KR20200133177A - Functional cleaning solution containing hydrogen water and wafer cleaning method after CMP process using the same - Google Patents
Functional cleaning solution containing hydrogen water and wafer cleaning method after CMP process using the same Download PDFInfo
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- KR20200133177A KR20200133177A KR1020200054976A KR20200054976A KR20200133177A KR 20200133177 A KR20200133177 A KR 20200133177A KR 1020200054976 A KR1020200054976 A KR 1020200054976A KR 20200054976 A KR20200054976 A KR 20200054976A KR 20200133177 A KR20200133177 A KR 20200133177A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004140 cleaning Methods 0.000 title claims abstract description 54
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 23
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 8
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007517 polishing process Methods 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 41
- 238000005498 polishing Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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Classifications
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- 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
- C11D3/0042—Reducing agents
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0005—Special cleaning or washing methods
- C11D11/0011—Special cleaning or washing methods characterised by the objects to be cleaned
- C11D11/0023—"Hard" surfaces
- C11D11/0047—Electronic devices, e.g. PCBs or semiconductors
-
- 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
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- C11D2111/22—
Abstract
Description
본 발명은 수소수를 포함하는 기능성 세정액 및 이를 이용한 CMP 공정 후 웨이퍼 세정 방법에 관한 것이다. 보다 구체적으로 산화 세륨(ceria) 입자를 사용한 CMP 연마 공정 후 웨이퍼 표면을 효과적으로 세정할 수 있는 기능성 세정액 및 이를 이용한 CMP 공정 후 웨이퍼 세정 방법에 관한 것이다. The present invention relates to a functional cleaning solution containing hydrogen water and a wafer cleaning method after a CMP process using the same. More specifically, it relates to a functional cleaning solution capable of effectively cleaning a wafer surface after a CMP polishing process using cerium oxide particles, and a wafer cleaning method after a CMP process using the same.
반도체 웨이퍼는 일반적으로 규소 웨이퍼와 같은 기판으로 구성된다. 기판 표면의 평면화, 평탄화를 위해 화학적-기계적 연마 (CMP) 공정이 필요하며, CMP 공정에서는 일반적으로 산성 또는 염기성 용액으로서, 연마 슬러리를 포함하는 연마 용액을 사용한다. 그러나 CMP 공정에서 웨이퍼 표면 상에 연마 조성물이나 이의 잔존물이 남아있게 되고, 이는 반도체 웨이퍼의 성능에 부정적인 영향을 미칠 수 있다. 따라서, CMP 공정을 완료한 후 일반적으로 연마 조성물을 세정 용액으로 웨이퍼 표면에서 씻어내는 단계가 필요하다.Semiconductor wafers are generally composed of a substrate such as a silicon wafer. A chemical-mechanical polishing (CMP) process is required to planarize and planarize the surface of the substrate, and in the CMP process, a polishing solution including a polishing slurry is generally used as an acidic or basic solution. However, in the CMP process, the polishing composition or its residue remains on the wafer surface, which may negatively affect the performance of the semiconductor wafer. Therefore, after completing the CMP process, it is generally necessary to wash the polishing composition from the wafer surface with a cleaning solution.
산화 세륨(ceria, CeO2) 입자를 사용하는 CMP 공정의 경우 산화 세륨 입자와 SiO2 웨이퍼 표면과의 화학적 결합에 의해 연마량 측면에서 매우 유리하다. 하지만 산화 세륨의 Se 입자와 웨이퍼의 산소 입자 간의 강한 화학적 결합 때문에 CMP 공정 후 입자를 세정하는 세정 측면에서는 불리하다.In the case of the CMP process using cerium oxide (Ceria, CeO 2 ) particles, it is very advantageous in terms of the amount of polishing due to chemical bonding between the cerium oxide particles and the SiO 2 wafer surface. However, because of the strong chemical bonding between the Se particles of cerium oxide and the oxygen particles of the wafer, it is disadvantageous in terms of cleaning the particles after the CMP process.
