KR20090030204A - Process for cleaning a semiconductor wafer - Google Patents
Process for cleaning a semiconductor wafer Download PDFInfo
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- KR20090030204A KR20090030204A KR1020080074518A KR20080074518A KR20090030204A KR 20090030204 A KR20090030204 A KR 20090030204A KR 1020080074518 A KR1020080074518 A KR 1020080074518A KR 20080074518 A KR20080074518 A KR 20080074518A KR 20090030204 A KR20090030204 A KR 20090030204A
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- Prior art keywords
- liquid film
- semiconductor wafer
- cleaning
- hydrogen fluoride
- ozone
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 51
- 238000004140 cleaning Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 26
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 62
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 abstract description 7
- 238000005498 polishing Methods 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 42
- 238000005406 washing Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
-
- 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
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- C11D2111/22—
Abstract
Description
본 발명은 불화수소 및 오존을 함유하는 수성 액체막을 이용한 반도체 웨이퍼의 세척 방법에 관한 것이다.The present invention relates to a method for cleaning a semiconductor wafer using an aqueous liquid film containing hydrogen fluoride and ozone.
전자 부품의 제조를 위해 필요한 반도체 웨이퍼는 정기적으로 입자 및 금속 오염 물질이 세척되어야 한다. 상기 세척 단계는, 전자 부품의 제작자 및 그 공급자, 즉 반도체 웨이퍼의 제작자 모두에 대해 통상적이다.Semiconductor wafers, which are required for the manufacture of electronic components, must be cleaned of particulate and metal contaminants on a regular basis. This cleaning step is common for both the manufacturers of electronic components and their suppliers, ie the manufacturers of semiconductor wafers.
불화수소(HF) 및 오존(O3)을 함유하는 수성 용액이 효과적인 세척제인 것으로 판명되었다. US 5,759,971은, 0.03 내지 0.05 중량% 농도의 HF 및 포화상태까지 용해된 오존을 함유한 수성 배스(aqueous bath)에 동시에 복수 개의 반도체 웨이퍼를 침지시키는 세척 공정을 개시하고 있다. 종래의 공정은 단일 웨이퍼 처리를 위해 설계되는데, 이는 특히 세척액이 적게 소비되게 하기 때문이다. 상기 공정에서 세척액이 반도체 웨이퍼의 한쪽 표면 또는 양쪽 표면에 액체막으로서 도포된다. US 7,037,842 B2는 회전하는 반도체 웨이퍼의 한쪽 표면에 불화수소 및 오존을 함유한 수성 세척액이 분무되는 공정을 개시하고 있다.Aqueous solutions containing hydrogen fluoride (HF) and ozone (O 3 ) have proven to be effective cleaning agents. US 5,759,971 discloses a cleaning process in which a plurality of semiconductor wafers are simultaneously immersed in an aqueous bath containing 0.03 to 0.05% by weight of HF and ozone dissolved up to saturation. Conventional processes are designed for single wafer processing, in particular because less cleaning solution is consumed. In this process, the cleaning liquid is applied as a liquid film on one or both surfaces of the semiconductor wafer. US 7,037,842 B2 discloses a process in which an aqueous cleaning liquid containing hydrogen fluoride and ozone is sprayed onto one surface of a rotating semiconductor wafer.
경제적인 이유로, 가능한 한 짧게 세척 사이클 타임을 형성하는 것, 즉 반도체 웨이퍼의 가능한 한 최대로 높은 처리량을 달성하는 것이 바람직하다. 이러한 목적과 상반되는 점은, 일반적으로, 적정하게는 세척이 더 오랜 시간 동안 실시될 때 더 완전하다는 사실이다. 이 문제에 대한 분명한 해법은 세척 작용을 발휘하는 성분, 즉 불화수소 및 오존 농도의 증가를 수반하는 것으로 여길 수 있다. 그러나, 이러한 방법은, 불화수소의 농도를 증가시키게 되면 이 성분의 에칭 작용이 증가할 것이고, 이에 의해 세척된 표면이 바람직하지 못하게 거칠게 된다는 단점을 갖는다.For economic reasons, it is desirable to form the wash cycle time as short as possible, i.e. to achieve the highest possible throughput of the semiconductor wafer. Contrary to this purpose, in general, the fact that the washing is suitably more complete when carried out for a longer time. An obvious solution to this problem may be considered to involve an increase in the components that exert a cleaning action, ie hydrogen fluoride and ozone concentrations. However, this method has the disadvantage that increasing the concentration of hydrogen fluoride will increase the etching action of this component, thereby making the cleaned surface undesirably rough.
