JPH04114428A - Cleaning process - Google Patents
Cleaning processInfo
- Publication number
- JPH04114428A JPH04114428A JP23378890A JP23378890A JPH04114428A JP H04114428 A JPH04114428 A JP H04114428A JP 23378890 A JP23378890 A JP 23378890A JP 23378890 A JP23378890 A JP 23378890A JP H04114428 A JPH04114428 A JP H04114428A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- solution
- silicon wafer
- cleaning
- ozone
- 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
- 238000004140 cleaning Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- -1 steam Chemical compound 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 8
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 5
- 239000012459 cleaning agent Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 229960002050 hydrofluoric acid Drugs 0.000 abstract 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 230000000391 smoking effect Effects 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241001189642 Theroa Species 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VSHBTVRLYANFBK-UHFFFAOYSA-N ozone sulfuric acid Chemical compound [O-][O+]=O.OS(O)(=O)=O VSHBTVRLYANFBK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
Landscapes
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、シリコン・ウェーハ等の主として半導体ウェ
ーへの洗浄法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of cleaning primarily semiconductor wafers, such as silicon wafers.
素水溶液又はアンモニア・過酸化水素水溶液中で洗浄す
る方法があった。There was a method of cleaning in an aqueous solution or an ammonia/hydrogen peroxide solution.
又、従来、シリコン・ウェーハ上のホト・レジスト膜等
の有機物を洗浄・除去する方法として、オゾン雰囲気に
晒す方法や、発煙硝酸中あるいはオゾン・硫酸中に浸漬
する方法等が用いられ、ていブこ。In addition, conventional methods for cleaning and removing organic materials such as photoresist films on silicon wafers include exposing the silicon wafer to an ozone atmosphere, immersing it in fuming nitric acid, or ozone/sulfuric acid. child.
しかし、上記従来技術によると、洗浄液の劣化が早い事
や、洗浄液を多量に彼する等の課題があった。However, according to the above-mentioned conventional technology, there were problems such as the cleaning liquid deteriorating quickly and the cleaning liquid having to be used in a large amount.
本発明は、かかる従来技術のｗ題を解決し、洗浄液の劣
化の少ない洗浄法及び洗浄剤の使用量の少ない新しい洗
浄法を提供する事を目的どする。It is an object of the present invention to solve the problems of the prior art and to provide a new cleaning method that causes less deterioration of cleaning liquid and uses less amount of cleaning agent.
従来、シリコン・ウェーへの洗浄法としてシリコン・ウ
ェーハ表面から主として重金属を除去する目的で、ＥＣ
Ａ洗浄、すなわち塩酸、過酸化水〔課題を解決するため
の手段〕
上記課題を解決する為に、本１発明は、洗浄法に関し、
オゾンを添加した弗酸水溶液、塩酸水溶液アンモニア水
溶液、硝酸液又は、弗酸ガス、蒸気、塩酸ガス、蒸気、
アンモニア・ガス蒸気、酸化窒素ガス、蒸気に晒す手段
を取る事を基本とする。Conventionally, EC has been used as a cleaning method for silicon wafers for the purpose of mainly removing heavy metals from the silicon wafer surface.
A cleaning, i.e., hydrochloric acid, peroxide water [Means for solving the problem] In order to solve the above problem, the present invention 1 relates to a cleaning method,
Hydrofluoric acid aqueous solution with added ozone, hydrochloric acid aqueous solution, ammonia aqueous solution, nitric acid solution or hydrofluoric acid gas, steam, hydrochloric acid gas, steam,
Basically, take measures to expose the product to ammonia gas vapor, nitrogen oxide gas, and vapor.
以下、実施例により本発明を詳述する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
いま、弗酸水溶液中にオゾン・ガスを供給するかあるい
は酸素ガスを供給しつつ外部より紫外線を照射して前記
酸素ガスをオゾン化する等すると共に、シリコン−ウェ
ーハを浸漬する事によりシリコン・ウェーハが酸化され
つつエツチングされる事によりシリコン・ウェーハが洗
浄され、重金属等の汚染物が除去される。尚、弗酸と共
に塩酸を添加する事により一層洗浄効果が増巾される。Now, by supplying ozone gas into a hydrofluoric acid aqueous solution or by irradiating ultraviolet rays from outside while supplying oxygen gas to ozone the oxygen gas, and by immersing the silicon wafer, the silicon wafer can be made into a silicon wafer. The silicon wafer is cleaned by etching while being oxidized, and contaminants such as heavy metals are removed. Note that the cleaning effect is further enhanced by adding hydrochloric acid together with hydrofluoric acid.
次に、塩酸水溶液又はアンモニア水溶猷中にオ。Next, add water to an aqueous solution of hydrochloric acid or aqueous ammonia.
シンを添加すると共にシリコン・ウェーハを浸漬するこ
とにより、シリコン・ウェーハ表面から重金属が除去で
きる事はＲＯＡ洗浄液と同等であるしかし、本法の場合
は、酸化剤であるオゾンが耐えず供給される為に、ＲＯ
Ａ洗浄液で起こる過酸化水素の劣化と云う問題が発生し
ない為、洗浄液の寿命がＲＯＡ洗浄液より長くなると云
５効来がある。The ability to remove heavy metals from the silicon wafer surface by adding silica and immersing the silicon wafer is equivalent to that of the ROA cleaning solution. However, in the case of this method, ozone, an oxidizing agent, is not supplied properly. For the sake of RO
Since the problem of hydrogen peroxide deterioration that occurs with the A cleaning solution does not occur, the life of the cleaning solution is longer than that of the ROA cleaning solution.
