・・・・・ 1g Novolac resin ・・・・・・ 9I
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 17 were conducted. The results were as good as those in Examples 13-17.
（実施例１９） 以下の組成で試薬を調整しパターン形成材料とした。(Example 19) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例／〜／＃と同様の実験を行った。そ
の結果は実施例／Ｊ−／ｇと同様の良好なものであった
。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples/~/# were conducted. The results were as good as in Example/J-/g.
（実施例２０） 以下の組成で試薬を調整しパターン形成材料とした。(Example 20) A reagent was prepared with the following composition and used as a pattern forming material.
Ａｒ。Ar.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９Ｉ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜１９と同様の実験を行った。そ
の結果は実施例１３〜１９と同様の良好なものが得られ
た。・・・・・・ 1g Novolac resin ・・・・・・ 9I
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 19 were conducted. The results were as good as those in Examples 13-19.
（実施例２１） 以下の組成で試薬を調整しパターン形成材料とした。(Example 21) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ２
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０．９
これを用いて実施例１〜２ｏと同様の実験を行った。そ
の結果は実施例１３〜２ｏと同様の良好なものであった
。Mr2 ・・・・・・ 1g Novolak resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0.9 Using this, experiments similar to Examples 1 to 2o were conducted. The results were as good as Examples 13-2o.
（実施例２２） 以下の組成で試薬を調整しパターン形成材料とした。(Example 22) A reagent was prepared with the following composition and used as a pattern forming material.
Ａｒ２
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレンクリコールジメチルエーテル・・・・・・３
０．！９
これを用いて実施例１〜２１と同様の実験を行った。そ
の結果は実施例１３〜２１と同様の良好なものが得られ
た。Ar2 ・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0. ! 9 Using this, experiments similar to Examples 1 to 21 were conducted. The results were as good as those in Examples 13-21.
（実施例２３） 以下の組成で試薬を調整しパターン形成材料としだ、。(Example 23) Prepare the reagent with the following composition and use it as a pattern forming material.
Ａｒ。Ar.
ムｒ。Mr.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜２２と同様の実験を行った。そ
の結果は実施例１３〜２２と同様の良好なものであった
。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 22 were conducted. The results were as good as Examples 13-22.
（実施例２４） 以下の組成で試薬を調整しパターン形成材料とした。(Example 24) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ１ｈｒ２
・・・・・・ １１
ノボラック樹脂 ・・・・・・ ９Ｉ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜２３と同様の実験を行った。そ
の結果は実施例１３〜２３と同様の良好なものが得られ
た。Mr1hr2 ・・・・・・ 11 Novolac resin ・・・・・・ 9I
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 23 were conducted. The results were as good as those of Examples 13-23.
（実施例２５） 以下の組成で試薬を調整しパターン形成材料とした。(Example 25) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレンクリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜２４と同様の実験を行った。そ
の結果は実施例１３〜２４と同様の良好なものであった
。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 24 were conducted. The results were as good as Examples 13-24.
（実施例２６）
以下の組成で試薬を調整しパターン形成材料とした１、
ノポラ・ツク樹脂 ・・・・・・ ９
ｇジエチレングリコールジメチルエーテル・・・・・・
ａｏｇ
これを用いて実施例１〜２５と同様の実験を行った。そ
の結果は実施例１３〜２５と同様の良好なものが得られ
た。(Example 26) A reagent was prepared with the following composition and used as a pattern forming material 1. Nopola Tsuku resin 9
g Diethylene glycol dimethyl ether...
aog Experiments similar to Examples 1 to 25 were conducted using this. The results were as good as those of Examples 13-25.
（実施例２７） 以下の組成で試薬を調整しパターン形成材料とした。(Example 27) A reagent was prepared with the following composition and used as a pattern forming material.
Ａｒ
／Ｃ＼
Ｎ
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテルこれを用いて実
施例１〜２６と同様の実験を行った。その結果は実施例
１３〜２６と同様の良好なものであった。Ar /C\N ・・・・・・ 1g Novolak resin ・・・・・・ 9g
Diethylene glycol dimethyl ether The same experiments as in Examples 1 to 26 were conducted using this diethylene glycol dimethyl ether. The results were as good as Examples 13-26.
