KR100805693B1 - Cleaning liquid and metal film cleaning method using the same - Google Patents
Cleaning liquid and metal film cleaning method using the same Download PDFInfo
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- KR100805693B1 KR100805693B1 KR1020010079240A KR20010079240A KR100805693B1 KR 100805693 B1 KR100805693 B1 KR 100805693B1 KR 1020010079240 A KR1020010079240 A KR 1020010079240A KR 20010079240 A KR20010079240 A KR 20010079240A KR 100805693 B1 KR100805693 B1 KR 100805693B1
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 238000004140 cleaning Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005530 etching Methods 0.000 claims abstract description 16
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012964 benzotriazole Substances 0.000 claims abstract description 11
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000000206 photolithography Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001412 amines Chemical class 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 241000282412 Homo Species 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 3
- -1 RhOx Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- UKTZJXRJZBVHKL-UHFFFAOYSA-N 2h-benzotriazole Chemical compound C1=CC=C2NN=NC2=C1.C1=CC=C2NN=NC2=C1 UKTZJXRJZBVHKL-UHFFFAOYSA-N 0.000 description 1
- 229910016062 BaRuO Inorganic materials 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- 229910019044 CoSix Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910002673 PdOx Inorganic materials 0.000 description 1
- 229910002842 PtOx Inorganic materials 0.000 description 1
- 229910019897 RuOx Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004121 SrRuO Inorganic materials 0.000 description 1
- 229910004491 TaAlN Inorganic materials 0.000 description 1
- 229910004200 TaSiN Inorganic materials 0.000 description 1
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- 229910010060 TiBN Inorganic materials 0.000 description 1
- 229910008482 TiSiN Inorganic materials 0.000 description 1
- 229910008486 TiSix Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
본 발명은 반도체 기술에 관한 것으로, 특히 인간에 유해한 성분을 포함하지 않으며, 생산 비용 및 폐수 처리 비용 감소시킬 수 있는 세정액 및 그를 이용한 금속막 형성 방법을 제공하기 위한 것으로, 이를 위해 본 발명은, 금속막 세정을 위한 세정액에 있어서, 암모늄 하이드록사이드(Ammonium hydroxide)와 아세트산(Acetic acid)과 하이드로겐 플로라이드(Hydrogen flouride)와 순수와 벤조트리아졸(Benzotriazole) 및 에틸렌글리콜(Ethlene glycol)을 포함하여 금속막을 식각하는 세정액을 제공한다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor technology, and in particular, to provide a cleaning liquid and a method of forming a metal film using the same, which do not contain harmful components and can reduce production costs and wastewater treatment costs. A cleaning solution for membrane cleaning, including ammonium hydroxide, acetic acid, hydrogen flouride, pure water, benzotriazole and ethylene glycol A cleaning liquid for etching a metal film is provided.
또한, 상기의 목적을 달성하기 위해 본 발명은, 테트라메틸암모늄 하이드록사이드와 디메틸설폭사이드와 에틸렌글리콜 및 순수를 포함하는 세정액을 이용한 금속막 형성 방법에 있어서, 기판 상에 금속막을 형성하는 단계; 상기 금속막을 이용한 소정의 사진식각 공정을 실시하여 금속막 패턴을 형성하는 단계; 및 상기 세정액을 이용하여 상기 금속막 패턴을 세정하는 단계포함하는 금속막 형성 방법을 제공한다.In addition, in order to achieve the above object, the present invention, a method of forming a metal film using a cleaning solution containing tetramethylammonium hydroxide, dimethyl sulfoxide, ethylene glycol and pure water, forming a metal film on a substrate; Forming a metal film pattern by performing a predetermined photolithography process using the metal film; And cleaning the metal film pattern by using the cleaning solution.
암모늄 하이드록사이드, 아세트산, 하이드로겐 플로라이드, 순수, 벤조트리아졸, 에틸렌글리콜, 아민, 카테콜.Ammonium hydroxide, acetic acid, hydrogen fluoride, pure water, benzotriazole, ethylene glycol, amine, catechol.
Description
도 1a 내지 도 1b는 본 발명의 일실시예에 따른 금속막 패턴 형성 공정을 도시한 단면도,1A to 1B are cross-sectional views illustrating a metal film pattern forming process according to an embodiment of the present invention;
도 2는 종래의 세정 공정을 포함한 일련의 반도체 소자 제조 단계와 본 발명의 세정 공정을 포함한 제조 단계를 비교한 플로우챠트.
2 is a flow chart comparing a series of semiconductor device fabrication steps including a conventional cleaning process with fabrication steps including a cleaning process of the present invention.
* 도면의 주요부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
10 : 기판 11 : 금속막 패턴
10
본 발명은 반도체 기술에 관한 것으로, 특히 세정액 및 그를 이용한 금속막의 형성 방법에 관한 것이다.TECHNICAL FIELD This invention relates to semiconductor technology. Specifically, It is related with the cleaning liquid and the formation method of the metal film using the same.
고집적화 되어 가는 반도체 공정에서 W 또는 Al 등의 금속막이 도입됨으로 써, 기존의 황산, 암모니아 또는 염산 위주의 반도체 전공정에서 사용하던 식각후 세정 용액을 사용할 수가 없다. Since a metal film such as W or Al is introduced in a highly integrated semiconductor process, it is impossible to use a post-etch cleaning solution used in a conventional semiconductor pre-process mainly for sulfuric acid, ammonia, or hydrochloric acid.
따라서, 현재는 대부분의 금속식각후의 세정은 아민(Amine) 성분을 주로 포함하는 유기용제를 사용하고 있다. 이러한, 유기용제는 식각 후 금속표면에 있는 유기성폴리머 잔류물과 금속이온을 비교적 용이하게 제거하고 있다.Therefore, at present, most of the cleaning process after metal etching uses an organic solvent mainly containing an amine component. Such organic solvents relatively easily remove organic polymer residues and metal ions on the metal surface after etching.
그러나, 인간에 유해한 아민, 카테콜(Catechol) 등으로 구성되어 있는 단점이 있으며, 아민계열의 금속 세정액은 비용이 1킬로그램당 11달러 이상이며, 세정 온도가 80℃ 이상에서 진행되며 세정시간도 20분에서 30분 정도로 길어 공정 효율 측면에서 유리하지 못하며, 세정 후 폐수는 유해 유기물로써 처리비용 또한 큰 부담이 된다.However, there are disadvantages in that it is composed of amines, catechol, etc., which are harmful to humans.Amine-based metal cleaning liquids cost more than $ 11 per kilogram, and the cleaning temperature is higher than 80 ° C. As long as from 30 minutes to 30 minutes, it is not advantageous in terms of process efficiency, and the waste water after cleaning is a harmful organic material, and the treatment cost is also a great burden.
전술한 아민을 위주로 하는 유기용제의 케미컬 조성을 살펴Examine the chemical composition of the organic solvents mainly amines described above
보면, 아민으로 대표적으로 사용되고 있는 것이 하이드록실 아민(Hydroxyl amine)으로, 이는 유기성 폴리머를 제거하는 가장 강력한 물질이지만 LD50이 600㎎/㎏이나 되는 바, 어느 아민 종류보다도 치사량이 강하며 인간에 매우 유해한 물질이며, 금속부식방지제로서의 역할을 하는 카테콜 역시 페놀(Phenol) 성분으로 발암을 야기할 수 있는 물질이다. The most commonly used amine is hydroxyl amine, which is the most powerful substance to remove organic polymers, but has an LD50 of 600 mg / kg, which is more lethal than any amine type and extremely harmful to humans. Catechol, which acts as a metal corrosion inhibitor, is also a phenol (Phenol) component that can cause cancer.
이러한 유해 유기성 물질로 구성되는 금속식각 세정액은 동등한 역할을 하는 다른 물질로 대체될 수 있으나, 벌크(Bulk)성 감광잔류제 및 측벽(Sidewall) 폴리머의 완벽한 제거, 하이드록실 아민 또는 카테콜과 동등한 효과를 발휘하면서도 기존 공정의 어떤 변경 적용없이 그대로 대체될 수 있는 기능을 가진 케미컬의 개발 이 필요한 실정이다.
The metal etch cleaning liquid consisting of these harmful organic substances can be replaced with other substances having an equivalent role, but the complete removal of the bulk photoresist and sidewall polymer, the effect equivalent to hydroxyl amine or catechol However, there is a need for the development of a chemical having a function that can be replaced without changing any existing process.
본 발명은 상기한 종래기술의 문제점을 해결하기 위해 제안된 것으로서, 인간에 유해한 성분을 포함하지 않으며, 생산 비용 및 폐수 처리 비용 감소시킬 수 있는 세정액 및 그를 이용한 금속막 형성 방법을 제공하는 것을 그 목적으로 한다.
The present invention has been proposed to solve the above-mentioned problems of the prior art, and does not include components harmful to humans, and provides a cleaning liquid and a method for forming a metal film using the same, which can reduce production costs and wastewater treatment costs. It is done.
상기의 목적을 달성하기 위해 본 발명은, 금속막 세정을 위한 세정액에 있어서, 암모늄 하이드록사이드(Ammonium hydroxide)와 아세트산(Acetic acid)과 하이드로겐 플로라이드(Hydrogen flouride)와 순수와 벤조트리아졸(Benzotriazole) 및 에틸렌글리콜(Ethlene glycol)을 포함하여 금속막을 식각하는 세정액을 제공한다.In order to achieve the above object, the present invention, in the cleaning solution for cleaning the metal film, ammonium hydroxide (Ammonium hydroxide) and acetic acid (Acetic acid), hydrogen fluoride (Hydrogen flouride), pure water and benzotriazole ( Benzotriazole) and ethylene glycol (Ethlene glycol) to provide a cleaning solution for etching the metal film.
또한, 상기의 목적을 달성하기 위해 본 발명은, 암모늄 하이드록사이드와 아세트산과 하이드로겐 플로라이드와 순수와 벤조트리아졸 및 에틸렌글리콜을 포함하는 세정액을 이용한 금속막 형성 방법에 있어서, 기판 상에 금속막을 형성하는 단계; 상기 금속막을 이용한 소정의 사진식각 공정을 실시하여 금속막 패턴을 형성하는 단계; 및 상기 세정액을 이용하여 상기 금속막 패턴을 세정하는 단계를 포함하는 금속막 형성 방법을 제공한다.In order to achieve the above object, the present invention provides a metal film forming method using a cleaning solution containing ammonium hydroxide, acetic acid, hydrogen fluoride, pure water, benzotriazole and ethylene glycol. Forming a film; Forming a metal film pattern by performing a predetermined photolithography process using the metal film; And cleaning the metal film pattern by using the cleaning solution.
바람직하게, 본 발명의 상기 암모늄 하이드록사이드와 상기 아세트산의 비율이 1:1 내지 1:1.5인 것을 특징으로 하며, 상기 하이드로겐 플로라이드와 상기 순수의 비율이 0.005:7.5 내지 0.01:8인 것을 특징으로 하며, 상기 세정액의 페하(pH)가 5.0 내지 8.0인 것을 특징으로 하며, Preferably, the ratio of the ammonium hydroxide and the acetic acid of the present invention is 1: 1 to 1: 1.5, characterized in that the ratio of the hydrogen fluoride and the pure water is 0.005: 7.5 to 0.01: 8 Characterized in that, the pH of the cleaning liquid (pH) is characterized in that 5.0 to 8.0,
상기 세정하는 단계는 2분 내지 10분 동안 실시하는 것을 특징으로 하며, 상기 세정하는 단계는 25℃ 내지 40℃의 온도 하에서 실시하는 것을 특징으로 하며, 상기 세정하는 단계 후, 순수를 이용하여 린싱하는 단계; 및 건조하는 단계를 더 포함하는 것을 특징으로 한다.
The washing step is characterized in that carried out for 2 to 10 minutes, the washing step is carried out at a temperature of 25 ℃ to 40 ℃, after the washing step, rinsing with pure water step; And it is characterized in that it further comprises the step of drying.
본 발명은 아민 또는 카테콜이 함유되어 인체에 유해한 유기성 세정액 대신에 암모늄 하이드록사이드(Ammonium hydroxide)와 아세트산(Acetic acid)과 하이드로겐 플로라이드(Hydrogen flouride)와 순수와 벤조트리아졸(Benzotriazole) 및 에틸렌글리콜(Ethlene glycol)로 구성되는 유기 및 무기용제를 이용하므로 인체에 유해성이 적으며, 기존의 공정을 변화시키지 않고 적용할 수 있는 세정액을 이용하여 금속막 패턴 형성 후 잔류하는 감광성 폴리머 및 식각 잔류물을 효과적으로 제거할 수 있으며, 생산비용 및 폐수처리 비용을 절감할 수 있도록 하는 것을 기술적 특징으로 한다.
In the present invention, instead of organic cleaning solution containing amine or catechol, which is harmful to the human body, ammonium hydroxide, acetic acid, hydrogen flouride, pure water, benzotriazole, The organic and inorganic solvents composed of ethylene glycol are less harmful to the human body, and the photosensitive polymer and etching residue remaining after forming the metal film pattern by using a cleaning solution that can be applied without changing the existing process. The technical feature is that the water can be effectively removed and the production cost and wastewater treatment cost can be reduced.
이하, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 용이하게 실시할 수 있을 정도로 상세히 설명하기 위하여, 본 발명의 가장 바람직한 실시예를 첨부한 도 1a 내지 도 1b를 참조하여 상세하게 설명하는 바, 도 1a 내지 도 1b는 본 발명의 일실시예에 따른 금속막 형성 공정을 도시한 단면도로서, 이를 참조하여 후술한다.Hereinafter, in order to explain in detail enough that a person having ordinary skill in the art to which the present invention pertains can easily implement the technical idea of the present invention, refer to FIGS. 1A to 1B to which the most preferred embodiment of the present invention is attached. 1A to 1B are cross-sectional views illustrating a metal film forming process according to an embodiment of the present invention, which will be described later with reference to the drawings.
먼저, 도 1a에 도시된 바와 같이 반도체 소자를 이루기 위한 여러 요소가 형성된 기판(10) 상에 게이트전극, 비트라인, 워드라인, 전하저장전극 또는 금속배선 등 금속을 이용하는 모든 도전 패턴을 형성하기 위한 금속막을 증착한 다음, 전술한 바와 같은 패턴을 형성하기 위한 소정의 노광원을 이용한 노광 및 현상과 식각 공정 즉, 사진 식각 공정을 실시하여 금속막 패턴(11)을 형성한다.First, as shown in FIG. 1A, all conductive patterns using metals such as a gate electrode, a bit line, a word line, a charge storage electrode, or a metal wiring are formed on a
한편, 금속막은 Pt, Rh, Ru, Ir, Os, Pd, PtOx, RhOx, RuOx, IrOx, OsOx, PdOx, CaRuO3, SrRuO3, BaRuO3, BaSrRuO3, CaIrO3, SrIrO3, BaIrO3, (La,Sr)CoO3, Cu, Al, Ta, Mo, W, Au, Ag, WSix, TiSix, MoSix, CoSix, NoSix,TaSix, TiN, TaN, WN, TiSiN, TiAlN, TiBN, ZrSiN, ZrAlN, MoSiN, MoAlN, TaSiN 및 TaAlN로 이루어지는 군에서 선택되는어느 하나 또는 그 이상의 조합물을 이용하는 바, 전술한 금속막 물질은 식각 특성상 폴리머를 발생하는 식각 공정을 통해 이루어지는 바, 도시된 바와 같은 감광성 폴리머(12)와 식각 잔류물(13) 등이 금속막 패턴(11) 상에 잔류하게 된다.On the other hand, the metal film Pt, Rh, Ru, Ir, Os, Pd, PtOx, RhOx, RuOx, IrOx, OsOx, PdOx, CaRuO 3, SrRuO 3, BaRuO 3, BaSrRuO 3, CaIrO 3, SrIrO 3, BaIrO 3, ( La, Sr) CoO 3 , Cu, Al, Ta, Mo, W, Au, Ag, WSix, TiSix, MoSix, CoSix, NoSix, TaSix, TiN, TaN, WN, TiSiN, TiAlN, TiBN, ZrSiN, ZrAlN, MoSiN Using any one or more combinations selected from the group consisting of MoAlN, TaSiN, and TaAlN, the above-described metal film material is formed through an etching process for generating a polymer due to etching characteristics. ), The
따라서, 전술한 감광성 폴리머(12)와 식각 잔류물(13) 등을 제거하기 위한 세정 공정을 실시하는 바, 본 발명에서는 전술한 바와 같이 인체에 대한 유해성이 적으면서도 기존의 공정을 그대로 사용할 수 있고 비용 또한 저렴한 세정액을 사용한다.Therefore, the above-described cleaning process for removing the photosensitive polymer 12 and the
세정액을 구체적으로 살펴보면, 암모늄 하이드록사이드와 아세트산과 하이드로겐 플로라이드와 순수와 벤조트리아졸 및 에틸렌글리콜 등의 용제를 포함하며, 암모늄 하이드록사이드와 아세트산의 비율은 1:1 ∼ 1:1.5이며, 하이드로겐 플로라이드와 순수의 비율은 암모늄 하이드록사이드 1을 기준으로 0.005:7.5 ∼ 0.01:8이며, 이러한 세정액의 페하(pH)는 벤조트리아졸과 에틸렌글리콜의 첨가로 5.0 ∼ 8.0의 중성 범위를 유지하게 한다.Specifically, the cleaning solution includes ammonium hydroxide, acetic acid, hydrogen fluoride, pure water, solvents such as benzotriazole and ethylene glycol, and the ratio of ammonium hydroxide and acetic acid is 1: 1 to 1: 1.5. , The ratio of hydrogen fluoride and pure water is 0.005: 7.5 to 0.01: 8 based on ammonium hydroxide 1, and the pH of this cleaning solution is 5.0 to 8.0 in the neutral range by addition of benzotriazole and ethylene glycol. To keep.
여기서, 암모늄 하이드록사이드와 하이드로겐 플로라이드는 각각 염기성과 무기성 케미컬이고, 이세트산은 약 유기산이며 벤조트리아졸과 에틸렌글리콜은 유기성 용제이다. 그러나, 여기에서 주성분은 암모늄 하이드록사이드와 하이드로겐 플로라이드 등의 무기성 위주의 케미컬과, 아세트산이며, 벤조트리아졸과 에틸렌글리콜은 보조기능을 수행한다.Here, ammonium hydroxide and hydrogen fluoride are basic and inorganic chemicals, respectively, islet acid is a weak organic acid, and benzotriazole and ethylene glycol are organic solvents. However, the main components here are inorganic oriented chemicals such as ammonium hydroxide and hydrogen fluoride, acetic acid, and benzotriazole and ethylene glycol perform auxiliary functions.
따라서, 이러한 세정액 즉, 케미컬은 반응하여 암모늄 아세테이트를 형성하는 바, 이것은 유기물을 제거할 수 있으며, 아주 묽은 하이드로겐 플로라이드는 기반에 흡착되어 있는 폴리머를 식각하는 역할을 한다. 또한, 금속막의 손상을 방지하기 위하여 벤조트리아졸과 에틸렌글리콜을 사용하는 바, 이는 켈레이트 역할과 손상 방지제 역할을 한다.Thus, this cleaning solution, ie, the chemical, reacts to form ammonium acetate, which can remove organic matter, and the very dilute hydrogen fluoride serves to etch the polymer adsorbed on the substrate. In addition, benzotriazole and ethylene glycol are used to prevent damage to the metal film, which serves as a chelate and a damage preventive agent.
전술한 바와 같은 케미컬의 역할을 살펴 본다.Look at the role of the chemical as described above.
가. 암모늄 아세테이트의 생성end. Production of Ammonium Acetate
암모늄 아세테이트의 생성은 다음의 반응식1과 같다.The production of ammonium acetate is shown in Scheme 1 below.
따라서, 전술한 암모늄 아세테이트(CH3COO-NH4 +)는 다음의 반응식2와 같이 유기물과 금속 이동형 이온을 제거하는 바, 다음의 반응식2와 같다.Therefore, the above-described ammonium acetate (CH 3 COO - NH 4 + ) removes organic substances and metal transfer ions as in Scheme 2 below, and is as in Scheme 2 below.
