JPH01188856A - Method for removing resist - Google Patents
Method for removing resistInfo
- Publication number
- JPH01188856A JPH01188856A JP1341488A JP1341488A JPH01188856A JP H01188856 A JPH01188856 A JP H01188856A JP 1341488 A JP1341488 A JP 1341488A JP 1341488 A JP1341488 A JP 1341488A JP H01188856 A JPH01188856 A JP H01188856A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- oxide film
- metal oxide
- circuit
- metal
- 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
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000000206 photolithography Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000009832 plasma treatment Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 239000000758 substrate Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 101100493711 Caenorhabditis elegans bath-41 gene Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電子部品業界で一般に良く使用されているフ
ォトリソグラフィ法による微細な回路形成の製造工程に
おいて、回路形成後不用になった金属表面上のレジスト
の除去方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is applied to the manufacturing process of forming fine circuits by photolithography, which is commonly used in the electronic component industry. The present invention relates to a resist removal method.
従来の技術
一般に使用されているフォトリソグラフィ法による回路
形成工程の一例を第3図に示す。まずセラミックまたは
ガラスなどの基板1を洗浄2し、その上に回路素材とな
るクロム、銅、アルミニウムなどの被膜3を形成し、さ
らに洗浄4の後、この被膜上に回路部に対応したパター
ンを形成するため、レジスト塗布・プリベーク5、マス
ク合せ・露光6.@像・ポス1−ベーク7、デイスカム
8、エツチング9の各処理を行い、最後に不用になった
レジスト除去10を行う。その除去方法は、まずO,プ
ラズマアッシャ−で処理11をする。この処理でレジス
トの有機物成分は除去可能であるが。FIG. 3 shows an example of a circuit forming process by photolithography, which is commonly used in the prior art. First, a substrate 1 made of ceramic or glass is cleaned 2, and a coating 3 of chromium, copper, aluminum, etc., which is a circuit material, is formed on it. After cleaning 4, a pattern corresponding to the circuit part is formed on this coating. For forming, resist coating/prebake 5, mask alignment/exposure 6. @Image/Post 1--Bake 7, Discum 8, and Etching 9 are performed, and finally, unnecessary resist removal 10 is performed. As for the removal method, first, treatment 11 is performed using O and plasma asher. This process can remove the organic components of the resist.
レジスト中の微量な重金属などの不純物が残渣として残
る。このため、さらに発煙硝酸浸漬または硫酸と過酸化
水素水の混合液浸漬という処理12が行われている。Trace amounts of impurities such as heavy metals in the resist remain as residue. For this reason, a further treatment 12 of immersion in fuming nitric acid or immersion in a mixture of sulfuric acid and hydrogen peroxide is performed.
発明が解決しようとする課題
上記工程の発煙硝酸浸漬または硫酸と過酸化水素水の混
合液浸漬処理12においては、(1)発生するガスが強
劇物であり1作業性が悪い、(2)ガスの発生が著るし
く、液の劣化が早い、(3)使用薬品が強酸化剤であり
、金属表面にダメージを与える。といった問題がある。Problems to be Solved by the Invention In the above-mentioned process of immersion in fuming nitric acid or immersion in a mixed solution of sulfuric acid and hydrogen peroxide, (1) the gas generated is a powerful substance and the workability is poor; (2) (3) The chemical used is a strong oxidizing agent and damages the metal surface. There are problems like this.
本発明は上記の問題を解決するもので、02プラズマア
ッシャ−後の処理方法を改善し1作業性を良クシ、液の
劣化が少なく、金属表面にダメージを与えることのない
レジスト除去方法を提供することを目的とするものであ
る。The present invention solves the above problems and provides a resist removal method that improves the processing method after 02 plasma asher, improves workability, causes less deterioration of the solution, and does not damage the metal surface. The purpose is to
課題を解決するための手段
上記問題を解決するために、本発明のレジスト除去方法
は、まずフォトリソグラフィ法による回路形成における
レジスト塗布前に金属表面に02プラズマ処理などで酸
化膜を形成し、その後通常のフォトリソグラフィ法で回
路形成し、不用になったレジストを0□プラズマアッシ
ャ−で処理した後、金属酸化膜上に残った微量な不純物
を金属を侵さず金属酸化膜のみ溶解除去可能な液、たと
えばクエン酸系有機酸で金属酸化膜とともに除去するも
のである。Means for Solving the Problems In order to solve the above problems, the resist removal method of the present invention first forms an oxide film on the metal surface by 02 plasma treatment etc. before applying the resist in circuit formation by photolithography, and then After forming a circuit using the normal photolithography method and treating the unused resist with a 0□ plasma asher, the trace impurities remaining on the metal oxide film can be removed using a liquid that can dissolve and remove only the metal oxide film without damaging the metal. For example, the metal oxide film is removed together with a citric acid-based organic acid.