본 발명의 목적은 표면의 거칠기를 용인할 수 없을 정도로 증가시키지 않고 짧은 사이클 타임 및 효과적인 세척을 가능하게 하는 방법을 제공하는 것이다.It is an object of the present invention to provide a method that enables short cycle times and effective cleaning without unacceptably increasing the surface roughness.
상기 목적은, 반도체 웨이퍼의 세척될 표면상에 불화 수소 및 오존을 함유한 제1 수성 액체막을 형성하는 단계; 불화 수소 및 오존을 함유하며 불화 수소의 농도는 상기 제1 액체막보다 낮은, 제2 수성 액체막으로 상기 제1 액체막을 교체하는 단계; 및 상기 제2 액체막을 제거하는 단계를 포함하는, 반도체 웨이퍼의 세척 방법에 의해 달성된다.The object is to form a first aqueous liquid film containing hydrogen fluoride and ozone on a surface to be cleaned of a semiconductor wafer; Replacing the first liquid film with a second aqueous liquid film containing hydrogen fluoride and ozone and having a concentration of hydrogen fluoride lower than the first liquid film; And removing the second liquid film.
상기 방법의 이점은, 특히 아직 반도체 소자를 형성하지 않는 실리콘 반도체 웨이퍼의 세척과 관련하여 의미가 있다. 이러한 반도체 웨이퍼는 통상적으로 폴리싱, 열처리 후 또는 에피텍셜층의 증착 후에 세척된다. 세척액의 에칭 작용은 COP(crystal originated particles) 결함 및 산소 석출물(BMD; bulk microdefects)을 초래한다. 이는 산란광 측정 기구에 의해 입자로서 탐지되고, 이 입자는 표면 거칠기를 증가시키는 원인이다. 본 발명은 이러한 불리한 효과를 억제하지만, 세척의 신속한 완료를 포기하지는 않는다.The advantages of the method are particularly meaningful with regard to cleaning silicon semiconductor wafers that do not yet form semiconductor devices. Such semiconductor wafers are typically cleaned after polishing, heat treatment or after deposition of the epitaxial layer. Etching of the cleaning solution results in crystal originated particles (COP) defects and bulk microdefects (BMD). This is detected as a particle by the scattering light measuring instrument, which causes the surface roughness to increase. The present invention suppresses this adverse effect but does not give up the rapid completion of the wash.
회전하는 반도체 웨이퍼를 이용한 단일 웨이퍼 처리의 개념에 기초하는, 본 발명에 따른 세척 방법은, 주로 세척액 내의 불화 수소의 농도를 달리하여, 제1 단계의 세척액의 농도가 후속 단계의 세척액의 농도보다 높도록 한 두 개의 세척 단 계를 포함한다. 제1 단계는, 세척될 반도체 웨이퍼의 표면상에 제1 액체막의 형성에서부터 그 제1 액체막이 제2 액체막으로 대체될 때까지 지속된다. 제2 단계는, 이때부터 제2 액체막이 세척될 반도체 웨이퍼의 표면에서 제거될 때까지 지속된다. 두 단계는, 바람직하게는 각각 60초를 초과하여, 특히 바람직하게는 각각 30초를 초과하여 지속되지 않으므로, 본 발명에 따른 세척은 바람직하게는 120초 이하로, 특히 바람직하게는 60초 이하로 실시될 수 있다.Based on the concept of single wafer processing with rotating semiconductor wafers, the cleaning method according to the present invention mainly differs in the concentration of hydrogen fluoride in the washing liquid so that the concentration of the washing liquid of the first stage is higher than that of the washing liquid of the subsequent stage. Including two cleaning steps. The first step continues from the formation of the first liquid film on the surface of the semiconductor wafer to be cleaned until the first liquid film is replaced with the second liquid film. The second step continues from this time until the second liquid film is removed from the surface of the semiconductor wafer to be cleaned. The two stages preferably do not last more than 60 seconds each, particularly preferably more than 30 seconds each, so that the washing according to the invention is preferably at most 120 seconds, particularly preferably at most 60 seconds Can be implemented.
제1 세척 단계에서부터 제2 세척 단계로의 전환은, 바람직하게는 제1 액체막을 제2 액체막으로 대체하는 것에 의해 실시되고, 그 동안에 세척될 반도체 웨이퍼의 표면은 액체에 의해 일정하게 젖은 상태로 남아 있다.The transition from the first cleaning step to the second cleaning step is preferably carried out by replacing the first liquid film with a second liquid film, during which the surface of the semiconductor wafer to be cleaned remains constant wet by the liquid. have.