CMP 공정 이후 세정 방식에 있어서, 기존의 세정 방식은 암모니아, 과산화수소, 물을 혼합하여 세정하는 SC1 세정과, 염산, 과산화수소, 물을 혼합하는 SC2 세정으로 이루어지고, SC2에서 DHF 단계는 희석 불산을 이용해 자연 산화막을 제거하는 단계를 포함한다. 이러한 기존 세정 방식의 경우 웨이퍼 표면에 손상을 줄 수 있고 강한 화학물질(chemical)을 사용하므로 처리 비용이 많이 든다. 따라서 세정 공정에 대한 추가적인 연구가 요구되고 있는 실정이다.In the cleaning method after the CMP process, the conventional cleaning method consists of SC1 cleaning by mixing ammonia, hydrogen peroxide, and water, and SC2 cleaning by mixing hydrochloric acid, hydrogen peroxide and water. And removing the natural oxide film. In the case of such an existing cleaning method, it is possible to damage the wafer surface and use strong chemicals, so processing costs are high. Therefore, further research on the cleaning process is required.
이러한 배경하에서, 본 발명자들은 상기와 같은 문제점을 해결하기 위해 예의 노력한 결과, 친환경 원료인 수소를 반도체 웨이퍼의 세정 공정에 환원제로서 활용할 수 있음을 확인함으로써 본 발명을 완성하였다.Under this background, the present inventors have completed the present invention by confirming that hydrogen, an eco-friendly raw material, can be used as a reducing agent in the cleaning process of semiconductor wafers as a result of earnest efforts to solve the above problems.
본 발명의 하나의 목적은, 반도체 웨이퍼의 화학적 기계적 평탄화(CMP) 후 세정 또는 버프 클린(Buff clean)을 위한 세정 조성물을 제공하는 것이다.One object of the present invention is to provide a cleaning composition for cleaning or buff clean after chemical mechanical planarization (CMP) of a semiconductor wafer.
본 발명의 다른 하나의 목적은, 반도체 웨이퍼의 세정 방법을 제공하는 것이다.Another object of the present invention is to provide a method for cleaning a semiconductor wafer.
상기 목적을 달성하기 위한 본 발명의 하나의 양태는, 수소수를 포함하는, 반도체 웨이퍼의 화학적 기계적 평탄화(CMP) 후 세정 또는 버프 클린(Buff clean)을 위한 세정 조성물을 제공한다.One aspect of the present invention for achieving the above object is to provide a cleaning composition for cleaning or buff clean after chemical mechanical planarization (CMP) of a semiconductor wafer, including hydrogen water.
상기 목적을 달성하기 위한 본 발명의 다른 하나의 양태는, 탈이온수 (Deionized water)를 린스하는 단계; 린스된 상기 탈이온수가 소수성 중공섬유 막 (Hydrophobic hollow fiber membrane)으로 전달되는 단계; 및 상기 소수성 중공섬유 막을 통해 수소 기체가 탈이온수로 주입되어 수소수가 제조되는 단계를 포함하는, 반도체 웨이퍼의 세정 방법을 제공한다.Another aspect of the present invention for achieving the above object, the step of rinsing deionized water (Deionized water); Transferring the rinsed deionized water to a hydrophobic hollow fiber membrane; And it provides a method for cleaning a semiconductor wafer comprising the step of producing hydrogen water by injecting hydrogen gas into deionized water through the hydrophobic hollow fiber membrane.
본 발명의 세정 조성물 또는 세정 방법은 친환경적이고 적은 농도로도 효과를 이끌어낼 수 있는 수소를 사용하는 점에서 기술적 이점이 있으며, 안정성이 높으면서도 별도의 후처리가 필요하지 않은 점에서 경제적이라는 장점이 있다.The cleaning composition or cleaning method of the present invention has a technical advantage in that it is environmentally friendly and uses hydrogen that can elicit an effect at a small concentration, and it is economical in that it has high stability and does not require a separate post-treatment. have.
도 1은 수소수 제조 공정을 나타낸 도이다.
