KR20030002517A - Method for cleaning - Google Patents
Method for cleaning Download PDFInfo
- Publication number
- KR20030002517A KR20030002517A KR1020010038166A KR20010038166A KR20030002517A KR 20030002517 A KR20030002517 A KR 20030002517A KR 1020010038166 A KR1020010038166 A KR 1020010038166A KR 20010038166 A KR20010038166 A KR 20010038166A KR 20030002517 A KR20030002517 A KR 20030002517A
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- KR
- South Korea
- Prior art keywords
- acetic acid
- coo
- hydrogen fluoride
- ammonium hydroxide
- cleaning
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004140 cleaning Methods 0.000 title claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims description 24
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 abstract 3
- 229910021641 deionized water Inorganic materials 0.000 abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 3
- 239000002904 solvent Substances 0.000 description 8
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 i.e. Chemical compound 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
-
- C11D2111/22—
Abstract
Description
본 발명은 세정 방법에 관한 것으로, 특히 금속층의 식각 공정을 진행한 후 어시틱 애시드(Acetic acid), 암모늄 하이드럭시드(Ammonium hydroxide), 수소 플루오르화물 및 초순수로 구성된 화학 용액을 사용한 세정 공정으로 식각 잔류물을 제거하여 소자의 생산성을 향상시키는 세정 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning method, and in particular, an etching residue in a cleaning process using a chemical solution composed of acetic acid, ammonium hydroxide, hydrogen fluoride, and ultrapure water after performing an etching process of a metal layer. It relates to a cleaning method to improve the productivity of the device by removing the.
반도체 소자는 매년 집적도의 증가 추세를 보이고 있으며, 이러한 집적도의 증가는 소자 각각의 구성 요소 면적 및 크기의 감소를 수반하게 되어 여러 가지 공정상의 제약을 맞게 된다.Semiconductor devices show an increase in the degree of integration every year, and the increase in the density is accompanied by a reduction in the area and size of each component of the device to meet various process constraints.
종래의 세정 방법은 도 1에서와 같이, 금속층 식각 공정(11)을 진행한다.In the conventional cleaning method, as shown in FIG. 1, the metal layer etching process 11 is performed.
여기서, 상기 금속층 식각 공정(11) 시 유기성 잔류물, 폴리머(Polymer) 및이동성 이온 등의 식각 잔류물이 존재한다.Here, in the metal layer etching process 11, there is an etching residue such as an organic residue, a polymer, and a mobile ion.
그리고, 90℃의 온도에서 솔벤트(Solvent)를 사용한 솔벤트 세정 공정(12)을 20 ∼ 30분간 진행하여 상기 식각 잔류물을 제거한다.Then, the solvent cleaning step (12) using a solvent (Solvent) at a temperature of 90 ℃ proceeds for 20 to 30 minutes to remove the etching residue.
여기서, 상기 솔벤트 세정 공정(12)은 상기 금속층의 손상을 방지하면서 상기 식각 잔류물을 깨끗하게 제거한다.Here, the solvent cleaning process 12 cleanly removes the etching residue while preventing damage to the metal layer.
상기 솔벤트는 주로 아민(Amine) 계열이다.The solvent is mainly amine based.
그러나, 종래의 세정 방법은 금속층의 식각 공정을 진행한 후, 식각 잔류물을 솔벤트와 같은 유기성 화학 용액을 사용한 세정 공정으로 제거하기 때문에 고가의 비용이 들고 90℃의 온도에서 세정 공정이 진행되어 불안전하며 또한 세정 공정 후 폐수 처리가 어렵고 20 ∼ 30분의 세정 공정 시간이 필요하여 작업 처리량이 감소하는 문제점이 있었다.However, in the conventional cleaning method, since the etching process of the metal layer is performed, the etching residue is removed by the cleaning process using an organic chemical solution such as solvent, which is expensive and the cleaning process proceeds at a temperature of 90 ° C. In addition, it is difficult to treat the waste water after the cleaning process and a 20 to 30 minute cleaning process time is required, thereby reducing the throughput.
본 발명은 상기의 문제점을 해결하기 위해 안출한 것으로 금속층의 식각 공정을 진행한 후 어시틱 애시드(Acetic acid), 암모늄 하이드럭시드(Ammonium hydroxide), 수소 플루오르화물 및 초순수로 구성된 화학 용액을 사용한 세정 공정으로 식각 잔류물을 제거하므로, 종래의 솔벤트보다 저가의 비용이 들고 실내 온도에서 세정 공정이 진행되어 안전하며 4 ∼ 6분의 세정 공정 시간이 필요하여 작업 처리량이 증가하는 세정 방법을 제공하는데 그 목적이 있다.The present invention has been made in order to solve the above problems and proceeds to the etching process of the metal layer and then to a cleaning process using a chemical solution consisting of acetic acid (Acetic acid), ammonium hydroxide (Ammonium hydroxide), hydrogen fluoride and ultrapure water The purpose of the present invention is to provide a cleaning method that removes etching residues, which is lower in cost than conventional solvents, is safe to proceed with the cleaning process at room temperature, and requires 4 to 6 minutes of cleaning process time to increase throughput. have.
