JPS6161532B2 - - Google Patents
Info
- Publication number
- JPS6161532B2 JPS6161532B2 JP55101254A JP10125480A JPS6161532B2 JP S6161532 B2 JPS6161532 B2 JP S6161532B2 JP 55101254 A JP55101254 A JP 55101254A JP 10125480 A JP10125480 A JP 10125480A JP S6161532 B2 JPS6161532 B2 JP S6161532B2
- Authority
- JP
- Japan
- Prior art keywords
- resist
- pattern
- developer
- rinsing
- resist pattern
- 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
- 238000000034 method Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000012487 rinsing solution Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 230000007261 regionalization Effects 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 230000018109 developmental process Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 239000004065 semiconductor Substances 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)
- Electron Beam Exposure (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
【発明の詳細な説明】
本発明はレジストパターンの形成方法に関し、
更に詳細にはクロロメチル化ポリスチレンをレジ
ストとするレジストパターンの形成方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a resist pattern,
More specifically, the present invention relates to a method of forming a resist pattern using chloromethylated polystyrene as a resist.
従来、半導体集積回路などの微細パターンの形
成に当り、基体上にポジ型又はネガ型のフオトレ
ジスト膜を設け光照射した後、現像（溶解）して
所望のフオトレジスト膜のパターンを形成し、こ
のパターンをマスクとして基体加工又は回路形成
等を行なう手段が採用されている。ところでクロ
ロメチル化ポリスチレン（以下CMSという）は
例えば電子材料第18巻、第10号、第65〜69頁
（1979年）に記載されているように、高解像度で
あると共にプラズマエツチングに対する耐性が良
好で、微細パターン形成用のネガ型電子ビームレ
ジストとして有用である。該レジストは遠紫外
線、粒子線又はＸ線の照射によつて照射部の高分
子化合物間に重合反応が生起し、次の現像工程で
は照射部は現像液に溶解しなくなる性質を有して
いる。 Conventionally, when forming fine patterns such as semiconductor integrated circuits, a positive or negative photoresist film is provided on a substrate, irradiated with light, and then developed (dissolved) to form a desired photoresist film pattern. A method of processing a substrate or forming a circuit using this pattern as a mask is employed. By the way, chloromethylated polystyrene (hereinafter referred to as CMS) has high resolution and good resistance to plasma etching, as described in Electronic Materials Vol. 18, No. 10, pp. 65-69 (1979). Therefore, it is useful as a negative electron beam resist for forming fine patterns. This resist has the property that when irradiated with far ultraviolet rays, particle beams, or X-rays, a polymerization reaction occurs between the polymer compounds in the irradiated areas, and the irradiated areas will not dissolve in the developer in the next development process. .
CMSレジストの照射部、すなわち重合反応が
生じた部分は現像工程において現像液には溶解し
ないが、現像液が浸透して照射部が膨潤し、次の
リンス工程で膨潤部に含まれている重合反応に関
与しないレジストおよび重合度の小さいレジスト
並びに現像液は照射部（膨潤部）から抽出され、
一方照射部中の重合したレジスト部分は収縮して
形状の整つたレジストパターンが形成される。し
かしながらリンス工程での前記の収縮作用が強す
ぎると、前記未重合のレジストおよび現像液の抽
出孔（抜け穴）がレジストパターンに残存する。
その結果レジストパターンをマスクとして基体例
えばSiウエハをエツチングした場合、本来エツチ
ングされてはならないレジストパターンの下部の
基体も前記抜け穴を通してエツチングされるた
め、加工後の基体のパターンにピンホールが生
じ、良好な加工ができないという欠点がある。 The irradiated part of the CMS resist, that is, the part where a polymerization reaction has occurred, is not dissolved in the developer during the development process, but the developer penetrates and the irradiated part swells, and in the next rinsing process, the polymer contained in the swollen part Resist that does not participate in the reaction, resist with a low degree of polymerization, and developer are extracted from the irradiated area (swelled area),
On the other hand, the polymerized resist portion in the irradiated area contracts to form a well-shaped resist pattern. However, if the shrinkage effect in the rinsing step is too strong, extraction holes (holes) for the unpolymerized resist and developer remain in the resist pattern.
As a result, when a substrate such as a Si wafer is etched using the resist pattern as a mask, the substrate below the resist pattern, which should not be etched, is also etched through the hole, resulting in pinholes in the pattern of the substrate after processing. The disadvantage is that it cannot be processed.
