KR100305213B1 - Method of cleaning a semiconductor device - Google Patents
Method of cleaning a semiconductor device Download PDFInfo
- Publication number
- KR100305213B1 KR100305213B1 KR1019970079250A KR19970079250A KR100305213B1 KR 100305213 B1 KR100305213 B1 KR 100305213B1 KR 1019970079250 A KR1019970079250 A KR 1019970079250A KR 19970079250 A KR19970079250 A KR 19970079250A KR 100305213 B1 KR100305213 B1 KR 100305213B1
- Authority
- KR
- South Korea
- Prior art keywords
- cleaning
- metal
- semiconductor device
- organic solvent
- water
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004140 cleaning Methods 0.000 title claims abstract description 13
- 239000004065 semiconductor Substances 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012459 cleaning agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 0 CN1*CC(*)CCCC(C2)[C@]2[C@](C2)C2C1 Chemical compound CN1*CC(*)CCCC(C2)[C@]2[C@](C2)C2C1 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005406 washing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C11D2111/22—
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
Description
본 발명은 반도체 소자의 세정 방법에 관한 것으로, 특히 금속 식각 또는 비아 홀 식각 공정시 발생하는 폴리머(polymer)를 효과적으로 제거하기 위한 세정 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning a semiconductor device, and more particularly, to a method for effectively removing a polymer generated during a metal etching or via hole etching process.
현재 금속 또는 비아 홀을 식각한 후 생성된 폴리머를 제거하기 위한 세정(cleaning)공정시 사용하고 있는 ACT-935나 다른 일반적인 세정제(cleaning agent)의 주성분은 하이드록실아민(hydroxylamine)(NH2OH)이다. 이 화학종(chemical species)의 역할은 폴리머중의 금속과 배위 결합(coordination bond)을 일으켜 용매(solvent)에 잘 녹는 유기금속종(organometallic species)인 착화합물(chelated compound)을 형성하는 것이다. 그러나 하이드록실아민 자체로는 반응성이 매우 커서 폴리머내의 금속 뿐만 아니라 산화 상태(oxidation state)가 0인 금속 자체와도 반응을 일으켜 착화합물을 형성하므로, 하이드록실아민 이외에 주로아미노기(amino group)(-NH2)나 하이드록실기(hydroxyl group)(-OH)를 동시에 가지고 있는 물질을 사용한다. 그러나, 이 화합물들은 60∼80℃의 고온에서 세정 공정을 실시해야 하며, 상온에서는 세정이 잘되지 않는다.The main component of ACT-935 or other common cleaning agents currently used in the cleaning process to remove polymers formed by etching metals or via holes is hydroxylamine (NH 2 OH). to be. The role of this chemical species is to form a chelated compound, an organometallic species that is well soluble in the solvent by forming a coordination bond with the metal in the polymer. However, hydroxylamine itself is very reactive and reacts not only with metals in the polymer but also with metals with zero oxidation state (oxidation state) to form complexes, and in addition to hydroxylamine, mainly amino groups (-NH) 2 ) or a substance which has a hydroxyl group (-OH) at the same time. However, these compounds must be subjected to a cleaning process at a high temperature of 60 to 80 ℃, it is difficult to clean at room temperature.
따라서, 본 발명은 반도체 소자 제조 공정 중 생성되는 유기물을 금속의 손상 없이 제거할 수 있는 세정 방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a cleaning method capable of removing organic substances generated during a semiconductor device manufacturing process without damaging the metal.
상술한 목적을 달성하기 위한 본 발명은 금속층 식각 후 또는 비아 홀 식각 후 생성되는 폴리머 및 산화수가 0 이상인 산화금속만을 효과적으로 제거하기 위한 반도체 소자의 세정 방법에 있어서, 알킬디아민을 잘 녹이고 물과도 잘 섞일 수 있는 양성자성이면서 수-혼화성인 유기 용매에 1,3-디아미노프로판을 용해시킨 세정제를 이용하여 세정 공정을 실시하는 것을 특징으로 한다.In order to achieve the above object, the present invention provides a method of cleaning a semiconductor device for effectively removing only a polymer and a metal oxide having a number of 0 or more after metal layer etching or via hole etching, and dissolving alkyldiamine well and well with water. A cleaning process is performed by using a cleaning agent in which 1,3-diaminopropane is dissolved in an admixable protic and water-miscible organic solvent.
본 발명은 폴리머 상태로 있는 금속과 같이 산화 상태에 있는 금속, 즉 산화 수가 0보다 큰 금속에만 착화합 반응이 일어나고, 산화수가 0인 금속과는 반응하지 않도록 반응성(reactivity)과 선택성(selectivity)이 조절된 세정제를 제시한다.According to the present invention, the complexation reaction occurs only on a metal in an oxidized state, such as a metal in a polymer state, that is, a metal having an oxidation number greater than zero, and does not react with a metal having zero oxidation number. Present a controlled detergent.