도 1은 종래의 세정 방법을 나타낸 흐름도.1 is a flow chart showing a conventional cleaning method.
도 2는 본 발명의 실시 예에 따른 세정 방법을 나타낸 공정 흐름도.2 is a process flow diagram illustrating a cleaning method according to an embodiment of the present invention.
< 도면의 주요 부분에 대한 부호의 설명 ><Description of Symbols for Main Parts of Drawings>
31 : 금속층 식각 공정 33 : 무기물 세정 공정31 metal layer etching process 33 inorganic cleaning process
본 발명의 세정 방법은 금속층을 선택 식각하여 식각 잔류물이 발생된 상태에 있어서, 실내 온도에서 어시틱 애시드, 암모늄 하이드럭시드, 수소 플루오르화물 및 초순수로 구성된 화학 용액을 사용한 세정 공정을 4 ∼ 6분간 진행하여 상기 식각 잔류물을 제거하는 단계를 포함하여 이루어짐을 특징으로 한다.In the cleaning method of the present invention, in the state where etching residues are generated by selectively etching the metal layer, a cleaning process using a chemical solution composed of acetic acid, ammonium hydroxide, hydrogen fluoride and ultrapure water is performed at room temperature for 4 to 6 minutes. And removing the etching residues.
상기와 같은 본 발명에 따른 세정 방법의 바람직한 실시 예를 상세히 설명하면 다음과 같다.Referring to the preferred embodiment of the cleaning method according to the present invention as described above in detail.
본 발명의 실시 예에 따른 세정 방법은 도 2에서와 같이, 금속층 식각 공정(31)을 진행한다.In the cleaning method according to the embodiment of the present invention, as shown in FIG. 2, the metal layer etching process 31 is performed.
여기서, 상기 금속층의 식각 공정 시 유기성 잔류물, 폴리머 및 이동성 이온 등의 식각 잔류물이 존재한다.Here, in the etching process of the metal layer, there is an etching residue such as an organic residue, a polymer and a mobile ion.
그리고, 실내 온도에서 어시틱 애시드, 암모늄 하이드럭시드, 수소 플루오르화물 및 초순수로 구성된 화학 용액을 사용한 무기물 세정 공정(32)을 4 ∼ 6분간 진행하여 상기 식각 잔류물을 제거한다.Then, at room temperature, the inorganic cleaning process 32 using a chemical solution composed of acetic acid, ammonium hydroxide, hydrogen fluoride and ultrapure water is performed for 4 to 6 minutes to remove the etching residue.
여기서, 상기 무기물 세정 공정(32)에 사용되는 화학 용액의 구성비율은 어시틱 애시드와 암모늄 하이드럭시드는 1:1을 유지하고 수소 플루오르화물은 0.005 ∼ 0.01을 첨가하고 나머지 8은 초순수로 하며, 상기 화학 용액은 어시틱 애시드와 암모늄 하이드럭시드의 당량비 조정작용으로 즉 NH4OH + CH3COOH = CH3COO-NH4 ++ H2O로 유기물 및 이동성 이온을 제거할 수 있는 암모늄 아세테이트(Acetate)를 생성하게 되고 묽은 수소 플루오르화물은 상기 금속층에 손상을 가하지 않는다.Herein, the constituent ratio of the chemical solution used in the inorganic cleaning process 32 is maintained at 1: 1 in the acetic acid and the ammonium hydroxide, and the hydrogen fluoride is added in an amount of 0.005 to 0.01, and the remaining 8 is made of ultrapure water. The solution was prepared by adjusting the equivalence ratio of the acetic acid and ammonium hydroxide, i.e., ammonium acetate capable of removing organic and mobile ions with NH 4 OH + CH 3 COOH = CH 3 COO - NH 4 + + H 2 O. The resulting dilute hydrogen fluoride does not damage the metal layer.
그리고, 상기 암모늄 아세테이트는 CH3COO-NH4 ++ M++ H++ OH-= CH3COO-M++ NH4 +OH-+ H+의 반응식과 같이 이동성 이온(M+)을 제거하고, CH3COO-NH4 ++ R++ H++ OH-= CH3COO-R++ NH4 +OH-+ H+의 반응식과 같이 유기물(R+)을 제거한다.In addition, the ammonium acetate is CH 3 COO - NH 4 + + M + + H + + OH - = CH 3 COO - M + + NH 4 + OH - as shown in the reaction schemes + H + removal mobility ions (M +) to remove the organic materials, such as + reaction formula of H + (R +) -, and, CH 3 COO - NH 4 + + R + + H + + OH - = CH 3 COO - R + + + NH 4 OH.