本発明は前記現状に鑑みてなされたもので、そ
の目的はCMSレジストパターンにピンホールを
生ずることがなく、又基体に微細な高品質のパタ
ーンを形成できるレジストパターンの形成方法を
提供することである。 The present invention has been made in view of the above-mentioned current situation, and its purpose is to provide a method for forming a resist pattern that does not cause pinholes in a CMS resist pattern and can form a fine, high-quality pattern on a substrate. be.
前記目的を達成する本発明のレジストパターン
形成方法は基体上にクロロメチル化ポリスチレン
より成るレジスト膜を設け、遠紫外線、粒子線又
はＸ線を該レジスト膜の所定位置に照射した後、
現像液による現像及びリンス液によるリンスを行
なつて該レジスト膜のパターンを形成する方法に
おいて、現像工程とリンス工程との間で現像液と
リンス液との現像能力を有しない混合液により該
レジスト膜を処理するか又は該混合液によりリン
スを行なうことを特徴とする。 The resist pattern forming method of the present invention that achieves the above object includes providing a resist film made of chloromethylated polystyrene on a substrate, irradiating predetermined positions of the resist film with deep ultraviolet rays, particle beams, or X-rays, and then
In a method of forming a pattern on the resist film by developing with a developer and rinsing with a rinsing solution, between the development step and the rinsing step, the resist is The method is characterized in that the membrane is treated or rinsed with the mixed solution.
本発明によれば、現像液とリンス液との混合液
であつて、かつ現像能力を有しない混合液により
現像後のレジスト膜を処理するか又はこれを直接
リンス液として使用することにより前記の収縮作
用が緩和され、その結果抽出孔を残存することな
くパターン部が形成される。 According to the present invention, by treating the resist film after development with a mixed solution of a developer and a rinsing solution and having no developing ability, or using this directly as a rinsing solution, the above-mentioned method can be achieved. The shrinkage effect is relaxed, and as a result, the pattern is formed without leaving any extraction holes.
本発明において使用される現像液はアセトン、
メチルエチルケトン等であり、又リンス液はイソ
プロピルアルコール、ノルマルプロピルアルコー
ル、ノルマルブチルアルコール又は水等であり、
したがつて現像液とリンス液との混合液は現像能
力を有しない組成の範囲内で又均質な混合液を生
成する組成の範囲内で適宜現像液とリンス液との
組成を採択することができ、一般には容量比で
１：３ないし３：１である。 The developer used in the present invention is acetone,
Methyl ethyl ketone, etc., and the rinsing liquid is isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, water, etc.
Therefore, the composition of the developer and rinse solution can be appropriately selected within the range of composition that does not have developing ability or within the range of composition that produces a homogeneous mixed solution. Generally, the capacity ratio is 1:3 to 3:1.
現像液とリンス液との混合比に対する現像能力
の一例として、現像液にアセトン、リンス液にイ
ソプロピルアルコールを用いた場合のCMSレジ
ストに対する現像能力を示す実験データを第１図
に示す。現像能力は、レジストの初期膜厚で規格
化した残膜厚を表わしている。現像、リンス以外
の実験の条件は、後述の実施例１で述べる条件と
同じである。第１図から、現像液（アセトン）の
濃度が75％を超えるところで急激に現像されるこ
とがわかる。また、それ以下の濃度ではこの混合
液は現像能力を有しないことがわかる。 As an example of the developing ability with respect to the mixing ratio of the developer and the rinsing liquid, FIG. 1 shows experimental data showing the developing ability for a CMS resist when acetone is used as the developing liquid and isopropyl alcohol is used as the rinsing liquid. The developing ability represents the residual film thickness normalized by the initial film thickness of the resist. The experimental conditions other than development and rinsing were the same as those described in Example 1 below. From FIG. 1, it can be seen that development occurs rapidly when the concentration of the developer (acetone) exceeds 75%. Moreover, it can be seen that this mixed solution has no developing ability at a concentration lower than that.
次に本発明を実施例及び比較例について説明す
るが、本発明はこれによりなんら限定されるもの
ではない。 Next, the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto in any way.
