JPS6097352A - Developer for negative type electron beam resist - Google Patents
Developer for negative type electron beam resistInfo
- Publication number
- JPS6097352A JPS6097352A JP20494183A JP20494183A JPS6097352A JP S6097352 A JPS6097352 A JP S6097352A JP 20494183 A JP20494183 A JP 20494183A JP 20494183 A JP20494183 A JP 20494183A JP S6097352 A JPS6097352 A JP S6097352A
- Authority
- JP
- Japan
- Prior art keywords
- electron beam
- developer
- beam resist
- negative type
- type electron
- 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
Links
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 9
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- -1 methyl ethyl ketone Chemical class 0.000 abstract description 2
- 229920000582 polyisocyanurate Polymers 0.000 abstract 3
- 239000011495 polyisocyanurate Substances 0.000 abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000004644 polycyanurate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WWECJGLXBSQKRF-UHFFFAOYSA-N n,n-dimethylformamide;methanol Chemical compound OC.CN(C)C=O WWECJGLXBSQKRF-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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)
Abstract
Description
【発明の詳細な説明】
本発明は、ネガ型電子線しノスト用現像液忙関する。さ
らに詳しく言えば本発明は、一種もしくは二種以上の低
級ケトンを成分として用いることを特徴とする、式、
ＣＨ３
で表わされるジフェノール酸と式、
。ｔ−！”＼。−６え
ｌ Ｉｔ ｌ＋）
〜。／゛
Ｎ（ＣＨ２ＣＨ＝ＣＨ２）２
で表わされる２−ジアリルアミノ−４，６−ジクロロ−
θ−トリアジンとを、Ｊ？り縮合して得られるポリ／ア
メレート系ネガ型電子しレソスト用現像故に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer solution for negative type electron beam nozzle. More specifically, the present invention relates to a diphenolic acid represented by the formula CH3, characterized in that one or more lower ketones are used as a component; T-! 2-diallylamino-4,6-dichloro- represented by ``\.-6el It l+) ~./゛N(CH2CH=CH2)2
θ-triazine and J? The present invention relates to a poly/americate-based negative type electronic resistor development process obtained by condensation.
集積回路がＬＳＩから超ＬＳＩへと進展してゆく中で、
微細加工技術も、従来のフォトリングラフイーからサブ
ミクロン加工がｂ」能な′由、子練りソゲラフイーへ゛
と移行しつつある。まだ、電子線リソグラフィーに使用
される電子線レジストにおいても、高感度・高解像度な
ものが要求されている。As integrated circuits progress from LSI to VLSI,
Microfabrication technology is also transitioning from conventional photolithography to microfabrication technology due to its ability to perform submicron processing. High sensitivity and high resolution are still required for electron beam resists used in electron beam lithography.
従来使用されてきた電子線感応性樹脂については、ポリ
メチルメタクリレート（ＰＭＭＡ ）に代表されるポジ
型電子線レジストの場合は、低感度であるが、高解像度
であることが報告され、一方、ネガ型電子線レジストの
場合はホＩＪグリシジルメタクリレート（ＰＧＭＡ）に
代表される様に高感度であるが、ポジ型に比べ解像度が
劣ることが報告されている。この様にネガ型電子線レジ
ストが、ポジ型電子線レジストに比べて低解像度となる
原因としては、ネガ型電子線レジストの現像時における
現像液への膨潤の影響があげられる。そして現像時の膨
潤が激しい場合には、ブリッジの発生、パターンの蛇行
などをもたらし、結果的に低解像度となる。従って、感
度の面でポジ型電子線レジストよりも有利なネガ型電子
線レジストにおいて解像度を向上させるためには、現像
時における膨潤をできるだけ抑制する現像液を選択する
事が要求されている。Regarding electron beam-sensitive resins that have been used conventionally, it has been reported that positive electron beam resists such as polymethyl methacrylate (PMMA) have low sensitivity but high resolution; In the case of type electron beam resists, as typified by photo-IJ glycidyl methacrylate (PGMA), the sensitivity is high, but it has been reported that the resolution is inferior to positive type. The reason why the resolution of the negative electron beam resist is lower than that of the positive electron beam resist is due to the influence of swelling in the developer during development of the negative electron beam resist. If the swelling during development is severe, bridges may occur and the pattern may meander, resulting in low resolution. Therefore, in order to improve the resolution of negative electron beam resists, which are more advantageous than positive electron beam resists in terms of sensitivity, it is required to select a developer that suppresses swelling during development as much as possible.