도 2는 수소수에 의한 웨이퍼 표면과 세리아 입자간의 결합 변화를 나타낸 도이다.
도 3은 웨이퍼 표면의 입자 개수, Ce 이온에 대한 수소수의 효과를 나타낸 도이다.
도 4는 수소수 사용에 따른 세리아 입자 표면 상태 변화를 UV-visible 분석 결과로 나타낸 도이다.
도 5는 세정 전, 후의 웨이퍼 표면에 대한 XPS 분석 결과를 나타낸 도이다.1 is a diagram showing a hydrogen water manufacturing process.
2 is a diagram showing a change in bonding between a wafer surface and ceria particles due to hydrogen water.
3 is a diagram showing the effect of the number of particles on the wafer surface and the number of hydrogen on Ce ions.
4 is a diagram showing a change in surface state of ceria particles according to the use of hydrogen water as a result of UV-visible analysis.
5 is a diagram showing the results of XPS analysis on the wafer surface before and after cleaning.
이를 구체적으로 설명하면 다음과 같다. 한편, 본 발명에서 개시된 각각의 설명 및 실시형태는 각각의 다른 설명 및 실시 형태에도 적용될 수 있다. 즉, 본 발명에서 개시된 다양한 요소들의 모든 조합이 본 발명의 범주에 속한다. 또한, 하기 기술된 구체적인 서술에 의하여 본 발명의 범주가 제한된다고 볼 수 없다.This will be described in detail as follows. Meanwhile, each description and embodiment disclosed in the present invention can be applied to each other description and embodiment. That is, all combinations of various elements disclosed in the present invention belong to the scope of the present invention. In addition, it cannot be seen that the scope of the present invention is limited by the specific description described below.
본 발명은 수소수를 포함하는, 반도체 웨이퍼의 화학적 기계적 평탄화(CMP) 후 세정 또는 버프 클린(Buff clean)을 위한 세정 조성물을 제공한다.The present invention provides a cleaning composition for cleaning or buff clean after chemical mechanical planarization (CMP) of a semiconductor wafer comprising hydrogen water.
본 발명은 탈이온수 (Deionized water)를 린스하는 단계; 린스된 상기 탈이온수가 소수성 중공섬유 막 (Hydrophobic hollow fiber membrane)으로 전달되는 단계; 및 상기 소수성 중공섬유 막을 통해 수소 기체가 탈이온수로 주입되어 수소수가 제조되는 단계를 포함하는, 반도체 웨이퍼의 세정 방법을 제공한다.The present invention comprises the steps of rinsing deionized water; Transferring the rinsed deionized water to a hydrophobic hollow fiber membrane; And it provides a method for cleaning a semiconductor wafer comprising the step of producing hydrogen water by injecting hydrogen gas into deionized water through the hydrophobic hollow fiber membrane.
본 발명에서 수소수(Hydrogen water)는 수소분자(H2)가 분자 상태 그대로 녹아 있는 물을 의미하며, 전기분해식, 수소가스 혼합식으로 제조될 수 있으나, 구체적으로 수소가스 혼합식으로 제조된 것일 수 있다. 수소가스 혼합식은 원수를 정수처리 한 후, 헨리의 법칙에 따라 수소 기체를 고압으로 충진을 하는 방법이다.Hydrogen water in the present invention refers to water in which hydrogen molecules (H 2 ) are dissolved in a molecular state as it is, and may be prepared by an electrolysis method or a hydrogen gas mixture, but specifically, a hydrogen gas mixture. Can be. The hydrogen gas mixing method is a method of purifying raw water and then filling hydrogen gas at high pressure according to Henry's Law.
본 발명에서, 상기 수소수는 약염기성 또는 강염기성일 수 있고, 9 내지 12, 또는 10 내지 12, 또는 10.5 내지 11.5 의 pH 값을 갖는 것일 수 있다. 수소수의 pH가 강염기에 가까울수록 세정 능력이 더욱 우수할 수 있다.In the present invention, the hydrogen water may be weakly basic or strongly basic, and may have a pH value of 9 to 12, or 10 to 12, or 10.5 to 11.5. The closer the pH of hydrogen water is to a strong base, the better the cleaning ability can be.
