JPH0823697B2 - Positive electron beam resist - Google Patents
Positive electron beam resistInfo
- Publication number
- JPH0823697B2 JPH0823697B2 JP1087703A JP8770389A JPH0823697B2 JP H0823697 B2 JPH0823697 B2 JP H0823697B2 JP 1087703 A JP1087703 A JP 1087703A JP 8770389 A JP8770389 A JP 8770389A JP H0823697 B2 JPH0823697 B2 JP H0823697B2
- Authority
- JP
- Japan
- Prior art keywords
- electron beam
- resist
- cyclohexyl
- sensitivity
- beam resist
- 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 - Lifetime
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は高感度、高解像度のポジ型電子線レジストに
関するものである。更に詳しくは半導体工業におけるフ
ォトマスクの製造およびシリコンウェハーへの直接描画
による半導体の製造時における選択的エッチングや選択
的拡散のためのレジストの提供を目的とする。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a high-sensitivity, high-resolution positive electron beam resist. More specifically, it is an object of the present invention to provide a resist for selective etching or selective diffusion in manufacturing a photomask in the semiconductor industry and manufacturing a semiconductor by direct writing on a silicon wafer.
［従来技術とその問題点］ ネガ型レジストは高感度であるが、解像性が低い。こ
れに対して、ポジ型電子線レジストは解像性が高いため
にICの高集積化に伴い、ネガ型からポジ型に移行しつつ
ある。ポジ型電子線レジストの代表例としてポリメタク
リル酸メチル（PMMA）が知られているが、解像度は0.1
μｍと非常に高いが、感度が100μC/cm3と低いために電
子線描画装置のスループットが問題となり、感度を高め
るために数多くの研究がなされてきた。[Prior Art and its Problems] A negative resist has high sensitivity but low resolution. On the other hand, positive electron beam resists are shifting from a negative type to a positive type with high integration of ICs because of high resolution. Polymethyl methacrylate (PMMA) is known as a typical example of a positive-type electron beam resist.
Although it is extremely high at μm, the sensitivity of the electron beam lithography system becomes a problem because the sensitivity is low at 100 μC / cm 3, and many studies have been conducted to increase the sensitivity.
PMMAのα−メチル基をシアノ基に、エステル基のメチ
ル基をシクロヘキシル基に置換した２−シアノアクリル
酸シクロヘキシル重合体は、現像液にメチルセロソルブ
を用いると１μC/cm3と高感度であるが、現像時間は10
分以上かかり、スプレー現像に適さず、また現像時間が
長くなることにより、レジストパターン剥離が発生す
る。A cyclohexyl 2-cyanoacrylate polymer obtained by substituting the α-methyl group of PMMA with a cyano group and the methyl group of an ester group with a cyclohexyl group has a high sensitivity of 1 μC / cm 3 when methyl cellosolve is used as a developing solution. , Development time is 10
It takes more than a minute, is not suitable for spray development, and the development time becomes long, so that resist pattern peeling occurs.
［発明が解決しようとする課題］ 本発明は、例えば16メガビットDRAM以上の大規模集積
回路用としての高感度かつ高解像度を同時に有するポジ
型電子線レジストを提供することを目的とする。[Problems to be Solved by the Invention] It is an object of the present invention to provide a positive electron beam resist having high sensitivity and high resolution at the same time for a large-scale integrated circuit of, for example, 16 megabit DRAM or more.
［課題を解決する手段］ 本発明は、次式（１）： で表わされる２−シアノアクリル酸シクロヘキシル重合
体に、一般式（２）： （式中、R1、R2、R3、R4は炭素数１〜20のアルキル基を
示す）で表わされる過塩素酸第４級アンモニウム塩を添
加することより成るポジ型電子線レジストである。[Means for Solving the Problem] The present invention provides the following formula (1): The cyclohexyl 2-cyanoacrylate polymer represented by the general formula (2): A positive electron beam resist comprising adding a quaternary ammonium salt of perchloric acid represented by the formula (wherein R 1 , R 2 , R 3 and R 4 represent an alkyl group having 1 to 20 carbon atoms). is there.
本発明は、（１）式で表わされる２−シアノアクリル
酸シクロヘキシル重合体を主成分とするレジストに一般
式（２）で表わされる過塩素酸第４級アンモニウム塩を
添加することにより高感度と高解像度を同時に満たすポ
ジ型電子線レジストを提供する。The present invention provides high sensitivity by adding a quaternary ammonium salt of perchloric acid represented by the general formula (2) to a resist containing a cyclohexyl 2-cyanoacrylate polymer represented by the general formula (1) as a main component. A positive type electron beam resist that simultaneously satisfies high resolution is provided.
なお、過塩素酸第４級アンモニウム塩の添加量は前記
２−シアノアクリル酸シクロヘキシル重合体に対して１
〜30重量％で、感度および解像度を考慮すると５〜15重
量％が好ましい。The amount of the quaternary ammonium salt of perchloric acid added is 1 with respect to the cyclohexyl 2-cyanoacrylate polymer.