さらに、本発明は、フォトリソグラフィ法による回路形
成におけるレジスト塗布前に金属表面に酸化膜を形成し
、フォトリソグラフィ法で回路形成後に、不用になった
レジストを02プラズマアッシャ−後、l13極電解洗
浄により金属酸化膜とともにレジスト残渣を除去するも
のである。Furthermore, the present invention forms an oxide film on the metal surface before resist application in circuit formation by photolithography, and after forming the circuit by photolithography, removes the unused resist by 02 plasma ashering and then performs 113 electrode electrolytic cleaning. This method removes the resist residue along with the metal oxide film.
作用
上記構成により、まずレジスト塗布前に金属表面に酸化
膜を形成し、その後にフォトリソグラフィ法で回路形成
するので、回路形成後不用になったレジストを除去する
のに使用する除去剤は強劇物でないため、作業性が良く
、ガスの発生も少なく、液組成は安定し、液の劣化も少
ない。また、金属表面にタメージを与えることもなくな
る。Effect With the above configuration, an oxide film is first formed on the metal surface before applying the resist, and then the circuit is formed using photolithography, so the removal agent used to remove the resist that is no longer needed after the circuit is formed is not very strong. Since it is not a material, it is easy to work with, generates little gas, has a stable liquid composition, and has little deterioration of the liquid. Also, it will not damage the metal surface.
実施例 以下本発明の一実施例を図面に基づいて説明する。Example An embodiment of the present invention will be described below based on the drawings.
第1図は本発明の一実施例のフォトリソグラフィ法によ
る回路形成工程を示す図である。まずセラミックまたは
ガラスなどの基板21を洗浄22シ、その上に回路素材
となるクロム、銅、アルミニウムなどの被膜23を形成
し、洗浄24の後、o2プラズマ処理25で酸化膜を形
成する。このときの条件は次の通りである。すなわち、
02の流量:300cc/min、圧カニ 1.0To
rr、周波数: 13.56M1(z、パワー: 30
0W、基板温度=300℃1時間:5分で処理し、 1
00〜300人の厚さの酸化膜を形成した。その後金属
酸化膜上に回路形成するため、通常のレジスト塗布前
現象・ボス1ヘベーク28、デイスカム29、エツチン
グ30の各処理を行い、最後に不用になったレジスト除
去31を行う。この除去方法はまずo2プラズマアッシ
ャ−で処理32する。このときの条件は次の通りである
。すなわち、02の流量: 300cc /win、圧
カニ 0.3Torr、周波数: 2.45GHz、パ
ワm:1.5kW、基板温度:300℃、時間=2分で
処理し、レジスト中の有機成分を除去した。その後、金
属酸化膜上に残った有機成分以外の重金属などの不純物
をクエン酸を主成分とする有機酸液(商品名:シュシマ
200KA、大阪佐々木化学製の20%液)を60〜9
0℃に加温し、絶えず循環濾過した液中に5〜10分間
浸漬する処理33を行い、金属酸化膜とともに金属酸化
膜上の不純物を除去した。このとき、処理後の金属表面
上を顕微鏡でllt察した結果、金属面はエツチングさ
れていないことを確認した。FIG. 1 is a diagram showing a circuit forming process by photolithography according to an embodiment of the present invention. First, a substrate 21 made of ceramic or glass is cleaned 22, a film 23 of chromium, copper, aluminum, etc., which is a circuit material, is formed thereon, and after cleaning 24, an oxide film is formed by O2 plasma treatment 25. The conditions at this time are as follows. That is,
02 flow rate: 300cc/min, pressure crab 1.0To
rr, frequency: 13.56M1 (z, power: 30
0W, substrate temperature = 300℃ 1 hour: Processed in 5 minutes, 1
An oxide film was formed with a thickness of 0.00 to 300. Thereafter, in order to form a circuit on the metal oxide film, the usual pre-resist coating processes such as baking 28 for the boss 1, discum 29, and etching 30 are performed, and finally, the unnecessary resist is removed 31. In this removal method, first, treatment 32 is performed using an O2 plasma asher. The conditions at this time are as follows. That is, 02 flow rate: 300cc/win, pressure crab 0.3Torr, frequency: 2.45GHz, power m: 1.5kW, substrate temperature: 300°C, time = 2 minutes to remove organic components in the resist. did. After that, impurities such as heavy metals other than organic components remaining on the metal oxide film are removed with an organic acid solution (trade name: Shushima 200KA, 20% solution manufactured by Osaka Sasaki Chemical Co., Ltd.) containing citric acid as the main component.
Treatment 33 was performed in which the sample was heated to 0° C. and immersed in a solution that was constantly circulated and filtered for 5 to 10 minutes to remove impurities on the metal oxide film as well as the metal oxide film. At this time, as a result of observing the metal surface after the treatment using a microscope, it was confirmed that the metal surface was not etched.
次に+ 02プラズマアッシャ−処理後の金属酸化膜上
に残った有機成分以外の重金属などの不純物を除去する
他の実施例を図面を参照して説明する。第2図は陰極電
解洗浄法を示す構成図である。Next, another embodiment for removing impurities such as heavy metals other than organic components remaining on the metal oxide film after the +02 plasma asher treatment will be described with reference to the drawings. FIG. 2 is a block diagram showing the cathodic electrolytic cleaning method.
電解槽41の中に白金などの陽極42と陰極として基板
43を配置し、これらを基板43の材質に適した電解液
44の中に浸漬し、直流電圧を印加して洗浄する。電解
条件は次の通りである。クロムの場合は。An anode 42 made of platinum or the like and a substrate 43 as a cathode are placed in an electrolytic bath 41, immersed in an electrolytic solution 44 suitable for the material of the substrate 43, and cleaned by applying a DC voltage. The electrolysis conditions are as follows. In the case of chrome.
電解液組成:苛性ソーダ15g/Q、オルソケイ酸ソー
ダ50g/Q、非イオン系界面活性剤0.3g/Q、温
度:50℃、陰極電流密度: 10 A / dm2、
時間:1分で、また、銅の場合は、電解液組成:炭酸ソ
ーダ25g/(1、第3リン酸ソーダ8 g / Q、
非イオン系界面活性剤0.5 g / Q、温度:50
℃、陰極電流密度: 5 A / dm”、時間21分
で、また、アルミニウムの場合は、電解液組成:第3リ
ン酸ソーダ30g/Q、非イオン系界面活性剤0.5g
/Q、温度=50°C1陰極電流密度:5A/dm”、
時間:1分でそれぞれ処理し、金属酸化膜とともに金属
酸化膜上の不純物を除去した。このとき、電解液を全て
絶えず循環濾過し、処理後の金属表面上を顕微鏡でwn
察した結果、金属面はエツチングされていないことを確
認した。Electrolyte composition: caustic soda 15g/Q, sodium orthosilicate 50g/Q, nonionic surfactant 0.3g/Q, temperature: 50°C, cathode current density: 10 A/dm2,
Time: 1 minute, and in the case of copper, electrolyte composition: soda carbonate 25g/(1, tertiary sodium phosphate 8g/Q,
Nonionic surfactant 0.5 g/Q, temperature: 50
°C, cathode current density: 5 A/dm", time 21 minutes, and in the case of aluminum, electrolyte composition: tertiary sodium phosphate 30 g/Q, nonionic surfactant 0.5 g
/Q, temperature = 50°C1 cathode current density: 5A/dm",
Each treatment was performed for 1 minute to remove impurities on the metal oxide film as well as the metal oxide film. At this time, all the electrolyte is constantly circulated and filtered, and the treated metal surface is examined using a microscope.
As a result, it was confirmed that the metal surface was not etched.
発明の効果
以上本発明によれば、使用するレジスト除去剤が強劇物
でないため1作業性が良く、ガスの発生も少なく、液組
成が安定し、液の劣化が少ない。Effects of the Invention According to the present invention, since the resist removing agent used is not a strong substance, the workability is good, less gas is generated, the liquid composition is stable, and there is little deterioration of the liquid.