본 발명에서, 상기 수소수는 반도체 웨이퍼 표면의 세리아(Ceria) 입자에서 Ce4+ → Ce3+의 환원 반응을 촉진시키는 것일 수 있다. CMP 공정 후 웨이퍼 표면 세정을 위해 슬러리(Slurry) 대신 물을 이용하여 웨이퍼 표면을 린스(rinse) 한다. 세리아 입자의 경우 웨이퍼 표면에 Ce3+, Ce4+가 공존하는데 Ce3+가 SiO2의 웨이퍼 표면과 결합을 이루면 Ce4+가 되며, 결합력이 강하여 쉽게 세정되지 않는 문제가 있다. 이 때, 수소수를 이용해 Ce4+를 Ce3+로 환원시키면 SiO2의 웨이퍼 표면과의 화학적 결합력이 작아져, 웨이퍼 표면의 세정 측면에서 효과적이다. (도 2)In the present invention, the hydrogen water may promote a reduction reaction of Ce4+ → Ce3+ in ceria particles on the surface of a semiconductor wafer. After the CMP process, the wafer surface is rinsed using water instead of slurry to clean the wafer surface. In the case of ceria particles, Ce 3+ and Ce 4+ coexist on the wafer surface, but when Ce 3+ is bonded to the wafer surface of SiO 2 , it becomes Ce 4+ , and it is not easily cleaned due to strong bonding force. At this time, when Ce 4+ is reduced to Ce 3+ using hydrogen water, the chemical bonding strength of SiO 2 with the wafer surface is reduced, which is effective in terms of cleaning the wafer surface. (Figure 2)
본 발명의 상기 수소수, 또는 세정 조성물은 착화제, 부식 억제제, 소포제, 보존제, pH 조절제 또는 계면활성제를 추가로 포함하는 것일 수 있다.The hydrogen water or cleaning composition of the present invention may further include a complexing agent, a corrosion inhibitor, an antifoaming agent, a preservative, a pH adjusting agent or a surfactant.
본 발명에서, 상기 반도체 웨이퍼의 세정은 화학적 기계적 평탄화(CMP), 화학적 기계적 평탄화 후 세정(post-CMP cleaning) 또는 버프 클린(Buff clean)에 수반되는 것일 수 있다. In the present invention, the cleaning of the semiconductor wafer may be accompanied by chemical mechanical planarization (CMP), post-CMP cleaning, or buff clean.
본 발명의 상기 세정방법은, 탈이온수의 린스(rinse) 단계에서 인라인(in-line)으로 막 필터(membrane filter)를 이용해 탈이온수에 수소 기체가 직접적으로 주입되는 단계를 추가로 포함하는 것일 수 있다.The cleaning method of the present invention may further include the step of directly injecting hydrogen gas into the deionized water using a membrane filter in-line in the rinsing step of the deionized water. have.
본 발명에서, 상기 수소수는 화학적 기계적 평탄화(CMP), 화학적 기계적 평탄화 후 세정(post-CMP cleaning) 또는 버프 클린(Buff clean)을 위한 장비에 직접적으로 주입되는 것일 수 있다. 수소수가 장비에 직접 주입됨으로써 별도의 설비 없이 공정을 단순화할 수 있다.In the present invention, the hydrogen water may be injected directly into equipment for chemical mechanical planarization (CMP), post-CMP cleaning, or buff clean. As hydrogen water is injected directly into the equipment, the process can be simplified without additional equipment.
이하 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나 이들 실시예는 본 발명을 예시적으로 설명하기 위한 것으로 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.