-30% by weight, preferably 5-15% by weight in consideration of sensitivity and resolution.
また本発明で用いる２−シアノアクリル酸シクロヘキ
シル重合体は通常の合成法で得られた２−シアノアクリ
ル酸シクロヘキシル単量体をアニオン重合またはラジカ
ル重合することによって得られ、分子量は１万から300
万であるが、分子量が大きすぎると塗布性が低下し、ま
た分子量が小さいと感度が低下することから10万〜100
万が好ましい。The cyclohexyl 2-cyanoacrylate polymer used in the present invention is obtained by anionic or radical polymerization of the cyclohexyl 2-cyanoacrylate monomer obtained by a conventional synthesis method, and has a molecular weight of 10,000 to 300.
However, if the molecular weight is too high, the coatability will decrease, and if the molecular weight is low, the sensitivity will decrease.
10,000 is preferable.
［作用］ 図面の第１図は、分子量51万の２−シアノアクリル酸
シクロヘキシル重合体に過塩素酸テトラ−ｎ−ブチルア
ンモニウム塩を添加した本発明のポジ型電子線レジスト
と、無添加の場合の比較を示す残膜感度曲線である。な
お、照射電子線の加速電圧は10kVであり、照射後の現像
条件は 現像液……２−メチルセロソルブ:2−プロパノール＝8
5:15 現像時間……２分 現像温度……20℃ である。[Operation] FIG. 1 shows the positive type electron beam resist of the present invention obtained by adding tetra-n-butylammonium perchlorate to a cyclohexyl 2-cyanoacrylate polymer having a molecular weight of 510,000, and the case of no addition. 3 is a residual film sensitivity curve showing the comparison of FIG. The accelerating voltage of the irradiation electron beam is 10 kV, and the developing condition after irradiation is as follows.
5:15 Development time: 2 minutes Development temperature: 20 ° C.
この第１図からわかるように、本発明のポジ型電子線
レジストは感度の向上が顕著に見られる。As can be seen from FIG. 1, the positive type electron beam resist of the present invention is remarkably improved in sensitivity.
［実施例１］ 分子量51万の２−シアノアクリル酸シクロヘキシル重
合体の５重量％のシクロヘキサノン溶液を作り、さらに
過塩素酸テトラ−ｎ−ブチルアンモニウム塩を重合体に
対して10重量％加え、1000Åの厚さでクロム蒸着された
ガラス基板上に回転塗布法により1500rpmで4300Åの厚
さのレジスト被膜を形成し、120℃で30分間熱処理後、
照射量１μC/cm3、加速電圧10kVで電子線照射した。電
子線照射後、２−メトキシエタノール:2−プロパノール
＝85:15の混合溶媒に20℃において１分間浸漬し、２−
プロパノール中にてリンスして乾燥することによってポ
ジ型レジストパターンが得られた。さらに、120℃、30
分間加熱処理し、硝酸第２セリウムアンモニウムと過塩
素酸のクロムエッチング液にて50秒間、浸漬すると1000
Åのクロム層がエッチングされ、アセトンでレジスト被
膜を除去すると、ガラス基板上に0.5μｍ線幅のクロム
パターンが得られた。[Example 1] A cyclohexanone solution of 5% by weight of a cyclohexyl 2-cyanoacrylate polymer having a molecular weight of 510,000 was prepared, and 10% by weight of tetra-n-butylammonium perchlorate was added to the polymer. On a glass substrate with chromium vapor-deposited at a thickness of 4 to form a resist coating with a thickness of 4300Å at 1500 rpm by a spin coating method, after heat treatment at 120 ° C for 30 minutes,
Electron beam irradiation was performed at an irradiation dose of 1 μC / cm 3 and an acceleration voltage of 10 kV. After electron beam irradiation, it was immersed in a mixed solvent of 2-methoxyethanol: 2-propanol = 85: 15 at 20 ° C for 1 minute, and then 2-
A positive resist pattern was obtained by rinsing in propanol and drying. Furthermore, 120 ℃, 30
Heat treatment for 50 minutes and immerse in a chromium etchant of ceric ammonium nitrate and perchloric acid for 50 seconds for 1000 minutes
When the chromium layer was etched and the resist film was removed with acetone, a chromium pattern having a line width of 0.5 μm was obtained on the glass substrate.
［実施例２］ 実施例１と同様に被膜形成し、加熱処理後、１μC/cm
3で電子線照射した。電子線照射後、２−メトキシエタ
ノール:2−ブトキシエタノール＝60:40の混合溶媒に20
℃にて２分間浸漬し、その後２−プロパノールでリンス
し、乾燥した。得られたレジストパターンを走査型電子
顕微鏡（SEM）で観察したところ、非常にシャープなパ
ターンが観測された。Example 2 A film was formed in the same manner as in Example 1, and after heat treatment, 1 μC / cm
It was irradiated with electron beam at 3 . After the electron beam irradiation, 20 in a mixed solvent of 2-methoxyethanol: 2-butoxyethanol = 60: 40.