제1 액체막 및 제2 액체막의 두께는, 세척될 표면의 중심을 수직으로 가로지르는 회전축에 대해 반도체 웨이퍼가 회전되는 속도에 의해 제어된다. 바람직하게는, 회전 속도는 100 내지 2000 rpm의 범위 내에 있다. 200 내지 500 rpm의 범위가 특히 바람직하다. 제1 세척 단계 중의 회전 운동의 속도는 제2 세척 단계 중의 회전 운동의 속도와 상이할 수 있다. 바람직하게는, 제1 세척 단계에 대해 선택된 속도는 이 세척 단계 중에 변화되지 않을 것이다. 반도체 웨이퍼의 회전 운동에 기인하여, 사용된 세척액은 반도체 웨이퍼의 에지에서 입자 및 용해된 오염 물질과 함께 흘러나간다. 이에 기인한 세척액의 손실은, 하나 이상의 노즐을 통해 대응하는 양의 새로운 액체를 세척될 반도체 웨이퍼의 표면상에 계속하여 가함으로써 보상된다.The thickness of the first liquid film and the second liquid film is controlled by the speed at which the semiconductor wafer is rotated about an axis of rotation perpendicularly across the center of the surface to be cleaned. Preferably, the rotational speed is in the range of 100 to 2000 rpm. Particular preference is given to a range of 200 to 500 rpm. The speed of the rotational movement during the first washing step can be different from the speed of the rotational movement during the second washing step. Preferably, the rate selected for the first wash step will not change during this wash step. Due to the rotational motion of the semiconductor wafer, the used cleaning liquid flows out with the particles and dissolved contaminants at the edge of the semiconductor wafer. The loss of cleaning solution due to this is compensated for by continuously applying a corresponding amount of fresh liquid on the surface of the semiconductor wafer to be cleaned through one or more nozzles.
제1 세척 단계는, 본질적으로 비교적 높은 농도의 불화수소의 도움으로, 자 연적인 표면 산화물은 물론, 실리카 졸을 함유한 가능한 폴리싱제 잔류물을 신속하게 용해시키도록 의도되었다. 이에 의해 불용성 입자에 대한 접착성 베이스도 제거되어, 불용성 입자가 반도체 웨이퍼의 표면에서 계속하여 세정된다. 제2 단계는 본질적으로 그러한 세정 공정을 조장하는 조건하에 세정 공정을 유지하는, 반도체 재료의 에칭에 의해서 생성되는 재료의 부식을 최소화하도록 의도되었다.The first washing step is intended to rapidly dissolve natural surface oxides as well as possible polishing agent residues containing silica sol, with the aid of a relatively high concentration of hydrogen fluoride. As a result, the adhesive base to the insoluble particles is also removed, and the insoluble particles are continuously washed on the surface of the semiconductor wafer. The second step is intended to minimize corrosion of the material produced by etching of the semiconductor material, which essentially maintains the cleaning process under conditions that encourage such cleaning process.
제1 액체막에서, 불화수소의 농도는 바람직하게는 0.1 내지 10 중량%이고, 특히 바람직하게는 0.1 내지 2.0 중량%의 범위에 있다. 제2 액체막에서, 불화수소의 농도는 바람직하게는 0.001 내지 0.1 중량%이고, 특히 바람직하게는 0.02 내지 0.05 중량%의 범위에 있다. 오존의 농도는 두 액체막에서 동일할 수 있거나, 제1 액체막에서보다 제2 액체막에서 더 낮을 수 있다. 그러나, 여하튼, 오존의 농도는 친수성 웨이퍼 표면 뒤에 남길 정도로 충분히 높도록 선택되어야 한다. 액체막이 반도체 웨이퍼상에 도포될 때 오존이 세척액 내에 이미 포함될 수 있다. 그러나, 바람직한 방법은 주변 기체 상으로부터 확산에 의한 운송에 의해 액체막이 오존으로 가득하게 되는 것이다. 이러한 방법은 예컨대 US 2002/0050279 A1에 개시되어 있다. 이 경우에, 오존은 산소와의 혼합물로서 처리 챔버 내에 도입된다. 산소 내의 오존의 농도는 바람직하게는 3 내지 20 중량%이다.In the first liquid film, the concentration of hydrogen fluoride is preferably 0.1 to 10% by weight, particularly preferably in the range of 0.1 to 2.0% by weight. In the second liquid film, the concentration of hydrogen fluoride is preferably in the range of 0.001 to 0.1% by weight, particularly preferably in the range of 0.02 to 0.05% by weight. The concentration of ozone may be the same in both liquid films or may be lower in the second liquid film than in the first liquid film. In any case, however, the concentration of ozone should be chosen to be high enough to remain behind the hydrophilic wafer surface. Ozone may already be included in the cleaning liquid when the liquid film is applied onto the semiconductor wafer. However, the preferred method is that the liquid membrane is filled with ozone by transport by diffusion from the surrounding gas phase. Such a method is for example disclosed in US 2002/0050279 A1. In this case, ozone is introduced into the processing chamber as a mixture with oxygen. The concentration of ozone in oxygen is preferably 3 to 20% by weight.