本発明者らは、高感度であり、まだ優れた耐プラズマド
ライエツチング特性を示す前記式（＋１のジフェノール
酸と式ｆｎ）で表わされる２−ジアリルアミノ−４，６
−’；クロロー８−）リアジンとをポリ縮合して得られ
るポリシアヌレート系ネガ型電子線レジストの現像液と
解像度の関係を種々の溶剤について検討した結果、一種
もしくは二種以上の低級ケトンを成分とした現像液を使
用すると高解像度が得られることを見出した。本発明は
かかる知見にもとすくものである。The present inventors have discovered that 2-diallylamino-4,6 expressed by the above formula (+1 diphenolic acid and formula fn) exhibits high sensitivity and yet excellent plasma dry etching resistance.
-'; As a result of examining the relationship between the developer and resolution of a polycyanurate-based negative electron beam resist obtained by polycondensation with chloro(8-) riazine using various solvents, it was found that one or more lower ketones were used. It has been found that high resolution can be obtained by using a developer containing the above components. The present invention is based on this knowledge.
従って、本発明は、前記式（１）で表わされるジフェノ
ール酸と式（１１）で表わされる２−ジアリルアミノ−
４，６−’；クロロー８−トリアジノとをポリ縮合して
得られるポリシアヌレート系ネガ型電子線レジストの現
像液として、一種もしくは二種以上の低級ケトンを成分
として用いることを特徴とするものである。Therefore, the present invention provides a diphenolic acid represented by the formula (1) and a 2-diallylamino-acid represented by the formula (11).
4,6-'; A developer for a polycyanurate-based negative electron beam resist obtained by polycondensation with chloro-8-triazino, characterized in that one or more lower ketones are used as a component. It is.
本発明に係る現像液に使用される低級ケトンの例として
は、アセトン、メチルエチルケトン、メチルイソブチル
ケトン、ジエチルケトン、メチル−ｎ−プロピルケトン
、メチル−ｎ−ブチルケトンなどをあげることができ、
これらの低級ケトンは、そのままあるいは、種々の溶剤
と混合して使用することができる。混合して用いられる
溶剤としては、ジメチルホルムアミドメタノール、酢酸
−ｎ−ブチル、メチルセロンルブ、シクロヘキサノン、
ｍ−クレゾール、テトラヒドロフランなどがあり、これ
らを混合する場合の割合としては一般には、次の割合を
用いると好ましい結果を与える。Examples of lower ketones used in the developer according to the present invention include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, etc.
These lower ketones can be used as they are or mixed with various solvents. Solvents used in combination include dimethylformamide methanol, n-butyl acetate, methylceronelube, cyclohexanone,
Examples include m-cresol and tetrahydrofuran, and when these are mixed, the following ratios generally give preferable results.
ジメチルホルムアミド ・・・・・ ５〜４０係メタノ
ール −＝・５ 〜６０ ’％
酢酸−ｎ−ブチル ・・・・・ ５〜８０チメチルセロ
ソルブ ・・−・・・ ５〜８０チシクロヘキサノン
・・・・・・ ５〜８０チｍ−クレゾール ・・・・・
・５〜６０チテトラヒド口フラン ・・・・・・ ５〜
４０チまた、二種以上の低級ケトンを混合して使用する
場合ではアセトンとメチルエチルケトンの組み合せが好
ましい結果を与える。Dimethylformamide: 5-40% Methanol -=5-60'% n-butyl acetate: 5-80% methyl cellosolve: 5-80% cyclohexanone
・・・・・・ 5-80 cm-cresol ・・・・・・
・5~60 titetrahydrofuran ・・・・・・5~
Furthermore, when a mixture of two or more lower ketones is used, a combination of acetone and methyl ethyl ketone gives preferable results.
なお、これらの混合使用における現像液の各成分の最適
混合比は、選択された各成分に応じて適宜、最適の割合
を定めればよい。The optimum mixing ratio of each component of the developer in these mixed uses may be determined as appropriate depending on each selected component.
本発明の現像液を使用する態様につき説明すると、前記
構造式（りで表わされるジフェノール酸と式（ＩＩ）で
表わされるトリアジンとをポリ縮合して得られるポリシ
アヌレートを適当な溶剤に溶解し、目的とする基板、例
えばＳｉやＳｉ０２上にスピンコーティング法により塗
布し、オーブン中でベーキングした後、電子線照射を行
なう。To explain the mode of using the developer of the present invention, polycyanurate obtained by polycondensation of diphenolic acid represented by the above structural formula (RI) and triazine represented by formula (II) is dissolved in an appropriate solvent. Then, it is applied onto a target substrate such as Si or Si02 by spin coating, baked in an oven, and then irradiated with an electron beam.