It was soaked at ℃ for 2 minutes, then rinsed with 2-propanol and dried. When the obtained resist pattern was observed with a scanning electron microscope (SEM), a very sharp pattern was observed.
［比較例１］ 分子量51万の２−シアノアクリル酸シクロヘキシル重
合体の５重量％のシクロヘキサノン溶液を作り、過塩素
酸テトラ−ｎ−ブチルアンモニウム塩は添加せず、実施
例１と同様に処理したが、電子線照射部のレジストはす
べて溶解せず、膜残りが生じた。なお、電子線照射部を
すべて溶解させるには12分の現像時間を必要としたが、
このとき、レジストパターンは膨潤し、剥離が発生し
た。Comparative Example 1 A 5 wt% cyclohexanone solution of a cyclohexyl 2-cyanoacrylate polymer having a molecular weight of 510,000 was prepared and treated in the same manner as in Example 1 without adding tetra-n-butylammonium perchlorate. However, all the resist in the electron beam irradiation part did not dissolve, and a film residue was generated. In addition, it took 12 minutes to develop all the electron beam irradiation parts,
At this time, the resist pattern swelled and peeling occurred.
［発明の効果］ 上記より本発明のレジストを用いることにより、高感
度かつ高解像度でレジストパターンを形成することが可
能となり、半導体の製造において高生産性とコスト低減
に大きな効果をもたらすことができる。[Effects of the Invention] From the above, by using the resist of the present invention, it is possible to form a resist pattern with high sensitivity and high resolution, and it is possible to bring about great effects on high productivity and cost reduction in the manufacture of semiconductors. .
第１図は、２−シアノアクリル酸シクロヘキシル重合体
に過塩素酸テトラ−ｎ−ブチルアンモニウム塩を10重量
％添加した場合と無添加の場合の残膜感度曲線の比較を
示すグラフ図である。FIG. 1 is a graph showing a comparison of residual film sensitivity curves when a 10% by weight tetra-n-butylammonium perchlorate salt was added to a cyclohexyl 2-cyanoacrylate polymer and when it was not added.
Claims (1)
体に、一般式（２）： （式中、R1、R2、R3、R4は炭素数１〜20のアルキル基を
示す）で表わされる過塩素酸第４級アンモニウム塩を添
加することより成るポジ型電子線レジスト。1. The following equation (1): The cyclohexyl 2-cyanoacrylate polymer represented by the general formula (2): A positive electron beam resist comprising adding a quaternary ammonium salt of perchloric acid represented by the formula: wherein R 1 , R 2 , R 3 and R 4 represent an alkyl group having 1 to 20 carbon atoms.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087703A JPH0823697B2 (en) | 1989-04-06 | 1989-04-06 | Positive electron beam resist |
| KR1019890006845A KR900018743A (en) | 1988-05-24 | 1989-05-22 | Positive electron beam resist and resist pattern formation method using the same |
| DE68917521T DE68917521T2 (en) | 1988-05-24 | 1989-05-23 | Highly sensitive positive resist with high resolving power for electron beams. |
| EP89109284A EP0343603B1 (en) | 1988-05-24 | 1989-05-23 | High-sensitivity, high-resolution positive-type electron-beam resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087703A JPH0823697B2 (en) | 1989-04-06 | 1989-04-06 | Positive electron beam resist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02264955A JPH02264955A (en) | 1990-10-29 |
| JPH0823697B2 true JPH0823697B2 (en) | 1996-03-06 |
Family
ID=13922280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087703A Expired - Lifetime JPH0823697B2 (en) | 1988-05-24 | 1989-04-06 | Positive electron beam resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0823697B2 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58108213A (en) * | 1981-12-22 | 1983-06-28 | Toagosei Chem Ind Co Ltd | Preparation of polymer of 2-cyanoacrylic acid ester |
| JPH0623835B2 (en) * | 1986-10-06 | 1994-03-30 | 富士写真フイルム株式会社 | Photosensitive material for heat development |
| JPH0670105B2 (en) * | 1986-12-29 | 1994-09-07 | 凸版印刷株式会社 | Method for producing monodisperse polymer |
| JPH0667980B2 (en) * | 1986-12-29 | 1994-08-31 | 凸版印刷株式会社 | Method for producing α-cyanoacrylic acid ester polymer |
| JP2550655B2 (en) * | 1988-04-26 | 1996-11-06 | 凸版印刷株式会社 | Positive electron beam resist |
| JPH0675196B2 (en) * | 1989-11-08 | 1994-09-21 | 凸版印刷株式会社 | Positive electron beam resist |
-
1989
- 1989-04-06 JP JP1087703A patent/JPH0823697B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02264955A (en) | 1990-10-29 |
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