KR20020002749A - Method of cleaning in a semiconductor device - Google Patents
Method of cleaning in a semiconductor device Download PDFInfo
- Publication number
- KR20020002749A KR20020002749A KR1020000037035A KR20000037035A KR20020002749A KR 20020002749 A KR20020002749 A KR 20020002749A KR 1020000037035 A KR1020000037035 A KR 1020000037035A KR 20000037035 A KR20000037035 A KR 20000037035A KR 20020002749 A KR20020002749 A KR 20020002749A
- Authority
- KR
- South Korea
- Prior art keywords
- hydroxypiperidine
- cleaning
- metal
- semiconductor device
- deionized water
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004140 cleaning Methods 0.000 title claims abstract description 17
- 239000004065 semiconductor Substances 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- HDOWRFHMPULYOA-UHFFFAOYSA-N piperidin-4-ol Chemical compound OC1CCNCC1 HDOWRFHMPULYOA-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 abstract 4
- 229910021641 deionized water Inorganic materials 0.000 abstract 4
- 150000001875 compounds Chemical class 0.000 description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 3
- -1 amine alcohols Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
Description
본 발명은 반도체 소자의 세정 방법에 관한 것으로, 특히 반도체 소자의 제조 공정중 금속 배선 또는 비아 홀을 형성하기 위한 식각 공정 후 발생되는 폴리머를 제거하기 위한 세정제로 4-하이드록시피페리딘(4-Hydroxypiperidine)을 이용함으로써 식각 공정후의 세정 공정을 개선할 수 있는 반도체 소자의 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. In particular, 4-hydroxypiperidine (4- is used as a cleaning agent for removing polymers generated after an etching process for forming metal wirings or via holes in a semiconductor device manufacturing process. The present invention relates to a method for cleaning a semiconductor device capable of improving the cleaning process after an etching process by using hydroxypiperidine).
현재 금속 배선 또는 비아 홀을 형성하기 위한 식각 공정을 실시한 후 생성된 폴리머를 제거하기 위한 세정 공정에 사용되는 ACT-935나 다른 일반적인 세정제(Cleaning Agent)의 주성분은 하이드록실아민(Hydroxylamine; NH2OH)과 에틸메틸아민(Ethylmethylamin; CH3CH2NHCH3, MEA)이다. 이들 화학종(Chemical Species)은 폴리머중의 금속과 배위 결합(Coordination Bond)을 하여 용매에 잘 녹은 유기금속종(Organometallic Species)인 착화합물(Chelated Compound)을 형성하는 역할을 한다.Currently, the main component of ACT-935 or other common cleaning agents used in the cleaning process to remove the formed polymer after the etching process to form metal wiring or via holes is hydroxylamine (NH 2 OH). ) And ethylmethylamine (CH 3 CH 2 NHCH 3 , MEA). These chemical species form coordination bonds with the metals in the polymer to form complex compounds, which are organometallic species that are well dissolved in solvents.
그러나, 하이드록실아민이나 MEA 자체로는 반응성(Reactivity)이 매우 커서 폴리머내의 금속 뿐만 아니라 산화 상태(Oxidation State)가 0인 금속 자체와도 반응을 일으켜 착화합물을 형성하므로 금속 배선이나 Ti, TiN등의 장벽 금속층이 손상되게 된다. 그러므로 하이드록실아민이나 MEA 이외에 주로 아미노 그룹(Amino Group)(-NH2)이나 하이드록실 그룹(Hydroxyl Group)(-OH)을 동시에 가지고 있는 물질을 사용하여 세정 공정을 실시한다. 그런데, 이 화합물들은 60∼80℃ 정도의 고온에서 세정 공정을 진행해야 하며 상온에서는 세정이 잘되지 않는다.However, the hydroxylamine or MEA itself has a very high reactivity, so it reacts not only with the metal in the polymer but also with the metal with the oxidation state of 0, thereby forming a complex compound. The barrier metal layer is damaged. Therefore, in addition to hydroxylamine and MEA, the cleaning process is carried out using a substance which simultaneously contains an amino group (-NH 2 ) or a hydroxyl group (-OH). However, these compounds have to proceed with the cleaning process at a high temperature of about 60 ~ 80 ℃ and are not well cleaned at room temperature.
본 발명의 목적은 폴리머 상태로 있는 금속과 같이 산화 상태에 있는 산화수가 0 이상인 금속에 국한하여 착화합 반응이 일어나고 산화수가 0인 금속과는 반응하지 않도록 반응성(Reactivity)과 선택성(Selectibity)이 조절된 세정제를 이용한 반도체 소자의 세정 방법을 제공하는데 있다.An object of the present invention is to control the reactivity and selectivity so that the complexation reaction is limited to a metal having an oxidation number greater than or equal to zero, such as a metal in a polymer state, and not reacting with a metal having an oxidation number of zero. The present invention provides a method for cleaning a semiconductor device using the cleansing agent.
본 발명에 따른 반도체 소자의 세정 방법은 금속 배선 또는 비아 홀을 형성하기 위한 식각 공정에서 발생된 폴리머를 제거하기 위한 세정 공정을 4-하이드록시피페리딘을 이용하여 실시하되, 용매로서 순수를 사용하거나, 순수에 암모니아를 첨가하여 용매로 사용하는 것을 특징으로 한다.In the method for cleaning a semiconductor device according to the present invention, a 4-hydroxypiperidine may be used to perform a cleaning process for removing polymer generated in an etching process for forming metal wirings or via holes, using pure water as a solvent. Or ammonia is added to the pure water to be used as a solvent.
