JPS6360376B2 - - Google Patents
Info
- Publication number
- JPS6360376B2 JPS6360376B2 JP16557579A JP16557579A JPS6360376B2 JP S6360376 B2 JPS6360376 B2 JP S6360376B2 JP 16557579 A JP16557579 A JP 16557579A JP 16557579 A JP16557579 A JP 16557579A JP S6360376 B2 JPS6360376 B2 JP S6360376B2
- Authority
- JP
- Japan
- Prior art keywords
- radiation
- copolymer
- acetate
- developer
- film
- 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.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 9
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 9
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229940117955 isoamyl acetate Drugs 0.000 description 9
- 238000010894 electron beam technology Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- POXAGMZRZMSXIP-UHFFFAOYSA-N CC(C)CCC(O)=O.CC(C)COC(C)=O Chemical compound CC(C)CCC(O)=O.CC(C)COC(C)=O POXAGMZRZMSXIP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004528 spin coating Methods 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
【発明の詳細な説明】
本発明は、ポジ型放射線感応性材料の改良され
た現像液に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improved developers of positive-working radiation-sensitive materials.
半導体素子の製造などに際し、所望のパターン
を得るために感光性組成物の塗膜にマスクを介し
て露光する方法が行なわれている。しかしながら
この方法は、光の回折現像などの影響により微細
なパターンを描くことができない。そのため電子
線、Ｘ線などの放射線感応性材料を用い、放射線
によつて1μｍ又はそれ以下の線幅のパターンを
描くことが行なわれている。このような放射線感
応性材料のうちポジ型、すなわち塗膜に放射線を
照射したとき照射をうけた部分が可溶性になるも
のは、放射線に対する感度が低いものが大部分で
ある。 2. Description of the Related Art In manufacturing semiconductor devices, a method is used in which a coating film of a photosensitive composition is exposed to light through a mask in order to obtain a desired pattern. However, this method cannot draw fine patterns due to the effects of light diffraction and development. Therefore, radiation-sensitive materials such as electron beams and X-rays are used to draw patterns with line widths of 1 μm or less using radiation. Among such radiation-sensitive materials, most of the positive-type materials, that is, those in which the irradiated portion becomes soluble when the coating film is irradiated with radiation, have low sensitivity to radiation.
本発明者らの一部のものは、すでに特公昭
5164108として、メチルメタクリレート・アクリ
ロニトリル共重合体（以下MMA・AN共重合体
と略す）、メチルメタクリレート・メタアクリロ
ニトリル共重合（以下MMA・MAN共重合体と
略す）などのポジ型放射線感応性材料を開示し
た。これらの材料は、従来公知のポジ型放射線感
応性材料であるポリメチルメタクリレートに比較
し、電子線に対して約２〜10倍も高感度である。 Some of the inventors have already
5164108 discloses positive radiation-sensitive materials such as methyl methacrylate/acrylonitrile copolymer (hereinafter abbreviated as MMA/AN copolymer) and methyl methacrylate/methacrylonitrile copolymer (hereinafter abbreviated as MMA/MAN copolymer). did. These materials are about 2 to 10 times more sensitive to electron beams than polymethyl methacrylate, which is a conventionally known positive radiation-sensitive material.
これらの材料の現像液としては、酢酸イソアミ
ル若しくは酢酸イソアミル・酢酸ｎ−アミル１：
１混合液などが用いられているが、このような現
像液では15〜20分程度の現像時間を要し、スプレ
イ現像を行なうとき多量の現像液を必要とするこ
とが明らかとなつた。またその他の現像液も上記
材料を膨潤させることなく、速やかに現像できる
現像液は知られていない。従つて作業性が好まし
くなかつた。 As a developer for these materials, isoamyl acetate or isoamyl acetate/n-amyl acetate 1:
However, it has become clear that such a developer requires a development time of about 15 to 20 minutes, and that a large amount of developer is required when spray development is performed. Furthermore, no other developer is known that can rapidly develop the above-mentioned material without causing it to swell. Therefore, workability was not favorable.
本発明は、上記問題を解決し、上記材料を膨潤
させることなく、速やかに現像し得る、作業性に
優れた現像液を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems and provide a developing solution with excellent workability, which can rapidly develop the above-mentioned materials without causing them to swell.
本発明の現像液は、アクリロニトリル、メタア
クリロニトリルの内の少なくとも一種のメチルメ
タクリレートとの共重合体よりなるポジ型放射線
感応性材料に用いられるもので、酢酸イソブチル
若しくはこれに上記材料の貧溶媒を加えた液より
なる。 The developer of the present invention is used for a positive radiation-sensitive material made of a copolymer of at least one of acrylonitrile and methacrylonitrile with methyl methacrylate, and is used in a positive radiation-sensitive material made of a copolymer of at least one of acrylonitrile and methacrylonitrile with methyl methacrylate. It consists of liquid.
このような貧溶媒としては、酢酸イソアミル、
酢酸ｎ−アミルなどがある。 Such poor solvents include isoamyl acetate,
Examples include n-amyl acetate.