実施例 １
Siウエハの表面に厚さ0.5μｍにCMSを塗布
し、90℃で30分間プリベークした後、加速電圧
20KVの電子ビームより照射量2.4×10-5c／cm2で
Siウエハ上にLSIの回路パターンを描画した。こ
の被照射Siウエハをアセトン中に浸漬、撹拌して
現像を行なつた。現像に引き続いてイソプロピル
アルコール（70容量％）−アセトン（30容量％）
の混合液にSiウエハを浸漬した後、イソプロピル
アルコールに浸漬してリンスを行なつた。次に窒
素ガスをSiウエハの表面に吹きつけてイソプロピ
ルアルコールを蒸発させ、100℃で30分間ポスト
ベークを行ない、電子ビームの照射部分に厚さ
0.4μｍのCMSの残存膜すなわちレジストパター
ンを有するSiウエハを得た。Example 1 CMS was applied to the surface of a Si wafer to a thickness of 0.5 μm, and after prebaking at 90°C for 30 minutes,
The irradiation amount is 2.4×10 -5 c/cm 2 from a 20KV electron beam.
An LSI circuit pattern was drawn on a Si wafer. This irradiated Si wafer was immersed in acetone and stirred for development. Development followed by isopropyl alcohol (70% by volume) - acetone (30% by volume)
After immersing the Si wafer in the mixed solution, it was rinsed by immersing it in isopropyl alcohol. Next, nitrogen gas is blown onto the surface of the Si wafer to evaporate the isopropyl alcohol, and post-baking is performed at 100°C for 30 minutes to create a thick layer in the area irradiated with the electron beam.
A Si wafer having a 0.4 μm CMS residual film, ie, a resist pattern, was obtained.
このレジストパターンを走査電子顕微鏡を用い
て観察したところ、レジストパターンに微細なピ
ンホールは全く観察されなかつた。 When this resist pattern was observed using a scanning electron microscope, no fine pinholes were observed in the resist pattern.
次にこのウエハをフレオンガスを用いたプラズ
マエツチングで深さ約0.5μｍになるようにSiを
エツチングし次いでレジストパターンを酸素プラ
ズマで炭化して除去した。このウエハを走査電子
顕微鏡で観察したところ、レジストパターンで覆
われていた部分はフレオンガスプラズマエツチン
グによる影響を全く受けてなく、良好なSiパター
ンが形成された。 Next, the Si was etched on this wafer to a depth of about 0.5 μm by plasma etching using Freon gas, and the resist pattern was then carbonized and removed with oxygen plasma. When this wafer was observed with a scanning electron microscope, it was found that the portion covered by the resist pattern was not affected by the Freon gas plasma etching at all, and a good Si pattern was formed.
比較例 １
現像後のイソプロピルアルコール−アセトン混
合液にSiウエハを浸漬する工程を省略した以外
は、実施例１と同様にしてレジストパターンを有
するSiウエハを作製し、このSiウエハについて実
施例１と同様の観察を行なつた。Comparative Example 1 A Si wafer with a resist pattern was prepared in the same manner as in Example 1, except that the step of immersing the Si wafer in the isopropyl alcohol-acetone mixture after development was omitted, and this Si wafer was subjected to the same procedure as in Example 1. Similar observations were made.
Siウエハのレジストパターンを走査電子顕微鏡
で観察したところパターン内に直径約0.1μｍの
ピンホールが多数認められた。又Siをエツチング
した後の観察ではパターン形成部に直径0.2μｍ
の穴が所々に認められ、良好なSiパターンは形成
されなかつた。 When the resist pattern of the Si wafer was observed using a scanning electron microscope, many pinholes with a diameter of approximately 0.1 μm were observed within the pattern. In addition, observation after etching Si shows that the pattern formation area has a diameter of 0.2 μm.
Holes were observed here and there, and a good Si pattern was not formed.
実施例 ２
実施例１の方法においてイソプロピルアルコー
ル−アセトン混合液による処理を行なうことな
く、リンス液としてイソプロピルアルコールの代
りに該混合液を使用してリンスを行なつた以外は
実施例１と同様にしてレジストパターンを有する
Siウエハを作製した。Example 2 The same procedure as in Example 1 was carried out, except that the method of Example 1 was not performed with the isopropyl alcohol-acetone mixture, but the mixture was used instead of isopropyl alcohol as the rinsing agent. has a resist pattern
A Si wafer was fabricated.
このレジストパターンについて実施例１と同様
の観察を行なつたところ、略同様な結果が得られ
た。 When this resist pattern was observed in the same manner as in Example 1, substantially the same results were obtained.