（実施例２８） 以下の組成で試薬を調整しパターン形成材料とした。(Example 28) A reagent was prepared with the following composition and used as a pattern forming material.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
ｏｙ
これを用いて実施例１〜２７と同様の実験を行った。そ
の結果は実施例１３〜２７と同様の良好なものが得られ
た。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
oy Using this, experiments similar to Examples 1 to 27 were conducted. The results were as good as those of Examples 13-27.
（実施例２９） 以下の組成で試薬を調整しパターン形成材料とした。(Example 29) A reagent was prepared with the following composition and used as a pattern forming material.
Ａｒ。Ar.
、ｃ＼
Ｎ
・・・・・・ １！１
ノボラ・ツク樹脂 ・・・中９ｇジエ
チレングリコールジメチルエーテル・・・・・・３ｏｙ
これを用いて実施例１〜２８と同様の実験を行った。そ
の結果は実施例１３〜２８と同様の良好なものであった
。, c\N...1!1 Novola Tsuku resin...9g diethylene glycol dimethyl ether...3oy Using this, the same experiments as in Examples 1 to 28 were conducted. The results were as good as Examples 13-28.
（実施例３０） 以下の組成で試薬を調整しパターン形成材料とした。(Example 30) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ２
■
Ａｒ ２Ａｒ ２
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレンクリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜２９と同様の実験を行った。そ
の結果は実施例１３〜２９と同様の良好なものが得られ
た。Mu r2 ■ Ar 2Ar 2 ・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 29 were conducted. The results were as good as those of Examples 13-29.
（実施例３１） 以下の組成で試薬を調整しパターン形成材料とした。(Example 31) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ、ムｒ。Mr, Mr.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜３ｏと同様の実験を行った。そ
の結果は実施例１３〜３ｏと同様の良好なものであった
。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 3o were conducted. The results were as good as Examples 13-3o.
（実施例３２） 以下の組成で試薬を調整しパターン形成材料とした。(Example 32) A reagent was prepared with the following composition and used as a pattern forming material.
↑ｒ１
Ａｒ、 ムｒ２
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜３１と同様の実験を行った。そ
の結果は実施例１３〜３１と同様の良好なものが得られ
た。↑r1 Ar, mr2 ・・・・・・ 1g Novolak resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 31 were conducted. The results were as good as those of Examples 13-31.
（実施例３３） 以下の組成で試薬を調整しパターン形成材料とした。(Example 33) A reagent was prepared with the following composition and used as a pattern forming material.
Ａｒ２ Ａｒ。Ar2 Ar.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜３２と同様の実験を行った。そ
の結果は実施例１３〜３２と同様の良好なものであった
。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 32 were conducted. The results were as good as Examples 13-32.
（実施例３４） 以下の組成で試薬を調整しパターン形成材料とした。(Example 34) A reagent was prepared with the following composition and used as a pattern forming material.
物
ムｒ２ ムｒ２
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜３３と同様の実験を行った。そ
の結果は実施例１３〜３３と同様の良好なものが得られ
た。Material r2 Mu r2 ・・・・・・ 1g Novolak resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 33 were conducted. The results were as good as those of Examples 13-33.
（実施例３６） 以下の組成で試薬を調整しパターン形成−材料とした。(Example 36) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ、 Ａｒ２
・・・・・・ １９
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０ｇ
これを用いて実施例１〜３４と同様の実験を行った。そ
の結果は実施例１３〜３４と同様の良好なものであった
。Mr, Ar2 ・・・・・・ 19 Novolak resin ・・・・・・ 9g
Diethylene glycol dimethyl ether...3
0g Using this, experiments similar to Examples 1 to 34 were conducted. The results were as good as Examples 13-34.
（実施例３６） 以下の組成で試薬を調整しパターン形成材料とした。(Example 36) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ２ ムｒ。Mr2 Mr.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９！
ｊジエチレングリコールジメチルエーテル・・・・・・
３０ｇ
これを用いて実施例１〜３６と同様の実験を行った。そ
の結果は実施例１３〜３５と同様の良好なものが得られ
た。・・・・・・ 1g Novolac resin ・・・・・・ 9!
jDiethylene glycol dimethyl ether...