실시예 1: 탈이온수 린스 단계에서의 수소수 제조 및 세정 효과 확인Example 1: Confirmation of hydrogen water production and cleaning effect in the deionized water rinse step
1-1. CMP 공정 및 버프 클린 공정의 수행1-1. CMP process and buff clean process
표 1과 같이 슬러리, 패드 및 웨이퍼를 준비한 후, 표 2 또는 표 3의 조건으로 각각 CMP 공정 또는 버프 클린(Buff clean) 공정을 수행하였다. 이때 도 1에 나타난 순서대로 수소수를 제조하여, 수소수, 탈이온수(DIW) 또는 강염기성의 pH 11의 수소수 각각을 CMP 공정, CMP 이후 공정과 버프 클린 공정에 공급하였다. After preparing a slurry, a pad, and a wafer as shown in Table 1, a CMP process or a buff clean process was performed under the conditions of Table 2 or Table 3, respectively. At this time, hydrogen water was prepared in the order shown in FIG. 1, and hydrogen water, deionized water (DIW), or hydrogen water having a strongly basic pH of 11 was supplied to the CMP process, the post-CMP process, and the buff clean process.
(희석 비율: 1 to 3)Ceria slurry
(Dilution ratio: 1 to 3)
1-2. 웨이퍼 표면 입자 변화 확인1-2. Wafer surface particle change check
상기 실시예 1-1과 같이 수소수를 제조하여 처리할 경우 다음과 같은 반응이 수반될 것으로 예상되었으며, 이를 웨이퍼 표면상 입자 개수, Ce 이온 수를 토대로 확인하였다.When hydrogen water was prepared and treated as in Example 1-1, it was expected that the following reaction would be accompanied, and this was confirmed based on the number of particles on the wafer surface and the number of Ce ions.
2CeO2 + H2 → Ce2O3 + H2O 2CeO 2 + H 2 → Ce 2 O 3 + H 2 O
Ce4+ → Ce3+ Ce 4+ → Ce 3+
도 3은 웨이퍼 세정 후 (a) 웨이퍼 표면에 남아있는 입자 개수와 (b) 웨이퍼 표면에 남아있는 Ce 이온을 나타낸 것이다. 도 3에서 볼 수 있듯이, 탈이온수(DIW)에 비해 수소수를 사용한 경우에서 웨이퍼 표면의 잔여 입자 수와, Ce 이온수가 현저히 감소하였다. 이는, 수소수에 의해 세리아 표면이 환원되어 화학 결합이 제거되고, 점착력이 낮아짐에 따라 세정이 효과적으로 진행됨을 알 수 있다.3 shows (a) the number of particles remaining on the wafer surface and (b) Ce ions remaining on the wafer surface after wafer cleaning. As can be seen from FIG. 3, when hydrogen water is used compared to DIW, the number of residual particles on the wafer surface and the number of Ce ions are significantly reduced. It can be seen that the surface of ceria is reduced by hydrogen water to remove chemical bonds, and as the adhesive strength decreases, cleaning proceeds effectively.
특히, 높은 pH 의 수소수에서 입자 수 및 Ce 이온수가 더욱 감소하였고, 이로써 높은 pH 특성과 전기적 특성을 갖는 수소수를 이용해 더 효과적인 세정이 가능함을 확인하였다.In particular, the number of particles and the number of Ce ions were further reduced in hydrogen water of high pH, and it was confirmed that more effective cleaning was possible using hydrogen water having high pH characteristics and electrical characteristics.
1-3. 파장 흡수도 확인1-3. Check wavelength absorption
DIW 또는 수소수를 각각 사용한 경우의 UV-visible 분석을 진행하였다.UV-visible analysis was performed when DIW or hydrogen water was used, respectively.
도 4는 세리아 입자가 DIW 또는 수소수와 각각 반응한 경우에 대한 UV-visible 분석 결과를 나타낸 것이다. 도 4에서 볼 수 있듯이, DIW에 비해 수소수를 사용한 경우에서 300-400 nm 파장대의 흡수도가 현저히 감소하였으며, 이는 세리아 입자가 수소수에 의해 환원되어 Ce4+ → Ce3+ 반응이 일어나, 결과적으로 Ce4+ 이온수가 감소한 것임을 알 수 있다.4 shows the results of UV-visible analysis when ceria particles react with DIW or hydrogen water, respectively. As can be seen in FIG. 4, the absorption of the 300-400 nm wavelength band was significantly reduced in the case of using hydrogen water compared to DIW, and this resulted in the reduction of ceria particles by hydrogen water, resulting in Ce 4+ → It can be seen that the Ce 3+ reaction occurred, resulting in a decrease in the number of Ce 4+ ions .