또한, 제1 액체막 및/또는 제2 액체막이 0.2 내지 2.0 중량% 농도의 염산(HCl)을 함유하는 것이 바람직하다. 염산의 첨가는 금속, 즉 구리, 철 및 니켈 이온과 같은 금속성 오염 물질의 제거를 촉진시킨다.It is also preferable that the first liquid film and / or the second liquid film contain hydrochloric acid (HCl) at a concentration of 0.2 to 2.0% by weight. The addition of hydrochloric acid facilitates the removal of metal contaminants such as copper, iron and nickel ions.
제1 액체막 및 제2 액체막은 바람직하게는 상온(25℃)에 있다. 그러나 온도 는 상온보다 낮거나 높을 수 있고, 95℃에 이를 수도 있다. 제1 액체막 및 제2 액체막의 온도는 동일하거나 상이할 수 있다.The first liquid film and the second liquid film are preferably at room temperature (25 ° C). However, the temperature may be lower or higher than room temperature and may reach 95 ° C. The temperature of the first liquid film and the second liquid film may be the same or different.
제2 액체막은 바람직하게는 제2 액체막을 세척제, 예컨대 초순수, 오존을 함유한 초순수, SC1 용액 또는 묽은 염산으로 대체함으로써 제거된다. 이어서, 반도체 웨이퍼는 예컨대 높은 회전 속도의 반도체 웨이퍼로부터 세척제를 원심분리하면서 질소를 유입함으로써, 또는 마란고니 건조(Marangoni drying)로서 알려진 건조 방법을 실시함으로써 건조될 수 있다.The second liquid film is preferably removed by replacing the second liquid film with a cleaning agent such as ultrapure water, ultrapure water containing ozone, SC1 solution or dilute hydrochloric acid. The semiconductor wafer can then be dried, for example, by introducing nitrogen while centrifuging the cleaning agent from a high rotational speed semiconductor wafer, or by carrying out a drying method known as Marangoni drying.
본 발명에 따른 반도체 웨이퍼의 세척 방법에 의하면, 표면의 거칠기를 용인할 수 없을 정도로 증가시키지 않고, 짧은 사이클 타임 및 효과적인 세척을 가능하게 하는 효과가 있다.According to the method of cleaning a semiconductor wafer according to the present invention, there is an effect of enabling a short cycle time and effective cleaning without increasing the surface roughness unacceptably.
실시예Example ::
300 mm의 직경을 갖는 실리콘 반도체 웨이퍼가 화학 기계적 폴리싱(CMP) 이후에 세척되었다. 조대 폴리싱제 잔류물이 롤러의 도움으로 사전 제거되었다. 이러한 방식으로 사전 처리된 반도체 웨이퍼의 폴리싱된 표면상에서 65 nm를 초과하는 평균 크기를 갖는 200 내지 500개의 입자가 검출되었다. 이러한 반도체 웨이퍼의 일부는 HF 및 O3를 함유한 세척액을 이용하여 본 발명에 따른 2 단계 세척을 받았다. 제1 세척 단계 중에, 단일 웨이퍼 처리 장치 내에서 반도체 웨이퍼의 폴리싱된 표면에 0.1 중량% 농도의 불화수소가 함유된 수용액이 분무되었다. 동시에, 230g 오존/Nm3(stp)을 갖는 산소/오존 혼합물이 장치의 기체 공간을 통해 보내졌다. 이러한 방식으로 처리된 반도체 웨이퍼의 표면상에, 0.1 중량% 농도의 HF와 더불어 오존을 함유한 액체막이 형성되었다. 30초가 경과한 후에, 제2 세척 단계에서 반도체 웨이퍼에 0.05 중량% 농도의 불화수소가 함유된 수용액이 분무되었다. 0.05 중량% 농도의 HF와 더불어 오존을 함유한 액체막이 폴리싱된 표면상에 형성되도록 오존의 공급을 어떠한 방식으로도 변경시키지 않았다. 30초가 더 경과된 후에, 세척된 반도체 웨이퍼는 초순수로 세정되고 건조되었다. 60초간 지속된 전체 세척 단계(제1 세척 단계 및 제2 세척 단계)가 300 rpm의 일정한 속도로 반도체 웨이퍼를 회전시킴으로써 실시되었다.A silicon semiconductor wafer with a diameter of 300 mm was cleaned after chemical mechanical polishing (CMP). The coarse polishing agent residue was preliminarily removed with the aid of a roller. In this way, 200 to 500 particles with an average size of greater than 65 nm were detected on the polished surface of the semiconductor wafer pretreated. Some of these semiconductor wafers were subjected to a two step cleaning according to the present invention using a cleaning solution containing HF and O 3 . During the first cleaning step, an