30g Using this, experiments similar to Examples 1 to 36 were conducted. The results were as good as those of Examples 13-35.
（実施例３７） 以下の組成で試薬を調整しパターン形成材料とした。(Example 37) A reagent was prepared with the following composition and used as a pattern forming material.
ムｒ２ ムｒ２
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
ジエチレングリコールジメチルエーテル・・・・・・３
０．ｊ９
これを用いて実施例１〜３６と同様の実験を行った。そ
の結果は実施例１３〜３６と同様の良好なものであった
。Mr2 Mr2 ・・・・・・ 1g Novolac resin ・・・・・・9g
Diethylene glycol dimethyl ether...3
0. j9 Using this, experiments similar to Examples 1 to 36 were conducted. The results were as good as Examples 13-36.
なお、パターン形成材料中の樹脂は感光材料の光表面吸
収の低減する為に、２４８．４ ｎ思などの遠紫外光に
対して透明性の高いものが必要とされる。実施例１〜１
９で用いたノボラック樹脂の他に、マレイミド系樹脂、
ヒドロキシスチレン樹脂、オルトフロロメタクレゾール
ノボラック樹脂などを用いても同様な結果が得られるが
、もちろんこれらに限定されるものではない。Note that the resin in the pattern forming material is required to be highly transparent to far ultraviolet light such as 248.4 nm in order to reduce the light surface absorption of the photosensitive material. Examples 1-1
In addition to the novolak resin used in 9, maleimide resin,
Similar results can be obtained using hydroxystyrene resin, orthofluorome cresol novolac resin, but the present invention is not limited to these.
溶媒についても同様の透明性が望まれ、本実施例では遠
紫外領域に吸収の少いジエチレングリコールジメチルエ
ーテルを用いたが、感光材料および樹脂が溶解可能なエ
チルセルンルブアセテート等も使用可能である。もちろ
ん溶媒に関しても、これらに限定されるものではない。Similar transparency is desired for the solvent, and in this example diethylene glycol dimethyl ether, which has little absorption in the deep ultraviolet region, was used, but ethyl cerene rub acetate, etc., which can dissolve photosensitive materials and resins, can also be used. Of course, the solvent is not limited to these.
（実施例３日）
以下の組成からなるパターン形成用コントラストエンハ
ンスト材料（以下ＯＥＭと略）を調整した。(Example 3) A contrast enhanced material for pattern formation (hereinafter abbreviated as OEM) having the following composition was prepared.
・・・・・・ １ｇ
ノボラック樹脂 ・・・・・・ ９ｇ
エチルセルソルブアセテート ・・・・・・６０ｇ
このように調整されたＯＥＭはこれを膜としてパターン
形成有機薄膜としたとき、厚さ０．１２μｍで２４８．
４μｍのＫｒＦエキシマレーザ光での露光前後で２４８
．４ｎｍにおける透過率の差が５０係以上と非常に大き
くなり、入射光のコントラストを向上させる働きをする
事がわかった。・・・・・・ 1g Novolac resin ・・・・・・ 9g
Ethyl cell solve acetate 60g
The OEM prepared in this way has a thickness of 0.12 μm and a thickness of 248 mm when used as a film to form a patterned organic thin film.
248 before and after exposure to 4μm KrF excimer laser light
．． It was found that the difference in transmittance at 4 nm was extremely large, with a factor of 50 or more, and that it worked to improve the contrast of incident light.
この本発明に係るＯＥＭを用いたレジストパターン形成
方法を第１０図を使って示す。A resist pattern forming method using OEM according to the present invention will be illustrated using FIG.
半導体等の基板１上にポジ型しジス）５（ＭＰ２４００
ニジプレイ社）を１．０μｍに回転塗布する（第１０図
ａ）。次にポジ型レジスト６上に水溶性有機薄膜６、例
えばプルランとポリビニルピロリドンの混合溶液を塗付
形成する（第１０図ｂ）。A positive type resistor) 5 (MP2400) is placed on a substrate 1 such as a semiconductor.
Nijiplay Co., Ltd.) to a thickness of 1.0 μm (Fig. 10a). Next, a water-soluble organic thin film 6, for example, a mixed solution of pullulan and polyvinylpyrrolidone, is applied and formed on the positive resist 6 (FIG. 10b).