이하, 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
현재 금속 배선 또는 비아 홀을 형성하기 위한 식각 공정을 실시한 후 세정제로 사용되고 있는 화합물들 대신에 하이드록실아민 보다는 반응성이 작고 일반적인 아민알코홀(Aminalcohol)류 보다는 반응성이 큰 동시에 하이드록실아민 보다는 선택성이 크고 아민아코홀 보다는 선택성이 작은 [화학식 1]에 나타낸 바와 같은 4-하이드록시피페리딘(4-Hydroxypiperidine)을 사용하면 산화 상태에 있는 금속과 착화합 반응을 일으켜 일으켜 용매, 즉 순수에 잘 녹는 유기금속종이 된다.After performing etching process to form metal wiring or via hole, it is less reactive than hydroxylamine, more reactive than general amine alcohols, and more selective than hydroxylamine instead of compounds used as cleaning agent. 4-Hydroxypiperidine as shown in [Formula 1], which is less selective than acohol, causes complex reaction with the metal in the oxidized state, which is an organic metal that is easily dissolved in a solvent, that is, pure water. It becomes a servant.
대체 물질로 4-하이드록시피페리딘을 착화합 리간드(Chelation Ligand)로 선택한 이유는 에탄올아민(Ethanolaimine, H2NCH2CH2OH)이 금속과 결합하여 [화학식 2]와 같은 오각형 고리 화합물(5-membered ring compound)을 형성하듯이 4-하이드록시피페리딘도 이와 유사한 [화학식 3]과 같은 육각형 고리 화합물을 형성하기 때문이다. 또한, 이렇게 형성된 육각형 고리 화합물은 플립(Flip)이 되면서 즉, 두가지 형태로 평형(Equilibrium)을 이루며 [화학식 4]와 같이 안정화되어 리 채털리어(Le Chatelier)의 법칙에 의해 일반적으로 생성물이 평형을 이루지 않는 아민알코홀(Aminoalcohol)류 보다는 폴리머를 형성하고 있는 산화 상태의 금속과 반응을 더 잘 일으키며 동시에 생성물이 안정화됨으로써 착화합물이 된 금속 이온이 다시 폴리머로 되는 것을 방지해 준다. 용매(Solvent)로는 순수(DI water)를 사용하며 배위 결합을 보다 더 잘 일으키기 위하여 암모니아수(NH4OH)를 첨가하면 된다.The reason for choosing 4-hydroxypiperidine as a complexing ligand (Chelation Ligand) is because ethanolamine (Ethanolaimine, H 2 NCH 2 CH 2 OH) is combined with a metal to form a pentagonal ring compound such as [Formula 2] ( This is because 4-hydroxypiperidine forms a hexagonal ring compound similar to [Formula 3], as it forms a 5-membered ring compound. In addition, the hexagonal ring compound thus formed is flipped, that is, equilibrium in two forms (Equilibrium) and stabilized as shown in [Formula 4] by the law of Le Chatelier generally the product is in equilibrium It reacts better with oxidized metals forming polymers than amine alcohols that do not form, and at the same time stabilizes the product, preventing complex metal ions from becoming polymers again. Pure water (DI water) is used as a solvent, and ammonia water (NH 4 OH) may be added to generate coordination bonds better.
상술한 바와 같이 본 발명에 의하면 4-하이드록시피페리딘을 사용하여 세정 공정을 실시하면 종래의 에탄올아민보다 비교적 순한 조건(mild condition)에서 산화 금속을 보다 쉽게 착화합하는 치환 반응(Substitution Reaction)을 일으키며 반응 속도는 용매내의 4-하이드록시피페리딘의 양을 통해 조절할 수 있다. 또한, 용매로는 순수를 사용하며, 반응을 촉진시키기 위해 암모니아를 첨가한다. 암모니아를 첨가하면 4-하이드록시피페리딘의 하이드록실 그룹에서 H+를 제거하여 4-하이드록시피페리딘의 음이온이 되어 보다 더 효과적으로 산화 상태의 금속과 배위 결합을 잘일으켜 폴리머를 제거할 수 있다.As described above, according to the present invention, when the washing process is performed using 4-hydroxypiperidine, a substitution reaction is performed to complex the metal oxide more easily in a mild condition than in the conventional ethanolamine. And the reaction rate can be controlled via the amount of 4-hydroxypiperidine in the solvent. In addition, pure water is used as the solvent, and ammonia is added to promote the reaction. The addition of ammonia removes H + from the hydroxyl group of the 4-hydroxypiperidine, becoming an anion of the 4-hydroxypiperidine, which allows more efficient coordination of the metal with the oxidized state to remove the polymer. have.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000037035A KR20020002749A (en) | 2000-06-30 | 2000-06-30 | Method of cleaning in a semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000037035A KR20020002749A (en) | 2000-06-30 | 2000-06-30 | Method of cleaning in a semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20020002749A true KR20020002749A (en) | 2002-01-10 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020000037035A KR20020002749A (en) | 2000-06-30 | 2000-06-30 | Method of cleaning in a semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20020002749A (en) |
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2000
- 2000-06-30 KR KR1020000037035A patent/KR20020002749A/en not_active Application Discontinuation
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