JPH0356469B2 - - Google Patents
Info
- Publication number
- JPH0356469B2 JPH0356469B2 JP20847182A JP20847182A JPH0356469B2 JP H0356469 B2 JPH0356469 B2 JP H0356469B2 JP 20847182 A JP20847182 A JP 20847182A JP 20847182 A JP20847182 A JP 20847182A JP H0356469 B2 JPH0356469 B2 JP H0356469B2
- Authority
- JP
- Japan
- Prior art keywords
- rinsing
- ipa
- resist
- chloroacrylate
- copolymer
- 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 27
- 229920001577 copolymer Polymers 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 3
- SZTBMYHIYNGYIA-UHFFFAOYSA-M 2-chloroacrylate Chemical compound [O-]C(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-M 0.000 description 4
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 3
- -1 fluoroalkyl α-chloroacrylate Chemical compound 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- BOASSOYETJYEJF-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-chloroprop-2-enoate Chemical compound FC(F)(F)COC(=O)C(Cl)=C BOASSOYETJYEJF-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
本発明は高感度ポジ型放射線レジストのリンス
処理工程に関し、更に詳しくは特定の構造を有す
る含ハロゲ放射線感応ポジ型レジストに本発明の
リンス処理工程を適用することによつてレジスト
残渣の無い従来よりも鮮明なレジストパターンを
形成せしめることを特徴とするレジスト像の形成
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to a rinsing process for a high-sensitivity positive radiation resist, and more specifically, the present invention relates to a rinsing process for a halogen-containing radiation-sensitive positive resist having a specific structure. The present invention relates to a method for forming a resist image, which is characterized by forming a resist pattern with no resist residue and clearer than the conventional method by applying a process.
従来、半導体素子、磁気バブル素子、光部品製
造の際の微細加工技術としては、4000〓以上の波
長をもつ紫外線を用いたフオトリソグラフイーが
採用されているが、近年、半導体素子の高密度
化、高集積化に伴い、電子線、Ｘ線等によるリソ
グラフイー技術が注目され、それに用いる高感度
かつ高解像度の放射線レジストが開発されてい
る。しかしいずれも実用的レベルに於て充分では
なく、プロセス面に於てもいくつかの欠点を内包
している。
Traditionally, photolithography using ultraviolet light with a wavelength of 4,000 or more has been used as a microfabrication technology for manufacturing semiconductor devices, magnetic bubble devices, and optical components, but in recent years, the density of semiconductor devices has increased. With the increase in integration, lithography techniques using electron beams, X-rays, etc. are attracting attention, and high-sensitivity and high-resolution radiation resists for use therein are being developed. However, none of these methods is sufficient on a practical level, and they also have some drawbacks in terms of process.
従来よりフルオロアルキルα−クロルアクリレ
ート系重合体例えばポリトリフルオロエチルα−
クロルアクリレートは高感度なポジ型放射線レジ
ストであることが報告されているが（Ｔ・Tada、
Ｊ・Electrochem、Soc、1261829（1979））、
本レジストを比較的溶解性の強い現像液で現像
し、通常のIPAリンスを行うと、レジスト残渣が
部分的に生じやすいという傾向があつた。特に用
いる基板が大面積であればある程その傾向が顕著
であつた。 Conventionally, fluoroalkyl α-chloroacrylate polymers such as polytrifluoroethyl α-
Chloracrylate has been reported to be a highly sensitive positive radiation resist (T. Tada,
J. Electrochem, Soc, 1261829 (1979)), When this resist was developed with a relatively highly soluble developer and subjected to normal IPA rinsing, there was a tendency for resist residue to be partially formed. In particular, the larger the area of the substrate used, the more remarkable this tendency was.