このときう°ルランとポリビニルピロリドンの混合重量
比は４：１であり、膜厚はパターン形成に影響のない様
に０．１〜°ｏ、３μｍ程度とした。なおこの中間層で
ある水溶性有機薄膜は下層レジストと上層レジストが混
同しない様に設けているもので必ずしも必要ではない。At this time, the mixing weight ratio of luran and polyvinylpyrrolidone was 4:1, and the film thickness was set to about 0.1 to 3 μm so as not to affect pattern formation. Note that the water-soluble organic thin film serving as the intermediate layer is provided so that the lower resist layer and the upper resist layer are not confused, and is not necessarily required.
次に本発明のＣＦＣＭ７を厚さ約０．１２１１ｍに回転
塗付した（第１０図Ｃ）。Next, CFCM7 of the present invention was spin-coated to a thickness of about 0.1211 m (FIG. 10C).
ここで下層レジストと中間層水溶性有機薄膜、水溶性有
機薄膜とＯＥＭ層は全く密着性良く積層できた。そして
２４８．４ｎｍのＫｒＦエキシマレーザ光３でマスク４
を介してＯＥＭ層７を選択的にパルス露光した（第１０
図ｄ）。そして最後にアルカリ現像液によってＣＥＭ層
７および中間層有機薄膜６を同時に除去するとともに下
地レジスト６の光照射部のみを現像除去し、レジストパ
ターン５ａを得た（第１０図ｅ）。このときレジストパ
ターン６ａは高アスペクト比な０．３μｍのラインアン
ドスペーステアった。Here, the lower resist layer, the intermediate water-soluble organic thin film, and the water-soluble organic thin film and the OEM layer were laminated with excellent adhesion. Then, the mask 4 is exposed to the 248.4 nm KrF excimer laser beam 3.
The OEM layer 7 was selectively exposed to pulse light through the 10th
Figure d). Finally, the CEM layer 7 and the intermediate organic thin film 6 were simultaneously removed using an alkaline developer, and only the light-irradiated portions of the base resist 6 were developed and removed to obtain a resist pattern 5a (FIG. 10e). At this time, the resist pattern 6a had line and space tear with a high aspect ratio of 0.3 μm.
発明の効果
本発明は、例えば２４８．４ｎｍのＫｒＦエキシマレー
ザ光などに対して優れた反応性を有する新規なレジスト
を提供するものであり、例えばＫｒＦエキシマレーザ光
（２４８，４ｎｍ）などの遠紫外ＩＷ（ｄａａｐ ｔｒ
ｙ ）露光用レジストやＯＥＭ等に応用した場合には
サブミクロンオーダの形状良い微細パターンが容易に得
られるので、半導体産業における超微細パターンの形成
にとって価値穴なるものである。Effects of the Invention The present invention provides a novel resist that has excellent reactivity to, for example, 248.4 nm KrF excimer laser light. IW (daap tr
y) When applied to exposure resists, OEM, etc., it is easy to obtain fine patterns with good shapes on the order of submicrons, so it is valuable for the formation of ultra-fine patterns in the semiconductor industry.