例えばMMA・AN共重合体の未照射の塗膜の
これらの溶媒による溶解速度を示すと、単独で現
像液として用いられる酢酸イソブチルに対しては
137Å／分であるのに比較し、酢酸イソアミルに
対しては５Å／分、酢酸ｎ−アミルに対しては37
Å／分である。この傾向はMMA・MAN共重合
体もほぼ同じ傾向にある。 For example, the dissolution rate of an unirradiated coating film of MMA/AN copolymer with these solvents is as follows:
137 Å/min compared to 5 Å/min for isoamyl acetate and 37 Å/min for n-amyl acetate.
Å/min. This tendency is almost the same for MMA/MAN copolymers.
なお、酢酸イソブチルよりも早い溶解速度が得
られる溶媒を使用すると未照射部の膜べりが起こ
り、切れの良い図形を得ることは困難である。 Note that if a solvent with a faster dissolution rate than isobutyl acetate is used, film peeling will occur in the unirradiated area, making it difficult to obtain sharp patterns.
現像液として酢酸イソブチルを単独で用いる場
合もその溶解速度がやや早いため、未照射部の膜
べりは多少起り得る。それ故この溶媒を単独で用
いるよりも前記貧溶媒と混合して用いる方が好ま
しい。さらに膜べりをほとんどなくすために前記
貧溶媒を20％（容量）以上混合して用いることが
より好ましい。第１図は、酢酸イソブチル（iso
BA）と酢酸イソアミル（iso AA）の混合溶媒
に対する未照射MMA・AN共重合体の溶解速度
を示したものである。図にみられるように酢酸イ
ソブチルが50％未満の混合溶媒では現像時間の短
縮はあまり期待できない。従つて酢酸イソブチル
が50％以上含まれる混合溶媒であることが好まし
い。 Even when isobutyl acetate is used alone as a developer, its dissolution rate is rather fast, so some film loss may occur in unirradiated areas. Therefore, it is preferable to use this solvent in combination with the poor solvent rather than using it alone. Further, it is more preferable to use a mixture of 20% (by volume) or more of the poor solvent in order to almost eliminate membrane sagging. Figure 1 shows isobutyl acetate (isobutyl acetate).
This figure shows the dissolution rate of unirradiated MMA/AN copolymer in a mixed solvent of BA) and isoamyl acetate (iso AA). As shown in the figure, a mixed solvent containing less than 50% isobutyl acetate cannot be expected to shorten the development time much. Therefore, it is preferable to use a mixed solvent containing 50% or more of isobutyl acetate.
以上の如く前記のポジ型放射線感応性材料を基
板上に塗布しプレベークして塗膜とし、これに放
射線好ましくは電子線によつてパターンを描画
し、現像し、乾燥し、必要ならポストベークし、
さらに通常はエツチングしその後塗膜を除去する
という工程において、本発明の現像液を用いるこ
とは極めて優れた効果を得ることができる。 As described above, the above-mentioned positive radiation-sensitive material is applied onto a substrate and pre-baked to form a coating film, a pattern is drawn on this by radiation, preferably an electron beam, developed, dried and, if necessary, post-baked. ,
Furthermore, the use of the developing solution of the present invention in the process of etching and then removing the coating film can provide extremely excellent effects.
以下実施例によつて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
膜厚900nｍのクロム膜を蒸着したガラス板
（以下クロムブランク板という）にMMA・AN
共重合体（アクリロニトリル比率約11％）の溶液
を回転塗布し、170℃で30分間熱処理する。この
塗膜を有するブランク板を電子線描画装置に入
れ、電子線を塗膜面に照射し、電子線を偏向、オ
ン・オフすることにより所定のパターンを描く。
このときの照射条件は、10KVの加速電圧で、３
マイクロクーロン／cm2の照射量である。Example 1 MMA/AN was applied to a glass plate (hereinafter referred to as a chrome blank plate) on which a chromium film with a thickness of 900 nm was deposited.
A solution of copolymer (acrylonitrile ratio of about 11%) is applied by spin coating and heat treated at 170°C for 30 minutes. The blank plate having the coating film is placed in an electron beam drawing device, and the coating surface is irradiated with an electron beam, and a predetermined pattern is drawn by deflecting the electron beam and turning it on and off.
The irradiation conditions at this time were an acceleration voltage of 10KV and 3
The irradiation dose is microcoulomb/ cm2 .
電子線照射後、装置からブランク板をとり出
し、約500rpmmで回転させながらスプレイ現像
機を用い、酢酸イソブチル・酢酸イソアミル１：
１の混合溶媒を８分間スプレイし、つぎに窒素を
吹きつけながら約1000rpmで回転して乾燥する。
これで0.5μｍの線幅の像を得ることができる。 After electron beam irradiation, take out the blank plate from the apparatus and use a spray developer while rotating it at about 500 rpm to develop isobutyl acetate/isoamyl acetate 1:
Spray the mixed solvent of step 1 for 8 minutes, then dry by rotating at about 1000 rpm while blowing nitrogen.
This allows an image with a line width of 0.5 μm to be obtained.
このあとさらに110℃で30分ポストベークし、
硝酸セリウムアンモニウム水溶液で露出したクロ
ム部分をエツチングし、最後に塗膜を除去してガ
ラス板上にクロムのパターンを得る。 After this, post-bake for another 30 minutes at 110℃,
The exposed chromium parts are etched with an aqueous solution of cerium ammonium nitrate, and finally the coating is removed to obtain a chromium pattern on the glass plate.
実施例 ２
現像液を酢酸イソブチル・酢酸イソアミル２：
１として同様の実験を行なつた。この場合も同様
の結果を得ることができた。Example 2 The developer is isobutyl acetate/isoamyl acetate 2:
A similar experiment was conducted as Example 1. Similar results were obtained in this case as well.
実施例 ３
表面にSiO2膜を形成したシリコーンウエーハ
上にさらにヘキサメチレンジシラザンの蒸気を吸
着させたのち180℃でベークする。この基板上に
実施例１と同様の共重合体溶液を回転塗布し、約
380nｍの膜とし、プレベークする。図射条件を
加速電圧20kV、照射量12マイクロクーロロン／
cm2として実施例１と同様に塗膜面に電子線を照射
する。塗膜を酢酸イソブチル：酢酸イソアミルで
１分間スプレイしてリンスし、回転乾燥する。Example 3 Hexamethylene disilazane vapor is further adsorbed onto a silicone wafer having a SiO 2 film formed on its surface, and then baked at 180°C. A copolymer solution similar to that in Example 1 was spin-coated onto this substrate, and approximately
A film of 380 nm is formed and prebaked. The illustration conditions were: acceleration voltage 20kV, irradiation amount 12 microcoulombs/
cm 2 and irradiate the coating surface with an electron beam in the same manner as in Example 1. The coating is rinsed by spraying with isobutyl acetate:isoamyl acetate for 1 minute and spun dry.
ポストベークしたのち、プラズマアツシヤーで
酸素0.5Torr ふん囲気中で放電させ、スカム除
去し、ふつ酸とふつ化アンモニウム溶液でエツチ
ングする。水洗、乾燥、塗膜を除去し、シリコー
ンウエーハ上にSiO2膜のパターンを得る。 After post-baking, the film is discharged in an atmosphere of 0.5 Torr of oxygen using a plasma assher to remove scum, and etched with hydrofluoric acid and ammonium fluoride solution. Wash with water, dry, and remove the coating film to obtain a pattern of SiO 2 film on the silicone wafer.
実施例 ４
実施例１と同様にクロムブランク上に約360n
ｍの塗膜を形成し、照射条件を加速電圧20kV、
照射量８マイクロクーロン／cm2としてパターンを
描く。Example 4 Approximately 360n on a chrome blank as in Example 1.
A coating film of m was formed, and the irradiation conditions were an accelerating voltage of 20 kV,
A pattern is drawn with a radiation dose of 8 microcoulombs/cm 2 .
つぎに酢酸イソブチルで７分間スプレ現像し、
酢酸イソアミルで１分間スプレしてリンスし、窒
素を吹きつけながら回転乾燥する。この場合、未
照射部に約100nｍのべりがあるが0.5μｍの線幅の
パターンが得られる。 Next, spray develop with isobutyl acetate for 7 minutes.
Rinse by spraying with isoamyl acetate for 1 minute and spin dry with nitrogen. In this case, a pattern with a line width of 0.5 μm is obtained although there is a deviation of about 100 nm in the unirradiated area.
以後実施例と同様に処理し、クロムパターンを
得る。 Thereafter, the same treatment as in the example is carried out to obtain a chrome pattern.
第１図は、本発明の効果を説明するための図で
ある。
FIG. 1 is a diagram for explaining the effects of the present invention.
Claims (1)
料の貧溶媒を加えた液よりなる、アクリロニトリ
ル、メタアクリロニトリルの内の少なくとも一種
とメチルメタクリレートとの共重合体よりなるポ
ジ型放射線感応性材料の現像液。1. A developer for a positive-working radiation-sensitive material made of a copolymer of at least one of acrylonitrile and methacrylonitrile and methyl methacrylate, which is made of isobutyl acetate or a solution obtained by adding a poor solvent for the material to be developed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16557579A JPS5688135A (en) | 1979-12-21 | 1979-12-21 | Developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16557579A JPS5688135A (en) | 1979-12-21 | 1979-12-21 | Developer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5688135A JPS5688135A (en) | 1981-07-17 |
| JPS6360376B2 true JPS6360376B2 (en) | 1988-11-24 |
Family
ID=15814954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16557579A Granted JPS5688135A (en) | 1979-12-21 | 1979-12-21 | Developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5688135A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6139041A (en) * | 1984-07-31 | 1986-02-25 | Tokyo Ohka Kogyo Co Ltd | Developing solution of positive type resist |
| JPS62175739A (en) * | 1986-01-30 | 1987-08-01 | Toshiba Corp | Pattern forming method |
| JPH0328851A (en) * | 1988-05-24 | 1991-02-07 | Toppan Printing Co Ltd | Method for forming electron beam resist pattern |
-
1979
- 1979-12-21 JP JP16557579A patent/JPS5688135A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5688135A (en) | 1981-07-17 |
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