JPH0584514B2 - - Google Patents
Info
- Publication number
- JPH0584514B2 JPH0584514B2 JP60099127A JP9912785A JPH0584514B2 JP H0584514 B2 JPH0584514 B2 JP H0584514B2 JP 60099127 A JP60099127 A JP 60099127A JP 9912785 A JP9912785 A JP 9912785A JP H0584514 B2 JPH0584514 B2 JP H0584514B2
- Authority
- JP
- Japan
- Prior art keywords
- energy
- sensitive
- present
- sensitivity
- resin
- 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 - Fee Related
Links
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- -1 quinone diazide compound Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
〔産業上の利用分野〕
本発明は半導体素子の製造プロセス等に用いら
れるエネルギー感応性樹脂液、特に電子線、Ｘ
線、イオンビーム等の高エネルギー線による露光
に用いるエネルギー感応性樹脂、いわゆるレジス
トに関する。
〔従来の技術〕
現在、電子線、Ｘ線、イオンビーム等の高エネ
ルギー線による露光に用いるボジ型レジストとし
ては、ノボラツク樹脂を本体としエネルギー感応
基としてナフトキノンジアジドやポリメチルペン
テンスルフオンを添加したものが、感度及び製造
プロセス性の点で優れ、よく用いられてい。
例えば、半導体素子製造の場合、レジスト材料
を塗布したあと、前記エネルギー線を選択的に照
射し、所望の場所のエネルギー感応基を分解、そ
の部分の現像液に対する溶解度を変化し、不要部
分を選択的に除去して、所望のレジストパターン
を形成する。その後、このレジストパターンを用
いて、下地基板の所望加工を行う。
〔従来の技術の問題点〕
従来、電子線に代表される高エネルギー線に対
するボジ型感応材としてはクレゾール−ホルムア
ルデヒド系のノボラツク樹脂とキノンジアジド化
合物あるいは２−メチルペンテン−１−スルフオ
ンの混合物を用いてきた。特に後者はエム・ジエ
ー・ボーデン（M.J.Bowden）等がジヤーナル・
オブ・エレクトロケミカル・ソサエテイー
（Journal of Electro−chemical Society）の第
128巻、第２号のページ1304から1313で1981年６
月に述べているように前者の感度20μC／cm2に対
して5μC／cm2と感度に優れており、日立化成社の
レイキヤスト−5000のように、多用されている。
しかしながら２−メチルペンテン−１−スルフ
オンの感応機構に関するジツピング機構がエネル
ギー線照射時の雰囲気による影響を受けやすく、
後者に比して微細パターン部分に、しばしば残渣
として残存するという問題があつた。
〔発明の目的〕
本発明は、上記の問題を解決するためになされ
たものであり、高エネルギー線を用いるのに有利
なエネルギー感応性樹脂を提供するものである。
〔発明の構成〕
本発明のエネルギー感応性脂は、アルカリ可溶
である樹脂とニトロセルロースの混合物よりな
り、高エネルギー線による露光に用いられること
を特徴とする。
〔構成の詳細な説明〕
半導体素子等の作製のためのリソグラフイー技
術において、高エネルギー線を用いることは、高
解像度を得る上で非常に有効な事である。その実
用化において、高感度で耐ドライエツチング性の
高い、エネルギー感応性樹脂液、いわゆるレジス
トの開発は欠く事のできない条件である。
一方、レジストの耐ドライエツチング性が増加
すると、微小な残渣でも、エツチング加工工程に
影響を与えることになる。
本発明者は鋭意研究を進めた結果、エネルギー
感応基としてニトロセルロース系化合物を用いる
と、分解生成物がCO2，N2等のガス状であるた
め、残渣分が少く、かつ感度及び耐ドライエツチ
ング性の要求も満足できる事がわかつた。
なお、ニトロセルロースとしては、硝化度５〜
15％のものを用い、調整には、水とアルコールが
１：３程度の溶媒を用いるのが安全性が高く、都
合がよい。また、通常の回転塗布後、70℃で10分
程度乾燥後使用し、電子線照射条件しては、10〜
50KV、照射量10-4〜10-5クローン／cm2が望まし
い。
実施例 １
オルト（ターシヤルブチル）フエノール5g、
オルトクレゾール4gおよび35％ホルムアルデヒ
ド水溶液5.8gをフラスコに入れ、35％塩酸水溶液
を触媒として0.8g加えて、120℃で１時間反応さ
せた。その後、反応物を水で再沈殿させて5gの
白色固体を得た。得られたオルト（ターシヤルブ
チル）フエノール−オルトクレゾール−ホルムア
ルヒデヒドより成るノボラツク樹脂はNMRより
構造を確認した。
NMR（核磁気共鳴スペクトル）（CD・Cl3中）
δ（ppm）：1.33 （−Ｃ（CH3）3）
2.13 （−CH3）
3.80 （−CH2−）
6.67〜7.0
[Industrial Field of Application] The present invention relates to an energy-sensitive resin liquid used in the manufacturing process of semiconductor devices, especially an energy-sensitive resin liquid used in the manufacturing process of semiconductor devices, etc.