aqueous solution containing 0.1% by weight of hydrogen fluoride was sprayed onto the polished surface of the semiconductor wafer in a single wafer processing apparatus. At the same time, an oxygen / ozone mixture with 230 g ozone / Nm 3 (stp) was sent through the gas space of the device. On the surface of the semiconductor wafer processed in this manner, a liquid film containing ozone with HF at a concentration of 0.1% by weight was formed. After 30 seconds had elapsed, an aqueous solution containing 0.05% by weight of hydrogen fluoride was sprayed onto the semiconductor wafer in the second cleaning step. The supply of ozone was not altered in any way so that a liquid film containing ozone with a concentration of 0.05% by weight of HF was formed on the polished surface. After 30 seconds had elapsed, the washed semiconductor wafers were cleaned and dried with ultrapure water. A full cleaning step (first cleaning step and second cleaning step) lasting 60 seconds was performed by rotating the semiconductor wafer at a constant speed of 300 rpm.
비교를 위하여, 상기한 바와 같이 사전 처리된 반도체 웨이퍼가 동일한 장치에서 1단계 세척만을 받았다. 세척될 반도체 웨이퍼의 폴리싱된 표면에 0.05 중량% 농도의 불화수소를 함유한 수용액이 분무되었다. 동시에, 230g 오존/Nm3(stp)을 갖는 산소/오존 혼합물이 장치의 기체 공간을 통해 보내졌다. 이러한 방식으로 처리된 반도체 웨이퍼의 표면에 0.05 중량% 농도의 HF와 더불어 오존을 함유한 액체막이 형성되었다. 세척 중에, 반도체 웨이퍼가 300 rpm의 일정한 속도로 회전되었다. 60초가 경과한 후에, 세척된 반도체 웨이퍼는 초순수로 씻겨졌고 건조되었다. 반도체 웨이퍼의 일부의 경우, 세척 지속 시간을 240초로 연장시켰고, 나머지의 경우, 불화수소의 농도를 0.1 중량%로 증가시켰다.For comparison, the semiconductor wafers pretreated as described above received only one step wash in the same apparatus. An aqueous solution containing 0.05% by weight of hydrogen fluoride was sprayed onto the polished surface of the semiconductor wafer to be cleaned. At the same time, an oxygen / ozone mixture with 230 g ozone / Nm 3 (stp) was sent through the gas space of the device. On the surface of the semiconductor wafer treated in this manner, a liquid film containing ozone with a concentration of 0.05% by weight of HF was formed. During the cleaning, the semiconductor wafer was rotated at a constant speed of 300 rpm. After 60 seconds had elapsed, the washed semiconductor wafers were washed with ultrapure water and dried. For some of the semiconductor wafers, the cleaning duration was extended to 240 seconds, and for others, the concentration of hydrogen fluoride was increased to 0.1% by weight.
세척의 효율을 시험한 결과, 본 발명에 따라 세척된 반도체 웨이퍼 상에서 세척한 후에 평균하여 80% 적은 입자가 발견되었다. 일 단계 세척에 있어서, 가장 좋은 경우에 입자의 45%가 제거되었다. 세척 시간의 연장의 결과는, 에칭 효과에 의해 입자 개수가 증가하여 세척 효율의 감소를 가져왔다는 점이었다.As a result of testing the efficiency of the cleaning, 80% fewer particles were found on average after washing on the semiconductor wafers cleaned according to the present invention. In one step washing, 45% of the particles were removed in the best case. The result of the extension of the washing time was that the number of particles increased due to the etching effect, resulting in a decrease in washing efficiency.
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