そして次に照射処理を了えた基板を本発明の現像液によ
り現像し、アセトン及び低級アルコールを主成分とした
リンス液でリンスを行なう。Then, the substrate that has undergone the irradiation treatment is developed with the developer of the present invention, and rinsed with a rinsing liquid containing acetone and lower alcohol as main components.
さらに現像した後に目的とする材料、例えばＳ】やＳｉ
０２をエツチングすることにより、所望する高精度微細
加工を行なうことができる。After further development, the desired material, such as S] or Si
By etching 02, desired high-precision microfabrication can be performed.
以下に本発明の現像液の実施例を掲げて本発明をさらに
詳細に説明するが、本発明は、これら実施例に限定され
るものではない。The present invention will be described in more detail below with reference to Examples of the developer of the present invention, but the present invention is not limited to these Examples.
実施例１
ジフェノール酸と２−ジアリルアミノ−４，６−ジクロ
ロ−〇−トリアジンとをポリ縮合して得られたポリシア
ヌレートをジメチルホルムアミドとシクロヘキサノンの
混合液に溶解して濃度１２ｗｔ％の溶液を調製した。次
にこの溶液をスピンコーティング法によりシリコンウェ
ハ上に０．８μｍの膜厚に塗布し、ｌｏＯ’Ｃのオーブ
ン中で１０分間ベーキングした後、加速電圧１５ ＫＶ
の電子線照射装置を用いて残膜率が約６０φとなる様な
照射量で、電子線照射した。照射後、アセトンを用いて
１分間デイツゾ現像を行ない、次に水／アセトン（体積
比１：１に混合したもの）を用いて（ト）秒間リンスを
行ない、得られた微細パターンを走査電子顕微鏡により
観察し、解像度の評価を行なったところ蛇行・ブリッジ
のないサブミクロンノミターンが得られた。Example 1 Polycyanurate obtained by polycondensation of diphenolic acid and 2-diallylamino-4,6-dichloro-〇-triazine was dissolved in a mixture of dimethylformamide and cyclohexanone to make a solution with a concentration of 12 wt%. was prepared. Next, this solution was applied to a film thickness of 0.8 μm on a silicon wafer by spin coating method, and after baking in a loO'C oven for 10 minutes, an acceleration voltage of 15 KV was applied.
Electron beam irradiation was performed using an electron beam irradiation device with an irradiation dose such that the residual film ratio was about 60φ. After irradiation, day-to-day development was performed using acetone for 1 minute, followed by rinsing for (t) seconds using water/acetone (mixed at a volume ratio of 1:1), and the resulting fine pattern was examined using a scanning electron microscope. When observed and evaluated for resolution, submicron nomiturns with no meandering or bridges were obtained.
以下に実施例２〜１９を表に掲げるが、実施例２以下は
実施例１において現像液として用いたアセトンを表に示
した組成の現像液に換えて、他は、実施例１と同様の操
作によったものである。Examples 2 to 19 are listed in the table below, but in Examples 2 and below, the acetone used as the developer in Example 1 was replaced with a developer having the composition shown in the table, and the rest was the same as in Example 1. This is due to manipulation.
Claims (1)
ｓ−トリアジノとをポリ縮合して得られる一すンアヌレ
ート系ネガ型電子線レノスト用の現像液であって、１種
もしくは２秒以上の低級ケトンを成分として用いること
を特徴とするネガ型電子線レジスト用現像液。[Scope of Claims] Diphenolic acid represented by the formula CH3 and 2-diallylamino-4,6-dichloro- represented by the formula N(CH2C,H=CH2)2
A negative-working electron beam developer obtained by polycondensation with s-triazino, which is characterized by using one type or a lower ketone of 2 seconds or more as a component. Developer for resist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20494183A JPS6097352A (en) | 1983-11-02 | 1983-11-02 | Developer for negative type electron beam resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20494183A JPS6097352A (en) | 1983-11-02 | 1983-11-02 | Developer for negative type electron beam resist |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6097352A true JPS6097352A (en) | 1985-05-31 |
Family
ID=16498877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20494183A Pending JPS6097352A (en) | 1983-11-02 | 1983-11-02 | Developer for negative type electron beam resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6097352A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03179453A (en) * | 1989-12-08 | 1991-08-05 | Oki Electric Ind Co Ltd | Pattern forming method |
| JPH08262738A (en) * | 1995-03-27 | 1996-10-11 | Agency Of Ind Science & Technol | Fine pattern forming method |
-
1983
- 1983-11-02 JP JP20494183A patent/JPS6097352A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03179453A (en) * | 1989-12-08 | 1991-08-05 | Oki Electric Ind Co Ltd | Pattern forming method |
| JPH08262738A (en) * | 1995-03-27 | 1996-10-11 | Agency Of Ind Science & Technol | Fine pattern forming method |
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