The present invention relates to energy-sensitive resins, so-called resists, used for exposure with high-energy rays such as ion beams and ion beams. [Prior art] At present, positive resists used for exposure with high-energy beams such as electron beams, X-rays, and ion beams are made of novolac resin as a main body and doped with naphthoquinone diazide or polymethylpentenesulfon as an energy-sensitive group. It is widely used due to its excellent sensitivity and manufacturing process. For example, in the case of semiconductor device manufacturing, after applying a resist material, the energy rays are selectively irradiated to decompose the energy-sensitive groups at desired locations, change the solubility of the regions in the developing solution, and select unnecessary regions. and then remove the resist pattern to form a desired resist pattern. Thereafter, using this resist pattern, desired processing of the base substrate is performed. [Problems with conventional technology] Conventionally, a mixture of a cresol-formaldehyde-based novolak resin and a quinone diazide compound or 2-methylpentene-1-sulfon has been used as a positive-type sensitive material for high-energy rays such as electron beams. Ta. Especially the latter, M.J.Bowden etc.
Journal of Electrochemical Society
Volume 128, Issue 2, Pages 1304-1313 June 1981
As mentioned in the previous article, it has a superior sensitivity of 5 μC/cm 2 compared to the former's sensitivity of 20 μC/cm 2 , and is widely used, such as Hitachi Chemical's Raycast-5000. However, the zipping mechanism related to the sensitivity mechanism of 2-methylpentene-1-sulfon is easily affected by the atmosphere during energy ray irradiation.
Compared to the latter, there was a problem in that it often remained as a residue in fine pattern parts. [Object of the Invention] The present invention was made to solve the above problems, and provides an energy-sensitive resin that is advantageous for use with high-energy rays. [Configuration of the Invention] The energy-sensitive fat of the present invention is characterized in that it is made of a mixture of an alkali-soluble resin and nitrocellulose, and is used for exposure to high-energy rays. [Detailed Description of Configuration] In lithography technology for manufacturing semiconductor devices, etc., the use of high-energy rays is very effective in obtaining high resolution. For its practical application, the development of energy-sensitive resin liquids, so-called resists, which are highly sensitive and highly resistant to dry etching are indispensable conditions. On the other hand, as the dry etching resistance of the resist increases, even minute residues will affect the etching process. As a result of intensive research, the present inventor has found that when a nitrocellulose compound is used as an energy-sensitive group, the decomposition products are gaseous such as CO 2 and N 2 , so the residue content is small and the sensitivity and dry resistance are improved. It was found that the requirements for etching properties were also satisfied. In addition, as nitrocellulose, the nitrification degree is 5~
It is safe and convenient to use a solvent containing 15% water and alcohol at a ratio of about 1:3. In addition, after normal spin coating, use after drying at 70℃ for about 10 minutes, and under electron beam irradiation conditions,
50KV and irradiation dose of 10 -4 to 10 -5 clones/cm 2 are desirable. Example 1 Ortho (tertiary butyl) phenol 5g,
4 g of orthocresol and 5.8 g of a 35% aqueous formaldehyde solution were placed in a flask, 0.8 g of a 35% aqueous hydrochloric acid solution was added as a catalyst, and the mixture was reacted at 120° C. for 1 hour. Thereafter, the reaction product was reprecipitated with water to obtain 5 g of a white solid. The structure of the obtained novolak resin consisting of ortho(tert-butyl)phenol-orthocresol-formalhydehyde was confirmed by NMR. NMR (Nuclear Magnetic Resonance Spectrum) (in CD/ Cl3 ) δ (ppm): 1.33 (-C( CH3 ) 3 ) 2.13 ( -CH3 ) 3.80 ( -CH2- ) 6.67-7.0
以上、述べてきたように、本発明のエネルギー
感応性樹脂は現像後の残渣がきわめて少く、かつ
感度も高いことがわかつた。従つて本発明である
ポジレジスト材料及びこれを使用するパターン形
成方法は半導体素子等の製造プロセスに有用なも
のである。
As described above, it has been found that the energy-sensitive resin of the present invention leaves very little residue after development and has high sensitivity. Therefore, the positive resist material of the present invention and the pattern forming method using the same are useful in the manufacturing process of semiconductor devices and the like.
第１図は、本発明のエネルギー感応性樹脂の感
応特性を示す図。
FIG. 1 is a diagram showing the sensitivity characteristics of the energy-sensitive resin of the present invention.
Claims (1)
の混合物よりなり、高エネルギー線による露光に
用いられることを特徴とするエネルギー感応性樹
脂。1. An energy-sensitive resin comprising a mixture of an alkali-soluble resin and nitrocellulose, and characterized in that it is used for exposure to high-energy rays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9912785A JPS61256348A (en) | 1985-05-10 | 1985-05-10 | Energy sensitive resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9912785A JPS61256348A (en) | 1985-05-10 | 1985-05-10 | Energy sensitive resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61256348A JPS61256348A (en) | 1986-11-13 |
| JPH0584514B2 true JPH0584514B2 (en) | 1993-12-02 |
Family
ID=14239088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9912785A Granted JPS61256348A (en) | 1985-05-10 | 1985-05-10 | Energy sensitive resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61256348A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5184640A (en) * | 1974-12-20 | 1976-07-24 | Ibm |
-
1985
- 1985-05-10 JP JP9912785A patent/JPS61256348A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5184640A (en) * | 1974-12-20 | 1976-07-24 | Ibm |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61256348A (en) | 1986-11-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |