KR102111056B1 - Non-aquaneous etching composition for silicon-based compound layer - Google Patents
Non-aquaneous etching composition for silicon-based compound layer Download PDFInfo
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- KR102111056B1 KR102111056B1 KR1020140036808A KR20140036808A KR102111056B1 KR 102111056 B1 KR102111056 B1 KR 102111056B1 KR 1020140036808 A KR1020140036808 A KR 1020140036808A KR 20140036808 A KR20140036808 A KR 20140036808A KR 102111056 B1 KR102111056 B1 KR 102111056B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- silicon oxide
- oxide film
- metal film
- film
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000005530 etching Methods 0.000 title claims description 35
- 239000002210 silicon-based material Substances 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 9
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
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- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- PASOAYSIZAJOCT-UHFFFAOYSA-N butanoic acid Chemical compound CCCC(O)=O.CCCC(O)=O PASOAYSIZAJOCT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
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- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 235000020830 overeating Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- 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
- H01L21/302—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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Weting (AREA)
Abstract
본 발명은 실리콘 산화막용 비수계 식각액 조성물에 관한 것으로, 보다 상세하게는 유기산, 탄소수 1 내지 20의 알킬암모늄플루오라이드 및 유기 용매를 포함함으로써, 하부 금속막을 손상시키지 않고, 실리콘 산화막을 선택적으로 식각할 수 있으며, 경시 안정성도 우수한 실리콘 산화막용 비수계 식각액 조성물 및 이를 이용한 실리콘 산화막의 패턴 형성 방법에 관한 것이다.The present invention relates to a non-aqueous etchant composition for a silicon oxide film, and more specifically, by including an organic acid, an alkylammonium fluoride having 1 to 20 carbon atoms, and an organic solvent, the silicon oxide film can be selectively etched without damaging the lower metal film. It relates to a non-aqueous etchant composition for a silicon oxide film with excellent stability over time and a method for forming a pattern of a silicon oxide film using the same.
Description
본 발명은 실리콘 산화막용 비수계 식각액 조성물에 관한 것으로서, 보다 구체적으로, 하부 금속막을 손상시키지 않고 실리콘 산화막을 선택적으로 식각할 수 있는 식각액 조성물에 관한 것이다.
The present invention relates to a non-aqueous etchant composition for a silicon oxide film, and more particularly, to an etchant composition capable of selectively etching the silicon oxide film without damaging the underlying metal film.
실리콘 산화물막(SiOx) 및 실리콘 질화물막(SiNx)은 반도체 제조공정에서 사용되는 대표적인 절연막으로 사용되며, 각각 단독으로 사용되거나 혹은 1층 이상의 실리콘 산화물막 및 1층 이상의 실리콘 질화물막이 교대로 적층되어 사용되 기도 한다. 또한 상기 실리콘 산화물막 및 실리콘 질화물막은 금속 배선과 같은 도전성 패턴을 형성하기 위한 하드마스크(Hard mask)로서도 사용된다.Silicon oxide film (SiOx) and silicon nitride film (SiNx) are used as typical insulating films used in semiconductor manufacturing processes, or used individually or by stacking one or more silicon oxide films and one or more silicon nitride films alternately. It also becomes. The silicon oxide film and silicon nitride film are also used as hard masks for forming conductive patterns such as metal wiring.
종래에는 실리콘 산화물막 및 실리콘 질화물막이 적층된 절연막을 식각하여 패턴을 형성하는 방법으로 상부의 실리콘 질화물막을 건식식각 방법으로 먼저 식각한 후, BOE(Buffered Oxide Etchant)와 같은 실리콘 산화물막 식각용 식각액 으로 하부의 실리콘 산화막을 습식식각하여 절연막 패턴을 형성하였다. 종래에 실리콘 산화물막 식각액으로 널리 사용되는 BOE(Buffered Oxide Etchant)는 불화수소(HF), 불화암모늄(NH4F) 및 물을 함유하는 식각액으로서, 불화수소(HF)로 인해 취급상 위험할 뿐 아니라, 알루미늄 등의 하부 금속막질을 손상시키는 문제가 있었다. 따라서, 산화막만을 선택적으로 식각하면서, 하부 금속막에 대한 어택이 없는 식각액 조성물의 개발이 요구된다.In the related art, a silicon oxide film and a silicon nitride film are etched to form a pattern by etching the insulating film, and the upper silicon nitride film is first etched by a dry etching method, followed by an etching solution for etching a silicon oxide film such as Buffered Oxide Etchant (BOE). An insulating film pattern was formed by wet etching the lower silicon oxide film. BOE (Buffered Oxide Etchant), which is widely used as a silicon oxide film etching solution, is an etching solution containing hydrogen fluoride (HF), ammonium fluoride (NH 4 F) and water, and is only dangerous in handling due to hydrogen fluoride (HF). No, there was a problem of damaging the underlying metal film such as aluminum. Accordingly, there is a need to develop an etchant composition that does not attack the lower metal film while selectively etching only the oxide film.
한편, 한국공개특허 제2004-0077043호에서는 10 ~ 35중량%의 불화수소(HF), 10 ~ 35중량%의 불화암모늄(NH4F) 및 탈이온수로 이루어진 세정액을 개시하고 있으나, 상기 세정액의 조성에서는 하부 금속막에 대한 부식의 문제를 해결하지는 못하고 있다.
On the other hand, Korean Patent Publication No. 2004-0077043 discloses a cleaning solution consisting of 10 to 35% by weight of hydrogen fluoride (HF), 10 to 35% by weight of ammonium fluoride (NH 4 F) and deionized water. The composition does not solve the problem of corrosion on the underlying metal film.
본 발명은 하부 금속막의 손상 없이, 선택적으로 실리콘 산화막을 식각할 수 있는 실리콘 산화막용 비수계 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a non-aqueous etchant composition for a silicon oxide film capable of selectively etching a silicon oxide film without damaging the underlying metal film.
또한, 본 발명은 상기 실리콘 산화막용 비수계 식각액 조성물을 사용하는 실리콘 산화막의 패턴 형성 방법을 제공하는 것을 또 다른 목적으로 한다.
In addition, another object of the present invention is to provide a method for forming a pattern of a silicon oxide film using the non-aqueous etchant composition for the silicon oxide film.
1. 유기산, 탄소수 1 내지 20의 알킬암모늄플루오라이드 및 유기 용매를 포함하고, 실리콘 산화막용 비수계 식각액 조성물.1. A non-aqueous etchant composition for a silicon oxide film, comprising an organic acid, an alkylammonium fluoride having 1 to 20 carbon atoms, and an organic solvent.
2. 위 1에 있어서, 상기 유기산은 아스코르브산(Ascorbic Acid), 아세트산(acetic acid), 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 옥살산(oxalic acid), 펜탄산(pentanoic acid), 설포벤조산(sulfobenzoic acid), 설포석신산(sulfosuccinic acid), 프탈산(phthalic acid), 설포프탈산(sulfophthalic acid), 살리실산(salicylic acid), 설포살리실산(sulfosalicylic acid), 벤조산(benzoic acid), 락트산(lactic acid), 글리세르산(glyceric acid), 석신산(succinic acid), 말산(malic acid), 타르타르산(tartaric acid), 이소시트르산(isocitric acid), 프로펜산(propenoic acid), 이미노디아세트산(imminodiacetic acid), 카프릴산(caprylic acid), 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid; EDTA), 메탄설폰산, 에탄설폰산, 벤젠설폰산 및 파라톨루엔셀폰산으로 이루어진 군에서 선택된 적어도 하나를 포함하는, 실리콘 산화막용 비수계 식각액 조성물.2. In the above 1, the organic acid is ascorbic acid (acetic acid), acetic acid (acetic acid), butanoic acid (butanoic acid), citric acid (citric acid), formic acid (formic acid), gluconic acid (gluconic acid), glycol Acids (glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, phthalic acid, sulfophthalic acid) sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, Tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid, caprylic acid, ethylenediaminetetraacetic acid (EDTA), methanesulfonic acid , Consisting of ethanesulfonic acid, benzenesulfonic acid and paratoluenecellonic acid It includes at least one selected from the group, the non-aqueous etchant composition for a silicon oxide film.
3. 위 1에 있어서, 상기 탄소수 1 내지 20의 알킬암모늄플루오라이드는 테트라메틸암모늄플루오라이드, 테트라에틸암모늄플루오라이드 및 테트라부틸암모늄플루오라이드로 이루어진 군에서 선택된 적어도 하나를 포함하는, 실리콘 산화막용 비수계 식각액 조성물.3. In the above 1, the alkyl ammonium fluoride having 1 to 20 carbon atoms includes at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride and tetrabutylammonium fluoride, the ratio for the silicon oxide film Aqueous etchant composition.
4. 위 1에 있어서, 상기 유기 용매는 극성 양성자성 용매인, 실리콘 산화막용 비수계 식각액 조성물.4. In the above 1, wherein the organic solvent is a polar protic solvent, a non-aqueous etchant composition for a silicon oxide film.
5. 위 1에 있어서, 조성물 총 중량 중 유기산 1 내지 40%, 탄소수 1 내지 20의 알킬암모늄플루오라이드 0.1 내지 20중량%, 유기 용매 50 내지 99중량%로 포함되는, 실리콘 산화막용 비수계 식각액 조성물.5. In the above 1, in the total weight of the composition, 1 to 40% of organic acid, 1 to 20 carbon atoms of alkylammonium fluoride, 0.1 to 20% by weight, 50 to 99% by weight of organic solvent, non-aqueous etching solution composition for silicon oxide film .
6. 위 1에 있어서, 실리콘 산화막은 그 하부에 금속막이 형성된 것인, 실리콘 산화막용 비수계 식각액 조성물.6. In the above 1, the silicon oxide film is a metal film is formed on the bottom, the non-aqueous etching solution composition for a silicon oxide film.
7. 위 6에 있어서, 상기 금속막은 알루미늄계 금속막인, 실리콘 산화막용 비수계 식각액 조성물.7. The method of 6 above, wherein the metal film is an aluminum-based metal film, a non-aqueous etching solution composition for a silicon oxide film.
8. Ⅰ)기판 상에 금속막을 형성하는 단계;8. Ⅰ) forming a metal film on the substrate;
Ⅱ)상기 금속막 상에 실리콘 산화막을 형성하는 단계;Ⅱ) forming a silicon oxide film on the metal film;
Ⅲ)포토리소그라피 공정으로 상기 실리콘 산화막 상에 포토레지스트 패턴을 형성하는 단계; 및Ⅲ) forming a photoresist pattern on the silicon oxide film by a photolithography process; And
Ⅳ)상기 실리콘 산화막을 위 1 내지 7 중 어느 한 항의 식각액 조성물로 식각하는 단계;Ⅳ) etching the silicon oxide film with the etching solution composition of any one of 1 to 7 above;
를 포함하는 실리콘 산화막의 패턴 형성 방법.
Method of forming a pattern of a silicon oxide film comprising a.
본 발명의 실리콘 산화막용 비수계 식각액 조성물은 하부 금속막의 손상을 억제할 수 있다.The non-aqueous etching solution composition for a silicon oxide film of the present invention can suppress damage to a lower metal film.
또한, 본 발명의 실리콘 산화막용 비수계 식각액 조성물은 실리콘 산화막만을 선택적으로 식각할 수 있다.In addition, the non-aqueous etching solution composition for a silicon oxide film of the present invention can selectively etch only the silicon oxide film.
또한, 본 발명의 실리콘 산화막용 비수계 식각액 조성물은 경시 안정성이 뛰어나다.
In addition, the non-aqueous etchant composition for a silicon oxide film of the present invention has excellent stability over time.
본 발명은 유기산, 탄소수 1 내지 20의 알킬암모늄플루오라이드 및 유기 용매를 포함함으로써, 하부 금속막의 손상 없이 실리콘 산화막을 선택적으로 식각할 수 있으며, 경시 안정성도 우수한 실리콘 산화막용 비수계 식각액 조성물 및 이를 사용하는 실리콘 산화막의 패턴형성 방법에 대한 것이다.
The present invention includes an organic acid, an alkylammonium fluoride having 1 to 20 carbon atoms, and an organic solvent, so that the silicon oxide film can be selectively etched without damaging the underlying metal film, and a non-aqueous etchant composition for silicon oxide film with excellent stability over time and the use thereof It relates to a method for forming a pattern of a silicon oxide film.
이하, 본 발명을 상세히 설명하기로 한다.
Hereinafter, the present invention will be described in detail.
<실리콘 산화막용 비수계 식각액 조성물><Non-aqueous etching solution composition for silicon oxide film>
본 발명의 실리콘 산화막용 비수계 식각액 조성물은 유기산, 탄소수 1 내지 20의 알킬암모늄플루오라이드 및 유기 용매를 포함한다.The non-aqueous etching solution composition for a silicon oxide film of the present invention includes an organic acid, an alkylammonium fluoride having 1 to 20 carbon atoms, and an organic solvent.
본 발명에서 “비수계”란, 용매로 물을 실질적으로 사용하지 않는 것을 의미하며, “실질적으로 사용하지 않는다”은 것은 본 발명의 범위, 효과를 벗어나지 않는 한도 내에서 물이 미량 포함되는 경우까지 제외하는 것은 아니라는 의미이다.In the present invention, "non-aqueous" means that substantially no water is used as a solvent, and "substantially not used" means that water is contained in a small amount within the scope of the present invention, without departing from the effect. It does not mean to be excluded.
본 발명의 실리콘 산화막용 비수계 식각액 조성물은 용매로 물을 사용하지 않아, 실리콘 산화막의 하부에 형성되는 금속막(예를 들면, 알루미늄계 금속막)의 손상 없이 실리콘 산화막을 선택적으로 식각할 수 있다.The non-aqueous etching solution composition for a silicon oxide film of the present invention does not use water as a solvent, so that the silicon oxide film can be selectively etched without damaging a metal film (for example, an aluminum-based metal film) formed under the silicon oxide film. .
유기산Organic acids
본 발명의 식각액 조성물에 사용되는 유기산은 후술하는 본 발명의 알킬암모늄플루오라이드와 반응하여, 실리콘 산화막을 식각하는 불화수소(HF)를 생성시키는 성분이다.The organic acid used in the etchant composition of the present invention is a component that reacts with the alkylammonium fluoride of the present invention, which will be described later, to produce hydrogen fluoride (HF) for etching the silicon oxide film.
상기 유기산의 종류는 특별히 한정되지 않으나, 예를 들면, 탄소수 1 내지 20의 카르복시산, 탄소수 1 내지 20의 알킬설폰산 또는 탄소수 6 내지 20의 아릴설폰산일 수 있으며,The type of the organic acid is not particularly limited, and may be, for example, carboxylic acid having 1 to 20 carbon atoms, alkylsulfonic acid having 1 to 20 carbon atoms, or aryl sulfonic acid having 6 to 20 carbon atoms,
탄소수 1 내지 20의 카르복시산의 보다 구체적인 예를 들면, 아스코르브산(Ascorbic Acid), 아세트산(acetic acid), 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 옥살산(oxalic acid), 펜탄산(pentanoic acid), 설포벤조산(sulfobenzoic acid), 설포석신산(sulfosuccinic acid), 프탈산(phthalic acid), 설포프탈산(sulfophthalic acid), 살리실산(salicylic acid), 설포살리실산(sulfosalicylic acid), 벤조산(benzoic acid), 락트산(lactic acid), 글리세르산(glyceric acid), 석신산(succinic acid), 말산(malic acid), 타르타르산(tartaric acid), 이소시트르산(isocitric acid), 프로펜산(propenoic acid), 이미노디아세트산(imminodiacetic acid), 카프릴산(caprylic acid) 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid; EDTA), 등을 들 수 있으며,More specific examples of carboxylic acids having 1 to 20 carbon atoms include ascorbic acid, acetic acid, butanoic acid, citric acid, formic acid, and gluconic acid. ), Glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, phthalic acid, Sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid acid), tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid, caprylic acid ethylenediaminetetraacetic acid (EDTA), etc. Can be
탄소수 1 내지 20의 알킬설폰산 또는 탄소수 6 내지 20의 아릴설폰산의 보다 구체적인 예를 들면, 메탄설폰산, 에탄설폰산, 벤젠설폰산, 파라톨루엔셀폰산 등을 들 수 있다.More specific examples of the alkyl sulfonic acid having 1 to 20 carbon atoms or the aryl sulfonic acid having 6 to 20 carbon atoms include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and paratoluenecellonic acid.
이들은 단독으로 또는 2종 이상 혼합하여 사용될 수 있다.These may be used alone or in combination of two or more.
또한, 상기 유기산은 본 발명에 따른 식각액 조성물의 1% 수용액이 pH 2 내지 pH 7을 만족하도록 선택되는 것이 보다 바람직하다.Further, the organic acid is more preferably selected so that the 1% aqueous solution of the etching solution composition according to the present invention satisfies pH 2 to pH 7.
상기 유기산의 함량은 특별히 한정되지 않으나, 예를 들면, 식각액 조성물 총 중량에 대하여, 1 내지 40중량%로 포함될 수 있으며, 바람직하게는 1 내지 30중량%일 수 있다. 또한, 상기 유기산은 본 발명에 따른 식각액 조성물의 1% 수용액이 pH 2 내지 pH 7을 만족하도록 포함되는 것이 보다 바람직하다. 상기 범위를 만족하는 경우, 실리콘 산화막에 대한 적정 식각 속도를 나타냄과 동시에, 하부 금속막에 대한 결함을 억제할 수 있다.The content of the organic acid is not particularly limited, for example, based on the total weight of the etchant composition, may be included in 1 to 40% by weight, preferably 1 to 30% by weight. In addition, the organic acid is more preferably included so that the 1% aqueous solution of the etching solution composition according to the present invention satisfies pH 2 to pH 7. When the above range is satisfied, the appropriate etching rate for the silicon oxide film is exhibited, and defects in the lower metal film can be suppressed.
탄소수Carbon number 1 내지 20의 1 to 20 알킬암모늄플루오라이드Alkyl ammonium fluoride
본 발명의 식각액 조성물에 포함되는 탄소수 1 내지 20의 알킬암모늄플루오라이드는 실리콘 산화막을 식각하는 성분으로, 전술한 유기산과의 반응 통해 불화수소(HF)를 생성시켜 효과적으로 실리콘 산화막을 식각할 수 있게 한다. The alkyl ammonium fluoride having 1 to 20 carbon atoms included in the etching solution composition of the present invention is a component for etching the silicon oxide film, and generates hydrogen fluoride (HF) through reaction with the organic acid described above to effectively etch the silicon oxide film. .
한편, 무기암모늄플루오라이드를 사용하는 경우, 유기용매 단독으로 용해가 불가능하여, 물을 용매로 사용해야하는데, 이 경우 물에 의해 불화수소(HF)의 활동도가 과도하게 상승하여, 하부 금속막의 과식각을 유발하는 문제가 있었다.On the other hand, when using an inorganic ammonium fluoride, the organic solvent alone cannot be dissolved, and water must be used as a solvent. In this case, the activity of the hydrogen fluoride (HF) is excessively increased by water, resulting in overeating of the lower metal film. There was a problem that caused the angle.
그러나, 본 발명은 상기 탄소수 1 내지 20의 알킬암모늄플루오라이드를 사용함으로써, 하부 금속막의 결함 없이 효과적으로 실리콘 산화막을 식각할 수 있게 한다. However, the present invention makes it possible to etch the silicon oxide film effectively without defects of the lower metal film by using the alkylammonium fluoride having 1 to 20 carbon atoms.
또한, 본 발명의 식각액 조성물은 유기산과 탄소수 1 내지 20의 알킬암모늄플루오라이드를 포함함으로써, 불화수소(HF)를 별도로 첨가하지 않게되어 사용상 보다 안전하다.In addition, the etchant composition of the present invention contains an organic acid and an alkylammonium fluoride having 1 to 20 carbon atoms, so that hydrogen fluoride (HF) is not added separately, and is safer to use.
상기 탄소수 1 내지 20의 알킬암모늄플루오라이드의 종류는 특별히 한정되지 않으며, 예를 들면, 알킬암모늄플루오라이드는 테트라메틸암모늄플루오라이드, 테트라에틸암모늄플루오라이드, 테트라부틸암모늄플루오라이드 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상 혼합하여 사용될 수 있다.The type of the alkyl ammonium fluoride having 1 to 20 carbon atoms is not particularly limited, and examples of the alkyl ammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, and tetrabutylammonium fluoride. These may be used alone or in combination of two or more.
상기 탄소수 1 내지 20의 알킬암모늄플루오라이드의 함량은 특별히 한정되지 않으나, 예를 들면, 식각액 조성물 총 중량에 대하여, 0.1 내지 20중량%로 포함될 수 있으며, 바람직하게는 0.1 내지 10중량%일 수 있다. 상기 범위를 만족하는 경우, 실리콘 산화막에 대한 적정 식각 속도를 나타냄과 동시에, 하부 금속막에 대한 결함을 억제할 수 있다.The content of the alkyl ammonium fluoride having 1 to 20 carbon atoms is not particularly limited, for example, based on the total weight of the etchant composition, may be included in 0.1 to 20% by weight, preferably 0.1 to 10% by weight . When the above range is satisfied, an appropriate etching rate for the silicon oxide film is exhibited, and defects in the lower metal film can be suppressed.
유기 용매Organic solvent
본 발명의 식각액 조성물에 사용되는 유기 용매는 상기 성분들을 용해시킬 수 있는 것으로서, 그 종류는 특별히 한정되지 않으나,The organic solvent used in the etching solution composition of the present invention is capable of dissolving the above components, but the type is not particularly limited,
구체적인 예를 들면, 에틸렌글리콜, 프로필렌글리콜, 부틸렌글리콜 등과 같은 글리콜류;Specific examples include glycols such as ethylene glycol, propylene glycol, and butylene glycol;
에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르 등의 에틸렌글리콜모노알킬에테르류;Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노프로필에테르, 프로필렌글리콜모노부틸에테르 등의 프로필렌글리콜모노알킬에테르류;Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디프로필에테르, 디에틸렌글리콜디부틸에테르 등의 디에틸렌글리콜디알킬에테르류;Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;
메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르아세테이트류;Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
메틸아세테이트, 부틸아세테이트, 프로필아세테이트 등의 알킬아세테이트류;Alkyl acetates such as methyl acetate, butyl acetate, and propyl acetate;
프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 메톡시부틸아세테이트, 메톡시펜틸아세테이트 등의 알킬렌글리콜알킬에테르아세테이트류;Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate;
벤젠, 톨루엔, 크실렌, 메시틸렌 등의 방향족 탄화수소류;Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene;
메틸에틸케톤, 아세톤, 메틸아밀케톤, 메틸이소부틸케톤, 시클로헥사논 등의 케톤류;Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;
에탄올, 프로판올, 부탄올, 헥사놀, 시클로헥산올, 디아세톤알코올, 테트라퍼퓨릴알코올, 테트라하이드로퍼퓨릴알코올 등의 알코올류;Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, diacetone alcohol, tetraperfuryl alcohol, and tetrahydrofurfuryl alcohol;
3-에톡시프로피온산에틸, 3-메톡시프로피온산메틸 등의 에스테르류, γ-부티롤락톤 등의 환상 에스테르류; 등을 들 수 있으며, 바람직하게는 극성 양성자성 용매가 적합하다.Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone; Etc. are mentioned, Preferably, a polar protic solvent is suitable.
상기 유기용매의 함량은 특별히 한정되지 않으나, 예를 들면, 식각액 조성물 총 중량에 대하여, 50 내지 99중량%로 포함될 수 있으며, 바람직하게는 70 내지 90중량%일 수 있다. 상기 범위를 만족하는 경우, 적정 식각 속도 및 용해도를 나타낼 수 있다.
The content of the organic solvent is not particularly limited, for example, with respect to the total weight of the etchant composition, may be included in 50 to 99% by weight, preferably 70 to 90% by weight. When the above range is satisfied, an appropriate etching rate and solubility may be exhibited.
또한, 본 발명의 식각액 조성물은 전술한 성분 이외에 필요에 따라, 통상의 첨가제를 더 포함할 수 있다. 첨가제의 예를 들면 식각 조절제, 금속 이온 봉쇄제, 부식 방지제, 계면활성제, pH 조절제 등을 들 수 있으나, 이에 한정되는 것은 아니다.
In addition, the etchant composition of the present invention may further contain a conventional additive, if necessary, in addition to the components described above. Examples of the additives include, but are not limited to, etching control agents, metal ion blockers, corrosion inhibitors, surfactants, pH adjusting agents, and the like.
<패턴형성 방법><Pattern formation method>
또한, 본 발명은 Ⅰ)기판 상에 금속막을 형성하는 단계; Ⅱ)상기 금속막 상에 실리콘 산화막을 형성하는 단계; Ⅲ)포토리소그라피 공정으로 상기 실리콘 산화막 상에 포토레지스트 패턴을 형성하는 단계; 및 Ⅳ)상기 실리콘 산화막을 본 발명에 따른 식각액 조성물로 식각하는 단계;를 포함하는 실리콘 산화막의 패턴 형성 방법.
In addition, the present invention is Ⅰ) forming a metal film on the substrate; Ⅱ) forming a silicon oxide film on the metal film; Ⅲ) forming a photoresist pattern on the silicon oxide film by a photolithography process; And Ⅳ) etching the silicon oxide film with an etchant composition according to the present invention.
상기 금속막의 종류는 특별히 한정되지 않으나, 예를 들면, 알루미늄계 금속막일 수 있으며, 상기 알루미늄계 금속막은 막의 구성 성분 중에 알루미늄(Al)이 포함되는 것으로서, 단일막 및 이중막, 삼중막 등의 다층막을 포함하는 개념이다.The type of the metal film is not particularly limited, but may be, for example, an aluminum-based metal film, and the aluminum-based metal film includes aluminum (Al) in the constituent components of the film, and is a multi-layer film such as a single film, a double film, and a triple film. It is a concept that includes.
예컨데, 알루미늄 또는 알루미늄의 합금의 단일막을 포함할 수 있으며, 알루미늄 합금막은 알루미늄(Al)과 함께, 니켈(Ni), 인듐(In), 마그네슘(Mg), 망간(Mn), 베릴륨(Be), 하프늄(Hf), 나이오븀(Nb), 텅스텐(W) 및 바나듐(V), 은(Ag), 몰리브데늄(Mo), 티타늄(Ti), 구리(Cu), 팔라듐(Pd), 란타늄(La)으로 이루어진 군으로부터 선택된 1종 이상을 함유하는 알루미늄 합금 또는 상기 알루미늄 합금의 질화물(예를 들면, TiAlN) 또는 탄화물(예를 들면, TiAlC)로 구성된 알루미늄 합금막을 의미한다. For example, it may include a single film of aluminum or an alloy of aluminum, and the aluminum alloy film together with aluminum (Al), nickel (Ni), indium (In), magnesium (Mg), manganese (Mn), beryllium (Be), Hafnium (Hf), Niobium (Nb), Tungsten (W) and Vanadium (V), Silver (Ag), Molybdenum (Mo), Titanium (Ti), Copper (Cu), Palladium (Pd), Lanthanum ( It means an aluminum alloy containing at least one selected from the group consisting of La) or an aluminum alloy film made of nitride (for example, TiAlN) or carbide (for example, TiAlC) of the aluminum alloy.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
Hereinafter, preferred embodiments are provided to help the understanding of the present invention, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims, and the embodiments are within the scope and technical scope of the present invention. It is apparent to those skilled in the art that various changes and modifications to the present invention are possible, and it is natural that such modifications and modifications belong to the appended claims.
실시예Example 및 And 비교예Comparative example
(중량%)division
(weight%)
플루오라이드Alkyl ammonium
Fluoride
플루오라이드ammonium
Fluoride
A-2: 카프릴산(98%)
B-1: 황산(96%)
B-2: HF(50%)
C-1: 테트라부틸암모늄플루오라이드
C-2: 테트라메틸암모늄플루오라이드
D-1: 암모늄플루오라이드
D-2: 암모늄바이플루오라이드
E-1: 에틸렌글리콜
E-2: 디에틸렌글리콜모노부틸에테르
E-3: 테트라하이드로퍼퓨릴알코올
E-4: 프로필렌글리콜모노메틸에테르아세테이트(극성 비양성자성 용매)A-1: Formic acid (99%)
A-2: Caprylic acid (98%)
B-1: sulfuric acid (96%)
B-2: HF (50%)
C-1: tetrabutylammonium fluoride
C-2: tetramethylammonium fluoride
D-1: Ammonium fluoride
D-2: Ammonium bifluoride
E-1: Ethylene glycol
E-2: Diethylene glycol monobutyl ether
E-3: Tetrahydroperfuryl alcohol
E-4: Propylene glycol monomethyl ether acetate (polar aprotic solvent)
시험방법Test Methods
1) 실리콘 1) Silicone 산화막의Oxide 식각Etch 평가 evaluation
실리콘 산화막의 식각 속도를 측정하기 위해, 실리콘 웨이퍼 상에 2000Å 두께로 증착된 실리콘 산화막을 포함하는 기판을 준비하였다. 상기 기판을 2x2cm 크기로 샘플링하여, 25℃의 항온조에 실시예 및 비교예의 식각액 조성물에 10분 동안 침지시킨 후 건져내었다. 이후에 주사 전자현미경(SEM, Hitachi S-4700)으로 실리콘 산화막의 두께를 확인하여 식각율을 산출하였고, 이를 하기 표 2에 나타내었다.
In order to measure the etching rate of the silicon oxide film, a substrate including a silicon oxide film deposited to a thickness of 2000 mm 2 on a silicon wafer was prepared. The substrate was sampled to a size of 2x2 cm, and then immersed in an etchant composition of Examples and Comparative Examples for 10 minutes in a constant temperature bath at 25 ° C and then dried. Subsequently, the thickness of the silicon oxide film was checked using a scanning electron microscope (SEM, Hitachi S-4700) to calculate the etch rate, which is shown in Table 2 below.
2) 2) AlAl 의 of 손상정도Degree of damage 평가 evaluation
알루미늄 막의 손상 정도를 평가하기 위해, 실리콘 웨이퍼 상에 3000Å 두께로 증착된 알루미늄막을 포함하는 기판을 준비하였다. 상기 기판을 2x2cm 크기로 샘플링하여, 25℃의 항온조에 실시예 및 비교예의 식각액 조성물에 5분 동안 침지시킨 후 건져내었다. 이후에 주사 전자현미경(SEM, Hitachi S-4700)으로 알루미늄 막의 두께를 확인하여 하기 기준에 따라 손상 정도를 평가하고, 그 결과를 하기 표 2에 나타내었다.
To evaluate the degree of damage to the aluminum film, a substrate including an aluminum film deposited to a thickness of 3000 mm 3 on a silicon wafer was prepared. The substrate was sampled to a size of 2x2 cm, and then immersed in an etchant composition of Examples and Comparative Examples for 5 minutes in a constant temperature bath at 25 ° C and then dried. Thereafter, the thickness of the aluminum film was checked with a scanning electron microscope (SEM, Hitachi S-4700) to evaluate the degree of damage according to the following criteria, and the results are shown in Table 2 below.
3)3) pHpH , , 색변화Color change 및 용해도 평가(경시 안정성 평가) And solubility evaluation (aging stability evaluation)
상기 실시예 및 비교예의 조성물을 각각 50ml씩 준비하여 pH 미터(메틀러토레도)에 침지하여 측정된 pH 값을 표 2에 표기하였다. 또한 실시예 및 비교예의 용해도 및 색변화를 육안으로 관찰하여 표2에 그 결과를 함께 표기하였다.50 ml of each of the compositions of Examples and Comparative Examples was prepared and immersed in a pH meter (Mettler Toredo) to indicate the measured pH values in Table 2. In addition, the solubility and color change of Examples and Comparative Examples were visually observed and the results are shown in Table 2.
<색변화 평가 기준><Criteria for evaluating color change>
○: APHA Color 값이 100 미만○: APHA Color value is less than 100
△: APHA Color 값이 100 이상 300 미만△: APHA Color value between 100 and 300
X: APHA Color 값이300 이상X: APHA Color value over 300
<용해도><Solubility>
○: 하부의 침전이 발생되지 않으며 투명함○: No sedimentation occurs at the bottom and is transparent
△: 하부에 침전이 발생되지 않으나 용액의 현탁이 발생됨△: No precipitation occurred at the bottom, but suspension of the solution occurred.
X: 하부에 침전과 용액의 현탁이 모두 발생됨X: Both precipitation and suspension of solution occurred at the bottom
(중량%)division
(weight%)
식각속도
(Å/min)Silicon oxide
Etch rate
(Å / min)
손상평가
(Å/min)Aluminum
Damage evaluation
(Å / min)
(1% 수용액)pH
(1% aqueous solution)
상기 표 2를 참고하면, 본 발명에 따른 식각액 조성물(실시예 1 내지 10)은 실리콘 산화막을 빠른 속도로 식각함과 동시에 하부 알루미늄막의 손상을 일으키지 않고, 경시 안정성도 뛰어난 것을 확인할 수 있었다.Referring to Table 2, it was confirmed that the etchant compositions according to the present invention (Examples 1 to 10) did not cause damage to the lower aluminum film at the same time as etching the silicon oxide film at a high speed, and also excellent stability over time.
유기산 대신 무기산을 사용한 비교예 1의 경우, 식각 속도는 실시예와 동등수준을 나타내었으나, 알루미늄막에 결함이 발생하였으며, 조성물의 색변화가 발생하는 등 경시 안정성이 저하된 것을 확인할 수 있었다.In the case of Comparative Example 1 using an inorganic acid instead of an organic acid, the etch rate was equivalent to that of the Example, but defects occurred in the aluminum film, and it was confirmed that stability over time, such as color change of the composition, was deteriorated.
비교예 3 및 4의 경우, 무기암모늄플루오라이드를 사용함으로써, 유기용매로 용해되지 않아, 식각액으로 사용할 수 없었으며, 무기암모늄플루오라이드를 사용하고 용매로 유기용매와 함께 탈이온수를 사용한 비교예 5의 경우, 알루미늄막의 손상 정도가 현저히 증가한 것을 확인할 수 있었다.In the case of Comparative Examples 3 and 4, by using inorganic ammonium fluoride, it was not dissolved as an organic solvent, so it could not be used as an etching solution. Comparative Example 5 using inorganic ammonium fluoride and using deionized water with an organic solvent as a solvent In the case of, it was confirmed that the degree of damage to the aluminum film was significantly increased.
Claims (8)
상기 유기산은 포름산(formic acid), 아세트산(acetic acid), 프로펜산(propenoic acid), 부탄산(butanoic acid), 펜탄산(pentanoic acid), 벤조산(benzoic acid), 카프릴산(caprylic acid), 메탄설폰산, 에탄설폰산, 벤젠설폰산 및 파라톨루엔설폰산으로 이루어진 군에서 선택된 적어도 하나를 포함하는, 금속막 상에 형성된 실리콘 산화막용 비수계 식각액 조성물.
Contains an organic acid, an alkylammonium fluoride having 1 to 20 carbon atoms and an organic solvent, and does not contain water,
The organic acid is formic acid, acetic acid, propenoic acid, butanoic acid, pentanoic acid, benzoic acid, caprylic acid, A non-aqueous etchant composition for a silicon oxide film formed on a metal film, comprising at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and paratoluenesulfonic acid.
The method according to claim 1, wherein the alkyl ammonium fluoride having 1 to 20 carbon atoms includes at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride and tetrabutylammonium fluoride, silicon formed on the metal film Non-aqueous etching solution composition for oxide film.
The method according to claim 1, The organic solvent is a polar protic solvent, a non-aqueous etchant composition for a silicon oxide film formed on a metal film.
The method according to claim 1, The composition of the total weight of the organic acid 1 to 40%, 1 to 20 carbon atoms of alkyl ammonium fluoride 0.1 to 20% by weight, the organic solvent 50 to 90% by weight, the silicon oxide film ratio formed on the metal film Aqueous etchant composition.
The method according to claim 1, The metal film is an aluminum-based metal film, a non-aqueous etchant composition for a silicon oxide film formed on a metal film.
Ⅱ)상기 금속막 상에 실리콘 산화막을 형성하는 단계;
Ⅲ)포토리소그라피 공정으로 상기 실리콘 산화막 상에 포토레지스트 패턴을 형성하는 단계; 및
Ⅳ)상기 실리콘 산화막을 청구항 1, 3 내지 5 및 7 중 어느 한 항의 식각액 조성물로 식각하는 단계;
를 포함하는, 금속막 상에 형성된 실리콘 산화막의 패턴 형성 방법.Ⅰ) forming a metal film on the substrate;
Ⅱ) forming a silicon oxide film on the metal film;
Ⅲ) forming a photoresist pattern on the silicon oxide film by a photolithography process; And
Ⅳ) etching the silicon oxide film with an etchant composition of any one of claims 1, 3 to 5 and 7;
The method of forming a pattern of a silicon oxide film formed on a metal film comprising a.
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