次に、オゾンを添加した発煙ｆｆ４酸中にホト・レジス
ト膜を塗布したシリコン・ウェーハを浸漬する事により
、速やかにホト・レジスト膜が洗浄除去される。本法は
、従来のオゾン硫酸あるいは発煙硝酸にホトレジスト膜
を塗布したシリコン°ウェーハを浸漬する方法と比べて
、ホト・レジスト膜の重合が進行した場合には、その除
去速度が速（なると云う効果がある。Next, the photoresist film is quickly cleaned and removed by immersing the silicon wafer coated with the photoresist film in fuming FF4 acid to which ozone has been added. Compared to the conventional method of immersing a silicon wafer coated with a photoresist film in ozone sulfuric acid or fuming nitric acid, this method has the effect of increasing the removal rate when the photoresist film has progressed to polymerization. There is.
更に、弗酸ガス−蒸気（蒸気とは水溶液からの蒸発成分
と云う意味で、水蒸気も含有されている）、弗酸ガス、
蒸気を塩酸ガス・蒸気の混合ガス蒸気、アンモニア・ガ
ス蒸気、酸化窒素ガス・蒸気（Ｎｏ 、Ｎｏ□ 、Ｎ、
０等）にオゾン・ガスを添加した雰囲気にシリコン・ウ
ェーハを晒す事により、ＲＣＡ洗浄と同等の効果やレジ
スト除去効果があると共に、ガス、蒸気洗浄では洗浄剤
が桁違いに少な（て済むと云う効果がある。Furthermore, hydrofluoric acid gas-steam (steam means an evaporated component from an aqueous solution, and also contains water vapor), hydrofluoric acid gas,
Steam is mixed with hydrochloric acid gas/steam, ammonia gas/steam, nitrogen oxide gas/steam (No, No□, N,
By exposing silicon wafers to an atmosphere containing ozone gas (e.g. 0, etc.), it has the same effect and resist removal effect as RCA cleaning, and requires an order of magnitude less cleaning agent than gas or steam cleaning. There is an effect.
尚、オゾン・ガスの添加方法として酸素ガスを添加して
該−素ガスを反応室外部からの紫外線でオゾン化する方
法をとっても良い。Incidentally, as a method for adding ozone gas, a method may be used in which oxygen gas is added and the ozone gas is converted into ozone by ultraviolet rays from outside the reaction chamber.
尚、本法において、過酸化水素水の添加や過酸化水素ガ
ス・蒸気の添加を行なっても良い事は云うまでもない。It goes without saying that in this method, hydrogen peroxide solution or hydrogen peroxide gas/steam may be added.
本発明により、洗浄液寿命の長い、又、洗浄効果の大な
る洗浄法が少ない洗浄剤にて可能となる効果がある。The present invention has the advantage that a cleaning method with a long cleaning solution life and a high cleaning effect can be performed using a small amount of cleaning agent.
以上that's all
Claims (1)
水溶液、硝酸液又は弗酸ガス、蒸気、塩酸ガス、蒸気、
アンモニア・ガス、蒸気、酸化窒素ガス、蒸気に晒す事
を特徴とする洗浄法。Hydrofluoric acid aqueous solution with added ozone, hydrochloric acid aqueous solution, ammonia aqueous solution, nitric acid solution or hydrofluoric acid gas, steam, hydrochloric acid gas, steam,
A cleaning method characterized by exposure to ammonia gas, steam, nitrogen oxide gas, or steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23378890A JPH04114428A (en) | 1990-09-04 | 1990-09-04 | Cleaning process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23378890A JPH04114428A (en) | 1990-09-04 | 1990-09-04 | Cleaning process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04114428A true JPH04114428A (en) | 1992-04-15 |
Family
ID=16960580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23378890A Pending JPH04114428A (en) | 1990-09-04 | 1990-09-04 | Cleaning process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04114428A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5632847A (en) * | 1994-04-26 | 1997-05-27 | Chlorine Engineers Corp., Ltd. | Film removing method and film removing agent |
| KR19990039400A (en) * | 1997-11-12 | 1999-06-05 | 윤종용 | Cleaning solution for semiconductor device manufacturing process and removing photoresist and polymer using same |
| JPH11217591A (en) * | 1998-02-02 | 1999-08-10 | Kurita Water Ind Ltd | Cleaning water for electronic material |
| US6431183B1 (en) | 1997-10-09 | 2002-08-13 | Mitsubishi Denki Kabushiki Kaisha | Method for treating semiconductor substrates |
-
1990
- 1990-09-04 JP JP23378890A patent/JPH04114428A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5632847A (en) * | 1994-04-26 | 1997-05-27 | Chlorine Engineers Corp., Ltd. | Film removing method and film removing agent |
| US6431183B1 (en) | 1997-10-09 | 2002-08-13 | Mitsubishi Denki Kabushiki Kaisha | Method for treating semiconductor substrates |
| KR19990039400A (en) * | 1997-11-12 | 1999-06-05 | 윤종용 | Cleaning solution for semiconductor device manufacturing process and removing photoresist and polymer using same |
| JPH11217591A (en) * | 1998-02-02 | 1999-08-10 | Kurita Water Ind Ltd | Cleaning water for electronic material |
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