本発明は上記実情に鑑みなされたもので、ポリ
トリフルオロエチルα−クロルアクリレート、な
いしはトリフルオロエチルα−クロルアクリレー
トと他のビニル系モノマーとの共重合体から成る
ポジ型放射線レジストに対し、特定のリンス液を
用いる２段階リンス処理を行うことによつてレジ
スト残渣が全くなく、鮮明な、従つて極めて実用
性の高いレジスト像形成法を提供しようとするも
のである。
The present invention has been made in view of the above-mentioned circumstances, and provides a specific method for a positive radiation resist made of polytrifluoroethyl α-chloroacrylate or a copolymer of trifluoroethyl α-chloroacrylate and other vinyl monomers. The present invention aims to provide a method of forming a resist image that is clear and has no resist residue by performing a two-step rinsing process using a rinsing liquid of 100%, and is therefore highly practical.
すなわち、本発明は次式
で示されるモノマーの単独重合体あるいは、これ
と他のビニル系モノマーとの共重合体のうちの少
くとも一種類以上を基板上に塗布し、所望の部分
を放射線で照射し、現像処理を行つた後リンス処
理を行う過程に於て次に示す２段階のリンス処理
を行うことによつて上記目的を達成しようとする
ものである。
That is, the present invention has the following formula At least one kind of a homopolymer of the monomer shown or a copolymer of this and another vinyl monomer is coated on a substrate, a desired portion is irradiated with radiation, and a development process is performed. The purpose is to achieve the above object by performing the following two-stage rinsing process in the process of rinsing after washing.
第１段階：MIBKの濃度が50％（体積比）以下で
あるIPA−MIBK混合液によるリンス処理。1st stage: Rinsing treatment with an IPA-MIBK mixed solution with a MIBK concentration of 50% (volume ratio) or less.
第２段階：IPA単独によるリンス処理。Second stage: Rinse treatment with IPA alone.
高感度ポジ型放射線レジストポリトリフルオロ
エチルα−クロルアクリレートに対し、従来の
IPAによる１段階リンス処理を行う場合、特に低
照射量で照射し、溶解性の高い現像液を用いる場
合には、レジスト残渣がかなりの頻度で生じてい
たが、本発明によれば、リンス処理を２段階に分
割し、第１段リンスとして、MIBK濃度が50％
（体積比）以下であるMIBK−IPA混合液による
リンス処理を行い、第２段リンスとしてIPAによ
るリンス処理を行うことによつて、レジスト残渣
の生じない鮮明なレジストパターンが得られるこ
とが確認された。
High-sensitivity positive radiation resist polytrifluoroethyl α-chloroacrylate
When performing a one-step rinsing process using IPA, resist residue was frequently generated, especially when irradiating with a low dose and using a highly soluble developer, but according to the present invention, the rinsing process Divide into two stages, and as the first stage rinse, MIBK concentration is 50%.
It has been confirmed that a clear resist pattern without resist residue can be obtained by rinsing with a MIBK-IPA mixed solution with a volume ratio of below (volume ratio) and rinsing with IPA as the second stage rinse. Ta.
ここで本発明が対象とするポジ型放射線レジス
トを例示すれば、ポリトリフルオロエチルα−ク
ロルアクリレート、トリフルオロエチルα−クロ
ルアクリレート−メタクリル酸共重合体、トリフ
ルオロエチルα−クロルアクリレート−メチルメ
タクリレート共重合体、トリフルオロエチルα−
クロルアクリレート−ｔ−ブチルメタクリレート
共重合体、トリフルオロエチルα−クロルアクリ
レート−トリフルオロイソプロピルα−クロルア
クリレート共重合体、トリフルオロエチルα−ク
ロルアクリレート−フエニルα−クロルアクリレ
ート共重合体、トリフルオロエチルα−クロルア
クリレート−α−メチルスチレン共重合体、トリ
フルオロエチルα−クロルアクリレート−ベンジ
ルα−クロルアクリレート共重合体等を挙げるこ
とが出来る。 Examples of positive radiation resists targeted by the present invention include polytrifluoroethyl α-chloroacrylate, trifluoroethyl α-chloroacrylate-methacrylic acid copolymer, and trifluoroethyl α-chloroacrylate-methyl methacrylate. Copolymer, trifluoroethyl α-
Chloracrylate-t-butyl methacrylate copolymer, trifluoroethyl α-chloroacrylate-trifluoroisopropyl α-chloroacrylate copolymer, trifluoroethyl α-chloroacrylate-phenyl α-chloroacrylate copolymer, trifluoroethyl Examples include α-chloroacrylate-α-methylstyrene copolymer, trifluoroethyl α-chloroacrylate-benzyl α-chloroacrylate copolymer, and the like.