CH3COO-NH4
+ + R+ + H+ + OH- = CH3COO-R+ + NH4+OH- + H+(R+
는 유기성 라디칼)
CH 3 COO - NH 4 + + R + + H + + OH - = CH 3 COO - R + + NH4 + OH - + H + (R + is an organic radical)
나. 완충작용에 의한 용액 특성 유지I. Maintain solution characteristics by buffering action
다음의 반응식3과 같은 반응에 의해 페하(pH)는 일정하게 되고 NH4F에 의한 HF의 F- 보충으로 균일한 식각을 유지하게 한다.Reaction (pH) is made constant by the reaction shown in Scheme 3 below to maintain uniform etching by F − replenishment of HF by NH 4 F.
CH3COO-NH4 + + H3O+ = CH3COOH + NH4 + + H2OCH 3 COO - NH 4 + + H 3 O + = CH 3 COOH + NH 4 + + H 2 O
NH4 + + H+F- + H2O = NH4F + H3 O+ NH 4 + + H + F - + H 2 O = NH 4 F + H 3 O +
다. 하이드로겐 플로라이드의 약한 식각All. Weak Etching of Hydrogen Floride
즉, 세정 전의 식각 공정에서 금속 기반과 층 표면에 있는 폴리머는 식각과 더불어 제거되는 바, 이 때 NH4F에 의해서 일정한 F- 농도를 유지하게 되며, 이러한 반응은 금속막의 표면 손상이 없어야 하는 조건이 있어야 하며, 반응식4는 이를 나타낸다.In other words, in the etching process before cleaning, the polymer on the metal base and the layer surface is removed along with the etching, whereby a constant F − concentration is maintained by NH 4 F, which is a condition that the surface of the metal film is not damaged. This should be
라. 금속 킬레이트와 부식 방지 역할la. Metal Chelates and Corrosion Protection Roles
에틸렌글리콜(OH-CH2CH2-OH)은 이동성 금속이온을 제거하는 역할을 하는 바, 반응식5와 같다.Ethylene glycol (OH-CH 2 CH 2 -OH) serves to remove the mobile metal ions, the same as in Scheme 5.
한편, 벤조트리아졸(C6H5N3)은 금속막에서 금속과 킬레이트를 형성하여 외부 케미컬에 의한 손상 방지 역할을 수행하는 바, 그 반응은 다음의 반응식6과 같다.Meanwhile, benzotriazole (C 6 H 5 N 3 ) forms a chelate with a metal in the metal film to play a role of preventing damage by external chemicals, and the reaction is shown in Scheme 6 below.
전술한 바와 같은 각 용제의 작용 원리로 도 1b에 도시된 바와 같이, 금속막 패턴(11)을 세정하면, 감광성 폴리머(12)과 식각 잔류물(13)은 모두 제거가 되며, 금속막 패턴(11)은 보호되어, 유니폼한 금속막 패턴(11)을 형성할 수 있게 된다.As shown in FIG. 1B according to the principle of operation of each solvent as described above, when the
여기서, 전술한 세정 공정은 25℃ ∼ 40℃의 온도 하에서 2분 ∼ 10분 동안 실시하는 바, 종래의 80℃ 이상의 온도에서 세정 공정을 진행하던 것에 비해 상대적으로 낮은 온도이므로 장비 측면에서 보다 안전하며, 종래의 경우 세정 공정 완료 후 이소프로필알콜을 이용하여 린싱(Rinsing)하는 공정이 필요하지 않으며, 단지 초순수에서 린싱한 후, 건조하는 공정 만이 필요하므로 공정 진행 시간이 단축되므로 웨이퍼 가공률이 증가하게 되는 바, 20% 이상의 공정 향상 효과가 있다. Here, the cleaning process described above is performed for 2 to 10 minutes at a temperature of 25 ° C to 40 ° C, and is relatively safer than the conventional cleaning process at a temperature of 80 ° C or higher. In the conventional case, a process of rinsing using isopropyl alcohol after the completion of the cleaning process is not required, and only a process of drying after rinsing in ultrapure water is needed, thus shortening the process time, thereby increasing the wafer processing rate. As a result, there is a process improvement effect of 20% or more.
또한, 유기성 아민 계열 케미컬은 킬로그램당 11달러 정도인 반면, 전술한 뮤기성 케미컬은 킬로그램당 1$ ∼ 2$로 80% 이상의 비용절감이 가능하다.In addition, the organic amine-based chemical is about $ 11 per kilogram, whereas the aforementioned organic chemicals can reduce costs by more than 80% at $ 1 to $ 2 per kilogram.