본 발명에서는 현재 금속 식각 후 세정제로 사용되고 있는 화합물 대신에 하이드록실아민보다는 작고 에탄올아민(ethanolamine)보다는 큰 반응성을 가지는 동시에 하이드록실아민보다는 크고 아미노알콜(aminoalcohol)보다는 작은 선택성을 갖는 1,3-디아미노프로판(1,3-diaminopropane)(H2NCH2CH2CH2NH2)을 사용한다. 이것을 사용하면 산화 상태에 있는 산화 금속(oxidated metal)과 착반응(chelation reaction)을 일으켜 용매에 잘 녹는 유기금속종이 된다.In the present invention, instead of the compound that is currently used as a cleaning agent after metal etching, 1,3-dia having smaller reactivity than hydroxylamine and greater reactivity than ethanolamine and larger selectivity than hydroxylamine and smaller than aminoalcohol Minopropane (1,3-diaminopropane) (H 2 NCH 2 CH 2 CH 2 NH 2 ) is used. When used, it forms a chelation reaction with an oxidized metal in an oxidized state, and becomes an organometallic species that is well soluble in a solvent.
본 발명에서 폴리머를 제거하기 위한 대체 물질로 1,3-디아미노프로판을 사용하는 이유는 에탄올아민(ethanolamine)(H2NCH2CH2OH)이 금속과 결합하여 [화학식 1]과 같은 오각형고리화합물(5-membered ring compound)을 형성하는 것과 유사하게 1,3-디아미노프로판도 [화학식 2]와 같은 육각형의 고리 화합물을 형성하기 때문이다.The reason for using 1,3-diaminopropane as an alternative material for removing the polymer in the present invention is that ethanolamine (H 2 NCH 2 CH 2 OH) is combined with a metal pentagram ring as shown in [Formula 1]. This is because 1,3-diaminopropane also forms a hexagonal ring compound as shown in [Formula 2] similarly to forming a 5-membered ring compound.
여기서, [화학식 1] 및 [화학식 2]의 M은 금속이다.Here, M in [Formula 1] and [Formula 2] is a metal.
용매로는 알킬디아민을 잘 녹이는 동시에 물과도 잘 섞일 수 있는 디메틸설폭사이드(dimethyl sulfoxide)나 [화학식 3]의 디메틸포름아미드(dimethyl formamide)(HC(O)N(CH3)2)와 같은 양성자성(Aprotic)이면서 수-혼화성(Water-misicble)인 유기 용매를 사용한다.As a solvent, such as dimethyl sulfoxide or dimethyl formamide (HC (O) N (CH 3 ) 2 ), which can dissolve alkyldiamine well and mix well with water. An organic solvent that is protic and water-misicble is used.
상술한 바와 같이 본 발명에 의한 1,3-디아미노프로판을 폴리머를 세정하기 위한 세정제로 사용하면, 종래의 에탄올아민보다 비교적 순한 조건(mild condition)에서 산화 금속을 보다 쉽게 착화하는 치환 반응을 일으킬 수 있으며, 치환 반응의 속도는 용매내의 1,3-디아미노프로판의 양을 통해 조절할 수 있다. 용매로서 유기 용매(organic solvent)인 디메틸 설폭사이드(dimethyl sulfoxide)나 디메틸 포름아미드(dimethyl formamide)를 사용하면 리간드가 착화된 유기금속종이 잘 녹고 유전 상수가 크므로 세척(washing) 공정에서 물과 잘 섞여 공정이 간단해 진다.As described above, when the 1,3-diaminopropane according to the present invention is used as a cleaning agent for cleaning the polymer, it causes a substitution reaction to complex the metal oxide more easily in a mild condition than a conventional ethanolamine. The rate of substitution reaction can be controlled via the amount of 1,3-diaminopropane in the solvent. When organic solvents such as dimethyl sulfoxide or dimethyl formamide are used as the solvent, the organometallic species complexed with the ligand are well dissolved and the dielectric constant is high, so it is well suited to water and water in the washing process. Mixing simplifies the process.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970079250A KR100305213B1 (en) | 1997-12-30 | 1997-12-30 | Method of cleaning a semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970079250A KR100305213B1 (en) | 1997-12-30 | 1997-12-30 | Method of cleaning a semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19990059053A KR19990059053A (en) | 1999-07-26 |
| KR100305213B1 true KR100305213B1 (en) | 2001-11-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970079250A KR100305213B1 (en) | 1997-12-30 | 1997-12-30 | Method of cleaning a semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100305213B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6457479B1 (en) * | 2001-09-26 | 2002-10-01 | Sharp Laboratories Of America, Inc. | Method of metal oxide thin film cleaning |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08157887A (en) * | 1994-12-06 | 1996-06-18 | Kao Corp | Water-based detergent composition |
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1997
- 1997-12-30 KR KR1019970079250A patent/KR100305213B1/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08157887A (en) * | 1994-12-06 | 1996-06-18 | Kao Corp | Water-based detergent composition |
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| Publication number | Publication date |
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| KR19990059053A (en) | 1999-07-26 |
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