本発明に用いるリンス処理に於ける第１段リン
スに用いるリンス液の組成は、使用する現像液に
よつて異なるが、MIBK濃度が50％以下、好まし
くは１〜５％である。 The composition of the rinsing liquid used in the first stage rinsing in the rinsing process used in the present invention varies depending on the developer used, but the MIBK concentration is 50% or less, preferably 1 to 5%.
実施例 １
ポリトリフルオルエチルα−クロルアクリレー
ト（分子量60万）をスピンコーテイングによつて
６インチCrマスク基板上0.5μの厚さに塗布した後
200℃１時間空気中でプリベーク処理を施した。
次いでプリベークされたレジスト膜の所望部分に
加速電圧20KVの電子線を4μC／cm2の照射密度で
照射した後、MIBK−IPA（８：２）から成る現
像液によつて現像処理を施した後、第１リンスと
してIPA−MIBK（99：１）混合液によるリンス
処理を行い、次いで第２段リンスとしてIPAによ
るリンス処理を行つた。また比較例として現像処
理後、従来のIPA1段階リンスを行つたサンプル
も作製した。
Example 1 After coating polytrifluoroethyl α-chloroacrylate (molecular weight 600,000) on a 6-inch Cr mask substrate to a thickness of 0.5μ by spin coating.
Prebaking treatment was performed in air at 200°C for 1 hour.
Next, a desired portion of the prebaked resist film is irradiated with an electron beam at an acceleration voltage of 20 KV at an irradiation density of 4 μC/cm 2 , and then developed with a developer consisting of MIBK-IPA (8:2). , a first rinse was performed using an IPA-MIBK (99:1) mixed solution, and then a second rinse was performed using IPA. As a comparative example, a sample was also prepared in which a conventional IPA one-step rinse was performed after development.
本発明による２段階リンス処理、及び従来の１
段階リンス処理を行つたサンプルをそれぞれ10サ
ンプルずつ作製した結果、１段階リンス処理サン
プル10サンプルのうち３サンプルに部分的なレジ
スト残渣の発生が認められたが、２段階リンス処
理サンプルについてはレジスト残渣の発生は無く
鮮明なレジストパターンが得られていることが確
認できた。 The two-stage rinsing process according to the present invention and the conventional one
As a result of preparing 10 samples for each step-rinsing process, it was found that 3 of the 10 1-step rinsing samples had partial resist residue, but resist residue did not appear in the 2-step rinsing samples. It was confirmed that a clear resist pattern was obtained without the occurrence of .
実施例 ２
トリフルオルエチルα−クロルアクリレート−
フエニルα−クロルアクリレート共重合体（組成
比90：10、分子量80万）をスピンコーテイングに
よつて６インチCrマスク基板上0.5μの厚さに塗布
した後200℃１時間空気中でプリベーク処理を施
した。次いでプリベークされたレジスト膜の所望
部分に加速電圧20KVの電子線を4μC／cm2の照射
密度で照射した後、MIBK−IPA（８：２）から
成る現像液によつて現像処理を施した後、第１段
リンスとしてIPA−MIBK（99：１）混合液によ
るリンス処理を行い、次いで第２段リンスとして
IPAによるリンス処理を行つた。また比較例とし
て現像処理後、従来のIPA1段階リンスを行つた
サンプルも作製した。Example 2 Trifluoroethyl α-chloroacrylate
Phenyl α-chloroacrylate copolymer (composition ratio 90:10, molecular weight 800,000) was applied to a thickness of 0.5μ on a 6-inch Cr mask substrate by spin coating, and then prebaked in air at 200°C for 1 hour. provided. Next, a desired portion of the prebaked resist film is irradiated with an electron beam at an acceleration voltage of 20 KV at an irradiation density of 4 μC/cm 2 , and then developed with a developer consisting of MIBK-IPA (8:2). , perform rinsing treatment with IPA-MIBK (99:1) mixed solution as the first stage rinse, and then perform rinsing treatment as the second stage rinse.