이어, 상기 수소 플루오르화물은 6HF + SiO2= H2SiF6+ 2H2O의 반응식으로 폴리머를 제거한다.Subsequently, the hydrogen fluoride removes the polymer by the reaction scheme of 6HF + SiO 2 = H 2 SiF 6 + 2H 2 O.
그리고, CH3COOH + H2O = CH3COO-+ H3O+, CH3COO-NH4 ++ H3O+= CH3COOH + NH4 ++ H2O 및 NH4 ++ H+F-+ H2O = NH4F + H3O+의 반응식으로 pH는 일정하게 되고 NH4F에 의한 HF의 F-보충으로 균일한 식각을 유지하게 된다. And, CH 3 COOH + H 2 O = CH 3 COO - + H 3 O +, CH 3 COO - NH 4 + + H 3 O + = CH 3 COOH + NH 4 + + H 2 O and NH 4 + + H + F - a + H 2 O = NH 4 F + reaction formula of H 3 O + pH is constant F of HF by NH 4 F - maintains a uniform etching as a replacement.
본 발명의 세정 방법은 금속층의 식각 공정을 진행한 후 어시틱 애시드, 암모늄 하이드럭시드, 수소 플루오르화물 및 초순수로 구성된 화학 용액을 사용한 세정 공정으로 식각 잔류물을 제거하므로, 종래의 솔벤트보다 저가의 비용이 들고 실내 온도에서 세정 공정이 진행되어 안전하며 4 ∼ 6분의 세정 공정 시간이 필요하여 작업 처리량이 증가하므로 소자의 생산성을 향상시키는 효과가 있다.Since the cleaning method of the present invention removes the etching residues by a chemical solution consisting of an acetic acid, ammonium hydroxide, hydrogen fluoride and ultrapure water after the etching process of the metal layer, the cost is lower than conventional solvents. It is safe to carry out the cleaning process at room temperature and the cleaning process time of 4 to 6 minutes is required and the throughput is increased, thereby improving the productivity of the device.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010038166A KR20030002517A (en) | 2001-06-29 | 2001-06-29 | Method for cleaning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010038166A KR20030002517A (en) | 2001-06-29 | 2001-06-29 | Method for cleaning |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20030002517A true KR20030002517A (en) | 2003-01-09 |
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| KR1020010038166A KR20030002517A (en) | 2001-06-29 | 2001-06-29 | Method for cleaning |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100678482B1 (en) * | 2006-01-17 | 2007-02-02 | 삼성전자주식회사 | Cleaning solution for a silicon surface and methods of fabricating a semiconductor device using the same |
| KR100805693B1 (en) * | 2001-12-14 | 2008-02-21 | 주식회사 하이닉스반도체 | Cleanung chemical and method for cleaning metal layer |
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|---|---|---|---|---|
| US5972123A (en) * | 1997-06-13 | 1999-10-26 | Cfmt, Inc. | Methods for treating semiconductor wafers |
| KR20000055067A (en) * | 1999-02-03 | 2000-09-05 | 윤종용 | Aqueous cleaning solution for removing contaminants from surface of integrated circuit substrate and cleaning method using thereof |
| US6132522A (en) * | 1996-07-19 | 2000-10-17 | Cfmt, Inc. | Wet processing methods for the manufacture of electronic components using sequential chemical processing |
| KR20020079038A (en) * | 2001-04-12 | 2002-10-19 | 삼성전자 주식회사 | A cleaning compsite of the metal etcher and the method thereof |
| KR20020095729A (en) * | 2001-06-15 | 2002-12-28 | 삼성전자 주식회사 | Mos transistor for semiconductor device and method for manufacturing the same |
-
2001
- 2001-06-29 KR KR1020010038166A patent/KR20030002517A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6132522A (en) * | 1996-07-19 | 2000-10-17 | Cfmt, Inc. | Wet processing methods for the manufacture of electronic components using sequential chemical processing |
| US5972123A (en) * | 1997-06-13 | 1999-10-26 | Cfmt, Inc. | Methods for treating semiconductor wafers |
| KR20000055067A (en) * | 1999-02-03 | 2000-09-05 | 윤종용 | Aqueous cleaning solution for removing contaminants from surface of integrated circuit substrate and cleaning method using thereof |
| KR20020079038A (en) * | 2001-04-12 | 2002-10-19 | 삼성전자 주식회사 | A cleaning compsite of the metal etcher and the method thereof |
| KR20020095729A (en) * | 2001-06-15 | 2002-12-28 | 삼성전자 주식회사 | Mos transistor for semiconductor device and method for manufacturing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100805693B1 (en) * | 2001-12-14 | 2008-02-21 | 주식회사 하이닉스반도체 | Cleanung chemical and method for cleaning metal layer |
| KR100678482B1 (en) * | 2006-01-17 | 2007-02-02 | 삼성전자주식회사 | Cleaning solution for a silicon surface and methods of fabricating a semiconductor device using the same |
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