1-4. 웨이퍼 표면에서의 입자 비율 확인1-4. Checking the particle ratio on the wafer surface
DIW 또는 수소수를 각각 사용한 경우에서, 웨이퍼 표면의 세정 전후 변화를 XPS 분석으로 확인하였다.When DIW or hydrogen water was used, respectively, changes before and after cleaning of the wafer surface were confirmed by XPS analysis.
도 5는 세정 전과 후의 웨이퍼 표면에 대한 XPS 분석 결과를 나타낸 것이다. 세리아를 이용한 CMP 공정 후 세리아 입자로 오염된 산화막 표면을 DIW 또는 수소수에 의해 각각 세정한 결과, DIW에 비해 수소수를 사용한 경우 표면에서 Ce3+ 비율이 더욱 높아짐을 확인하였다.5 shows the results of XPS analysis on the wafer surface before and after cleaning. After the CMP process using ceria, the surface of the oxide film contaminated with ceria particles was washed with DIW or hydrogen water, respectively. As a result, it was confirmed that the Ce 3+ ratio on the surface was further increased when hydrogen water was used compared to DIW.
따라서, 수소수에 의해 세리아 입자 표면이 효과적으로 환원되어, 슬러리 및 세리아와 웨이퍼 표면간 부착력이 감소됨으로써 우수한 세정 효과를 이끌어낼 수 있음을 확인하였다.Accordingly, it was confirmed that the surface of the ceria particles was effectively reduced by hydrogen water, and the adhesion between the slurry and the ceria and the wafer surface was reduced, thereby leading to an excellent cleaning effect.
이상의 설명으로부터, 본 발명이 속하는 기술분야의 당업자는 본 발명이 그 기술적 사상이나 필수적 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 이와 관련하여, 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적인 것이 아닌 것으로 이해해야만 한다. 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허 청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.From the above description, those skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not limiting. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the claims to be described later rather than the above detailed description and equivalent concepts are included in the scope of the present invention.
Claims (10)
A cleaning composition for cleaning or buff clean after chemical mechanical planarization (CMP) of a semiconductor wafer comprising hydrogen water.
The composition of claim 1, further comprising a pH adjusting agent.
The composition of claim 1, wherein the hydrogen water has a pH value of 9 to 12.
The composition of claim 1, wherein the hydrogen water promotes the reduction reaction of Ce 4+ → Ce 3+ in ceria particles on the surface of the semiconductor wafer.
린스된 상기 탈이온수가 소수성 중공섬유 막 (Hydrophobic hollow fiber membrane)으로 전달되는 단계; 및
상기 소수성 중공섬유 막을 통해 수소 기체가 탈이온수로 주입되어 수소수가 제조되는 단계를 포함하는, 반도체 웨이퍼의 세정 방법.
Rinsing deionized water;
Delivering the rinsed deionized water to a hydrophobic hollow fiber membrane; And
And producing hydrogen water by injecting hydrogen gas into deionized water through the hydrophobic hollow fiber membrane.
The method of claim 4, wherein the cleaning of the semiconductor wafer is accompanied by chemical mechanical planarization (CMP), post-CMP cleaning, or buff clean.
The cleaning of a semiconductor wafer according to claim 5, wherein the hydrogen water is directly injected into equipment for chemical mechanical planarization (CMP), chemical mechanical planarization and post-CMP cleaning, or buff clean. Way.
The semiconductor of claim 5, further comprising the step of directly injecting hydrogen gas into the deionized water using a membrane filter in-line in the rinsing step of the deionized water. Wafer cleaning method.
The method of claim 5, wherein the hydrogen water further comprises a pH adjusting agent.
The method of claim 5, wherein the hydrogen water has a pH value of 9 to 12.
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