Rinse treatment with IPA was performed. As a comparative example, a sample was also prepared in which a conventional IPA one-step rinse was performed after development.
本発明による２段階リンス処理、及び従来の１
段階リンス処理を行つたサンプルをそれぞれ10サ
ンプルずつ作製した結果、１段階リンス処理サン
プル10サンプルのうち４サンプルに部分的なレジ
スト残渣の発生が認められたが、２段階リンス処
理サンプルについてはレジスト残渣の発生は無く
鮮明なレジストパターンが得られていることが確
認できた。 The two-stage rinsing process according to the present invention and the conventional one
As a result of preparing 10 samples each subjected to the step-wise rinsing process, it was found that 4 of the 10 samples after the 1-step rinsing process had partial resist residue, but resist residue did not appear in the 2-step rinsing process samples. It was confirmed that a clear resist pattern was obtained without the occurrence of .
以上詳述した如く、特定のポジ型放射線レジス
トに対し本発明のリンス処理を施すことによつて
レジスト残渣の無い、従来よりも鮮明なレジスト
パターンの形成が可能となり、もつて半導体基
板、マスク基板などの微細加工に有効に利用出来
る実用性の高いレジスト像形成法を提供できるも
のである。 As detailed above, by applying the rinsing treatment of the present invention to a specific positive radiation resist, it is possible to form a resist pattern that is clearer than before without any resist residue, and is thereby useful for semiconductor substrates and mask substrates. It is possible to provide a highly practical resist image forming method that can be effectively used for microfabrication such as.
Claims (1)
これと他のビニル系モノマーとの共重合体のうち
少くとも１種類以上を基板上に塗布し、所望の部
分を放射線で照射し、現像処理を行つた後リンス
処理を行う過程に於て次に示す２段階のリンス処
理を行うことを特徴とするレジスト像形成法。 （第１段階：メチルイソブチルケトン（MIBK）
の濃度が50％（体積比）以下であるイソプロピ
ルアルコール（IPA）−メチルイソブチルケト
ン混合液によるリンス処理。 第２段階：上記リンス処理が終了した後のIPA単
独によるリンス処理。）[Claims] 1 At least one type of homopolymer of the monomer represented by the formula (1) or a copolymer of this and other vinyl monomers is coated on a substrate, desired areas are irradiated with radiation, and developed. A method for forming a resist image, characterized in that the following two steps of rinsing are performed in the process of rinsing after processing. (First step: Methyl isobutyl ketone (MIBK)
Rinsing treatment with a mixed solution of isopropyl alcohol (IPA) and methyl isobutyl ketone with a concentration of 50% (volume ratio) or less. Second stage: After the above rinsing process is completed, rinsing process using IPA alone. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20847182A JPS5999720A (en) | 1982-11-30 | 1982-11-30 | Forming method of resist image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20847182A JPS5999720A (en) | 1982-11-30 | 1982-11-30 | Forming method of resist image |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5999720A JPS5999720A (en) | 1984-06-08 |
| JPH0356469B2 true JPH0356469B2 (en) | 1991-08-28 |
Family
ID=16556720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20847182A Granted JPS5999720A (en) | 1982-11-30 | 1982-11-30 | Forming method of resist image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5999720A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424182B1 (en) * | 1989-10-19 | 1998-07-08 | Fujitsu Limited | Process for formation of resist patterns |
| JP2007191399A (en) * | 2006-01-17 | 2007-08-02 | Arakawa Chem Ind Co Ltd | Cycloaliphatic compound and method for producing the same |
| CN107735730B (en) * | 2015-06-23 | 2021-03-19 | 富士胶片株式会社 | Developing solution, pattern forming method and manufacturing method of electronic device |
-
1982
- 1982-11-30 JP JP20847182A patent/JPS5999720A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5999720A (en) | 1984-06-08 |
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