第１図は本発明の感光性化合物を含んでなるパターン形
成材料を用いたパターン形成方法の工程断面図、第２図
、第４図、第６図、第８図は本発明の一実施例のパター
ン形成材料の感度曲線図、第３図、第５図、第７図、第
９図は本発明の一実施例のパターン形成材料の紫外線分
光曲線図、第１０図は従来のレジス）（ＭＰ２４００）
を用いたパターン形成方法の工程断面図、第１１図は従
来のレジスト（ＭＰ２４００ ）の紫外線分光曲線図で
ある。
１・・・・・・基板、２・・・・・・本発明のパターン
形成用レジスト、３・・・・・・エキシマレーザ元、４
・・・・・・マスク、５・・・・・・ポジ型しジス）（
ＭＰ２４００）、６・・・・・・水溶性有機薄膜、７・
・・・・・パターン形成用コントラストエンハンスｌ−
ＭＩＮ。
代理人の氏名 弁理士 中 尾 敏 男 はが１名第１
図
１−Ｊｉ版
？−ハ゛グーン形成丁ト１テ
３・・−ｒキソマし−ｆた
４−ｖｚり
第２図
葛 ｊｔ ｔ （ｒｎ、ｙ）
第３図
ジ（長 （ｎｕｎ〕
第４図
蕗 た ｔ ＜ｒＪ）
第５ＷＡ
う皮 灸 （ｎｒｎ ）
第６図
茎 ｔ ｔ ＜ｒｎフ・ノ第７図
５皮 灸 （７１ｆｆｌ）
第８図
傾く 九 ｔ ＜ｍ７）
第 ９ 図
速２ 長 （ｎｒｎ）
５・−ぶｉノ４Ｌレジ又ト
３−−−二１シマＬ−７′九FIG. 1 is a process cross-sectional view of a pattern forming method using a pattern forming material containing the photosensitive compound of the present invention, and FIGS. 2, 4, 6, and 8 are examples of the present invention. FIGS. 3, 5, 7, and 9 are ultraviolet ray spectral curves of a pattern forming material according to an embodiment of the present invention, and FIG. 10 is a conventional resist) ( MP2400)
FIG. 11 is a process cross-sectional view of a pattern forming method using a conventional resist (MP2400). DESCRIPTION OF SYMBOLS 1...Substrate, 2...Resist for pattern formation of the present invention, 3...Excimer laser source, 4
...Mask, 5...Positive type) (
MP2400), 6...Water-soluble organic thin film, 7.
...Contrast enhancement l- for pattern formation
MIN. Name of agent: Patent attorney Toshio Nakao (1st person)
Figure 1 - Ji version? -Hagoon formation 1 te 3...-r chisomashi-f 4-vzriFig. 5th WA caries moxibustion (nrn) Fig. 6 Stem t t <rnf・ノ Fig. 7 i no 4L register matato 3---21shima L-7'9
Claims (7)
Ｏ＿３ＣＨ＿３を表し（但し、−ＳＯ＿２Ｃｌはその第
４級塩を含み、−ＳＯ＿３Ｈはそのアンモニウム塩、有
機塩基の塩及び第４級塩を含む）、Ｙは置換基、ｎは整
数を表す〕よりなる感応基を少くとも１つ有してなる感
光性化合物を用いたレジスト。(1) There are ▲mathematical formulas, chemical formulas, tables, etc. in the molecule▼ [X is a hydrogen atom, -SO_2Cl, -SO_3H, -S
represents O_3CH_3 (however, -SO_2Cl includes its quaternary salt, -SO_3H includes its ammonium salt, organic base salt, and quaternary salt), Y represents a substituent, and n represents an integer] A resist using a photosensitive compound having at least one sensitive group.
Ｏ＿３ＣＨ＿３を表し（但し、−ＳＯ＿２Ｃｌはその第
４級塩を含み、−ＳＯ＿３Ｈはそのアンモニウム塩、有
機塩基の塩及び第４級塩を含む）、ｎは整数を表す〕よ
りなる感応基を少くとも１つ有してなる感光性化合物を
用いたレジスト。(2) There are ▲mathematical formulas, chemical formulas, tables, etc. in the molecule▼ [X is a hydrogen atom, -SO_2Cl, -SO_3H, -S
O_3CH_3 (wherein -SO_2Cl includes its quaternary salt, -SO_3H includes its ammonium salt, salt of an organic base, and quaternary salt), and n represents an integer]. A resist using a photosensitive compound containing one.
ＳＯ＿３Ｈ、−ＳＯ＿３ＣＨ＿３を表し（但し、−ＳＯ
＿２Ｃｌはその第４級塩を含み、−ＳＯ＿３Ｈはそのア
ンモニウム塩、有機塩基の塩及び第４級塩を含む）、Ｙ
及びＹ′は夫々独立に置換基を表し、ｍ及びｎは夫々独
立で整数を表す〕で示される感光性化合物を用いたレジ
スト。(3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [X and X' are each independently a hydrogen atom, -SO_2Cl-
SO_3H, -SO_3CH_3 (however, -SO
_2Cl includes its quaternary salt, -SO_3H includes its ammonium salt, organic base salt and quaternary salt), Y
and Y' each independently represent a substituent, and m and n each independently represent an integer].