以上の説明から明らかなように、本発明によれ
ば現像液とリンス液との混合液を現像工程とリン
ス工程との中間における処理又はリンス液として
使用するという簡単な方法でレジストパターンの
性質を改善できるという利点がある。 As is clear from the above description, according to the present invention, the properties of a resist pattern can be improved by a simple method of using a mixed solution of a developer and a rinsing solution as an intermediate treatment or rinsing solution between the development process and the rinsing process. The advantage is that it can be improved.
第１図は現像液（アセトン）とリンス液（イソ
プロピルアルコール）の混合比（アセトン濃度）
に対するCMSレジストの現像能力を示す図であ
る。
Figure 1 shows the mixing ratio (acetone concentration) of developer (acetone) and rinse solution (isopropyl alcohol).
FIG.
Claims (1)
るレジスト膜を設け、遠紫外線、粒子線又はＸ線
を該レジスト膜の所定位置に照射した後、現像液
による現像及びリンス液によるリンスを行なつて
該レジスト膜のパターンを形成する方法におい
て、現像工程とリンス工程との間で現像液とリン
ス液との現像能力を有しない混合液により該レジ
スト膜を処理するか又は該混合液によりリンスを
行なうことを特徴とするレジストパターンの形成
方法。1. A resist film made of chloromethylated polystyrene is provided on a substrate, and predetermined positions of the resist film are irradiated with deep ultraviolet rays, particle beams, or X-rays, and then developed with a developer and rinsed with a rinse solution to remove the resist. In the method of forming a pattern on a film, the resist film may be treated with a mixed solution of a developer and a rinsing solution that does not have developing ability between the developing step and the rinsing step, or the resist film may be rinsed with the mixed solution. Characteristic resist pattern formation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10125480A JPS5727031A (en) | 1980-07-25 | 1980-07-25 | Formation of resist pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10125480A JPS5727031A (en) | 1980-07-25 | 1980-07-25 | Formation of resist pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5727031A JPS5727031A (en) | 1982-02-13 |
| JPS6161532B2 true JPS6161532B2 (en) | 1986-12-26 |
Family
ID=14295770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10125480A Granted JPS5727031A (en) | 1980-07-25 | 1980-07-25 | Formation of resist pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5727031A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4535054A (en) * | 1983-05-05 | 1985-08-13 | Hughes Aircraft Company | Wet process for developing styrene polymer resists for submicron lithography |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5511311A (en) * | 1978-07-10 | 1980-01-26 | Hitachi Ltd | Method of photoresist developing |
-
1980
- 1980-07-25 JP JP10125480A patent/JPS5727031A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5511311A (en) * | 1978-07-10 | 1980-01-26 | Hitachi Ltd | Method of photoresist developing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5727031A (en) | 1982-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8956981B2 (en) | Methods of eliminating pattern collapse on photoresist patterns | |
| US4426247A (en) | Method for forming micropattern | |
| US5660957A (en) | Electron-beam treatment procedure for patterned mask layers | |
| US3984582A (en) | Method for preparing positive resist image | |
| US7846623B2 (en) | Resist pattern and reflow technology | |
| KR20100056485A (en) | Composition for forming silicon-containing fine pattern and method for forming fine pattern using the same | |
| US4321317A (en) | High resolution lithography system for microelectronic fabrication | |
| JPS60115222A (en) | Ultra-fine pattern formation | |
| JPS6161532B2 (en) | ||
| JPH0262859B2 (en) | ||
| JPS60114575A (en) | Formation of dry pattern | |
| JP2867509B2 (en) | Method of forming resist pattern | |
| JPS59148335A (en) | Forming method of minute pattern | |
| JP2692059B2 (en) | Method for forming electron beam resist pattern | |
| JP2863225B2 (en) | Pattern formation method | |
| EP0334906A1 (en) | Silicon-containing negative resist material, and process for its use in patterning substrates. | |
| JPS6226174B2 (en) | ||
| JPH0462661B2 (en) | ||
| JPS5810828A (en) | Forming method for resist pattern | |
| JPS6029744A (en) | Process for forming pattern | |
| JPS6054775B2 (en) | Dry development method | |
| JPH02149854A (en) | Method for forming resist pattern | |
| JPS5984520A (en) | Developer | |
| JPH0113217B2 (en) | ||
| JPS59181534A (en) | Pattern formation |