また、金属表面にダメージを与えないという効果がある
。It also has the effect of not damaging the metal surface.
第1図は本発明の一実施例のフォトグラフィ法による回
路形成の工程図、第2図は本発明の他の実施例の陰極電
解洗浄によるレジスト除去を説明する模式図、第3図は
従来のフォトグラフィ法による回路形成の工程図である
。
21・・・基板、23・・・被膜形成、25・・・O□
プラズマ酸化処理、26・・・レジスト塗布・プリベー
ク、30・・・エツチング、31・・・レジスト除去、
32・・・02プラズマアッシャ−133・・・金属酸
化膜除去、41・・・電解槽。
42・・・陽極、43・・・陰極(基板)、44・・電
解液。
代理人 森 本 義 弘
第1図
第2図
41−・−電解槽
42・−陽極
43 、、、豫持(去WL)
4−一一電jらT1シ友FIG. 1 is a process diagram of circuit formation using a photography method according to an embodiment of the present invention, FIG. 2 is a schematic diagram illustrating resist removal by cathodic electrolytic cleaning according to another embodiment of the present invention, and FIG. 3 is a conventional method. FIG. 2 is a process diagram of circuit formation using a photography method. 21... Substrate, 23... Film formation, 25... O□
Plasma oxidation treatment, 26... Resist coating/prebake, 30... Etching, 31... Resist removal,
32...02 Plasma asher-133...Metal oxide film removal, 41...Electrolytic cell. 42... Anode, 43... Cathode (substrate), 44... Electrolyte. Agent Yoshihiro Morimoto Figure 1 Figure 2 41--Electrolytic cell 42--Anode 43,..., Yumochi (left WL) 4-11 Electric J and other T1 friends
Claims (1)
スト塗布前に金属表面に酸化膜を形成し、フォトリソグ
ラフィ法で回路形成後に、不用になったレジストをO_
2プラズマアッシャー後、金属を侵さず金属酸化膜のみ
溶解除去可能な液を用いて金属酸化膜とともにレジスト
残渣を除去するレジスト除去方法。 2、フォトリソグラフィ法による回路形成におけるレジ
スト塗布前に金属表面に酸化膜を形成し、フォトリソグ
ラフィ法で回路形成後に、不用になったレジストをO_
2プラズマアッシャー後、陰極電解洗浄により金属酸化
膜とともにレジスト残渣を除去するレジスト除去方法。[Claims] 1. An oxide film is formed on the metal surface before resist application in circuit formation by photolithography, and after circuit formation by photolithography, the unnecessary resist is removed by O_
2. A resist removal method that removes the resist residue along with the metal oxide film using a liquid that does not attack the metal and can dissolve and remove only the metal oxide film after plasma ashering. 2. Form an oxide film on the metal surface before applying resist during circuit formation using photolithography, and remove unnecessary resist after forming the circuit using photolithography.
2. A resist removal method that removes resist residue along with the metal oxide film by cathodic electrolytic cleaning after plasma ashering.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1341488A JPH01188856A (en) | 1988-01-22 | 1988-01-22 | Method for removing resist |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1341488A JPH01188856A (en) | 1988-01-22 | 1988-01-22 | Method for removing resist |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01188856A true JPH01188856A (en) | 1989-07-28 |
Family
ID=11832475
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1341488A Pending JPH01188856A (en) | 1988-01-22 | 1988-01-22 | Method for removing resist |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01188856A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6376364B1 (en) | 1998-11-26 | 2002-04-23 | Sharp Kabushiki Kaisha | Method of fabricating semiconductor device |
JP2009177102A (en) * | 2008-01-28 | 2009-08-06 | Nissan Motor Co Ltd | Method for manufacturing electrode of semiconductor device |
CN111834216A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院物理研究所 | Method for preparing nano-sized metal film pattern |
-
1988
- 1988-01-22 JP JP1341488A patent/JPH01188856A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6376364B1 (en) | 1998-11-26 | 2002-04-23 | Sharp Kabushiki Kaisha | Method of fabricating semiconductor device |
JP2009177102A (en) * | 2008-01-28 | 2009-08-06 | Nissan Motor Co Ltd | Method for manufacturing electrode of semiconductor device |
CN111834216A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院物理研究所 | Method for preparing nano-sized metal film pattern |
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