−ＳＯ＿３Ｈ、−ＳＯ＿３ＣＨ＿３を表し（但し、−Ｓ
Ｏ＿２Ｃｌはその第４級塩を含み、−ＳＯ＿３Ｈはその
アンモニウム塩、有機塩基の塩及び第４級塩を含む）、
Ｙは置換基を表し、ｍ及びｎは夫々独立で整数を表す〕
で示される感光性化合物を用いたレジスト。(4) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [X and X' are each independently a hydrogen atom, -SO_2Cl,
-SO_3H, -SO_3CH_3 (however, -S
O_2Cl includes its quaternary salts, -SO_3H includes its ammonium salts, salts of organic bases and quaternary salts),
Y represents a substituent, m and n each independently represent an integer]
A resist using a photosensitive compound shown in
−ＳＯ＿３Ｈ、−ＳＯ＿３ＣＨ＿３を表し（但し、−Ｓ
Ｏ＿２Ｃｌはその第４級塩を含み、−ＳＯ＿３Ｈはその
アンモニウム塩、有機塩基の塩及び第４級塩を含む）、
ｍ及びｎは夫々独立で整数を表す〕で示される感光性化
合物を用いたレジスト。(5) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [X and X' are each independently a hydrogen atom, -SO_2Cl,
-SO_3H, -SO_3CH_3 (however, -S
O_2Cl includes its quaternary salts, -SO_3H includes its ammonium salts, salts of organic bases and quaternary salts),
A resist using a photosensitive compound represented by m and n each independently representing an integer.
等があります▼ または▲数式、化学式、表等があります▼を表し、夫々
のＸ及びＸ′ は独立で水素原子、−ＳＯ＿２Ｃｌ、−ＳＯ＿３Ｈ、−
ＳＯ＿３ＣＨ＿３を表し（但し、−ＳＯ＿２Ｃｌはその
第４級塩を含み、−ＳＯ＿３Ｈはそのアンモニウム塩、
有機塩基の塩及び第４級塩を含む）、Ｙは置換基を表し
、Ｚは有機基を表し、ｍ及びｍ′及びｍ′及びｎ及びｎ
′及びｎ″は夫々独立で整数を表す〕で示される感光性
化合物を用いたレジスト。(6) General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [A, A' and A'' are each independent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. etc. Represents ▼, where each X and X' are independently hydrogen atoms, -SO_2Cl, -SO_3H, -
represents SO_3CH_3 (-SO_2Cl includes its quaternary salt, -SO_3H represents its ammonium salt,
(including salts of organic bases and quaternary salts), Y represents a substituent, Z represents an organic group, m and m' and m' and n and n
' and n'' are each independent and represent an integer] A resist using a photosensitive compound.
等があります▼又はベンゼン環又は置換基を含むベンゼ
ン環又はナフタレン環又は▲数式、化学式、表等があり
ます▼ である特許請求の範囲第６項に記載の感光性化合物を用
いたレジスト。(7) In general formula (IV), a patent claim in which Z is ▲There is a mathematical formula, chemical formula, table, etc.▼ or a benzene ring or a benzene ring or naphthalene ring containing a substituent, or ▲There is a mathematical formula, chemical formula, table, etc.▼ A resist using the photosensitive compound according to item 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63012937A JP2615742B2 (en) | 1988-01-22 | 1988-01-22 | Resist using photosensitive compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63012937A JP2615742B2 (en) | 1988-01-22 | 1988-01-22 | Resist using photosensitive compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01188852A true JPH01188852A (en) | 1989-07-28 |
| JP2615742B2 JP2615742B2 (en) | 1997-06-04 |
Family
ID=11819196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63012937A Expired - Fee Related JP2615742B2 (en) | 1988-01-22 | 1988-01-22 | Resist using photosensitive compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2615742B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01230033A (en) * | 1988-03-10 | 1989-09-13 | Matsushita Electric Ind Co Ltd | Resist formed by using photosensitive compound |
| JPH0355549A (en) * | 1989-07-25 | 1991-03-11 | Matsushita Electric Ind Co Ltd | Novel photosensitive compound |
| EP0456073A2 (en) * | 1990-05-08 | 1991-11-13 | Hoechst Aktiengesellschaft | Multifunctional compounds having alpha-diazo-beta-ketoester units and sulfonic acid ester units and process for their preparation. |