도 2는 종래의 세정 공정을 포함한 일련의 반도체 소자 제조 단계와 본 발명의 세정 공정을 포함한 제조 단계를 비교한 플로우챠트로서, 도시된 바와 같이 이소프로필알콜을 이용한 린싱 단계 'A'를 생략할 수 있다.
FIG. 2 is a flowchart comparing a series of semiconductor device manufacturing steps including a conventional cleaning process and a manufacturing step including a cleaning process of the present invention, and a rinsing step 'A' using isopropyl alcohol may be omitted as shown. have.
전술한 본 발명은, 아민 또는 카테콜 등의 유기성 케미컬을 사용하지 않고 인체에 유해성이 적은 무기성 용제를 주로하는 세정액을 이용하여 금속막에 대한 세정공정을 진행시 기존의 공정을 변경하지 않아 비용 증가가 발생하지 않으며 종래애 비해 낮은 온도에서 공정 진행이 가능하여 장비 측면에서 안전하고, 추가의 린싱 공정을 간단히 수행할 수 있게 함으로써, 웨이퍼 가공률을 높일 수 있으며, 제조비용을 절감할 수 있음을 실시예를 통해 알아 보았다.
The present invention described above does not change the existing process when the cleaning process for the metal film is performed using a cleaning solution mainly containing an inorganic solvent which is less harmful to the human body without using organic chemicals such as amine or catechol. It is possible to increase the wafer processing rate and reduce the manufacturing cost by making it possible to process at a lower temperature than the related art and making it safe in terms of equipment and simply performing an additional rinsing process. It was found through the examples.
본 발명의 기술 사상은 상기 바람직한 실시예에 따라 구체적으로 기술되었으나, 상기한 실시예는 그 설명을 위한 것이며 그 제한을 위한 것이 아님을 주의하여야 한다. 또한, 본 발명의 기술 분야의 통상의 전문가라면 본 발명의 기술 사상의 범위 내에서 다양한 실시예가 가능함을 이해할 수 있을 것이다.
Although the technical idea of the present invention has been described in detail according to the above preferred embodiment, it should be noted that the above-described embodiment is for the purpose of description and not of limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention.
상술한 바와 같은 본 발명은, 환경 또는 인체에 유해가 적은 물질을 세정액으로 사용함으로써, 공정의 안정성을 확보할 수 있으며, 웨이퍼 가공률과 제조비용 절감을 향상시킬 수 있어, 궁극적으로 반도체 소자의 수율 및 가격경쟁력을 향상시킬 수 있는 탁월한 효과를 기대할 수 있다.According to the present invention as described above, by using a substance that is less harmful to the environment or human body as the cleaning liquid, the stability of the process can be secured, the wafer processing rate and the manufacturing cost can be improved, and ultimately the yield of the semiconductor device. And excellent effect can be expected to improve the price competitiveness.
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US9869027B2 (en) | 2013-11-15 | 2018-01-16 | Samsung Display Co., Ltd. | Cleaning composition and method of manufacturing metal wiring using the same |
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KR100734669B1 (en) * | 2003-08-08 | 2007-07-02 | 동부일렉트로닉스 주식회사 | Method for manufacturing semiconductor device and apparatus therefor |
US20070254476A1 (en) * | 2006-04-28 | 2007-11-01 | Taiwan Semiconductor Manufacturing Company, Ltd. | Cleaning porous low-k material in the formation of an interconnect structure |
US7968506B2 (en) | 2008-09-03 | 2011-06-28 | Taiwan Semiconductor Manufacturing Co., Ltd. | Wet cleaning stripping of etch residue after trench and via opening formation in dual damascene process |
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US6132522A (en) * | 1996-07-19 | 2000-10-17 | Cfmt, Inc. | Wet processing methods for the manufacture of electronic components using sequential chemical processing |
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 |
KR20020095729A (en) * | 2001-06-15 | 2002-12-28 | 삼성전자 주식회사 | Mos transistor for semiconductor device and method for manufacturing the same |
KR20030002517A (en) * | 2001-06-29 | 2003-01-09 | 주식회사 하이닉스반도체 | Method for cleaning |
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