| US5256517A (en) * | 1990-05-08 | 1993-10-26 | Hoechst Aktiengesellschaft | Positive-working radiation-sensitive mixture and recording material for exposure to UV radiation containing polyfunctional compound having α-β-keto ester units and sulfonate units |
| US5350660A (en) * | 1990-01-30 | 1994-09-27 | Wako Pure Chemical Industries, Ltd. | Chemical amplified resist material containing photosensitive compound capable of generating an acid and specific polystyrene copolymer having functional groups that become alkali-soluble under an acid atmosphere |
| US5468589A (en) * | 1991-06-18 | 1995-11-21 | Wako Pure Chemical Industries, Ltd. | Resist material and pattern formation process |
| EP0704762A1 (en) | 1994-09-02 | 1996-04-03 | Wako Pure Chemical Industries Ltd | Resist material and pattern formation |
| EP0780732A2 (en) | 1995-12-21 | 1997-06-25 | Wako Pure Chemical Industries Ltd | Polymer composition and resist material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01154048A (en) * | 1987-12-10 | 1989-06-16 | Toshiba Corp | Photosensitive composition |
| JPH01154047A (en) * | 1987-12-10 | 1989-06-16 | Toshiba Corp | Photosensitive composition |
| JPH02865A (en) * | 1987-12-04 | 1990-01-05 | Matsushita Electric Ind Co Ltd | Photosensitive material and pattern forming method by using said material |
-
1988
- 1988-01-22 JP JP63012937A patent/JP2615742B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02865A (en) * | 1987-12-04 | 1990-01-05 | Matsushita Electric Ind Co Ltd | Photosensitive material and pattern forming method by using said material |
| JPH01154048A (en) * | 1987-12-10 | 1989-06-16 | Toshiba Corp | Photosensitive composition |
| JPH01154047A (en) * | 1987-12-10 | 1989-06-16 | Toshiba Corp | Photosensitive composition |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01230033A (en) * | 1988-03-10 | 1989-09-13 | Matsushita Electric Ind Co Ltd | Resist formed by using photosensitive compound |
| JPH0355549A (en) * | 1989-07-25 | 1991-03-11 | Matsushita Electric Ind Co Ltd | Novel photosensitive compound |
| US5350660A (en) * | 1990-01-30 | 1994-09-27 | Wako Pure Chemical Industries, Ltd. | Chemical amplified resist material containing photosensitive compound capable of generating an acid and specific polystyrene copolymer having functional groups that become alkali-soluble under an acid atmosphere |
| EP0456073A2 (en) * | 1990-05-08 | 1991-11-13 | Hoechst Aktiengesellschaft | Multifunctional compounds having alpha-diazo-beta-ketoester units and sulfonic acid ester units and process for their preparation. |
| US5191069A (en) * | 1990-05-08 | 1993-03-02 | Hoechst Aktiengesellschaft | Polyfunctional compounds containing α-diazo-β-keto ester units and sulfonate units |
| US5256517A (en) * | 1990-05-08 | 1993-10-26 | Hoechst Aktiengesellschaft | Positive-working radiation-sensitive mixture and recording material for exposure to UV radiation containing polyfunctional compound having α-β-keto ester units and sulfonate units |
| US5468589A (en) * | 1991-06-18 | 1995-11-21 | Wako Pure Chemical Industries, Ltd. | Resist material and pattern formation process |
| US5670299A (en) * | 1991-06-18 | 1997-09-23 | Wako Pure Chemical Industries, Ltd. | Pattern formation process |
| EP0704762A1 (en) | 1994-09-02 | 1996-04-03 | Wako Pure Chemical Industries Ltd | Resist material and pattern formation |
| EP0780732A2 (en) | 1995-12-21 | 1997-06-25 | Wako Pure Chemical Industries Ltd | Polymer composition and resist material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2615742B2 (en) | 1997-06-04 |
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