KR20170084600A - ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME - Google Patents
ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME Download PDFInfo
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- KR20170084600A KR20170084600A KR1020160003831A KR20160003831A KR20170084600A KR 20170084600 A KR20170084600 A KR 20170084600A KR 1020160003831 A KR1020160003831 A KR 1020160003831A KR 20160003831 A KR20160003831 A KR 20160003831A KR 20170084600 A KR20170084600 A KR 20170084600A
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- etching
- tin
- metal wiring
- film
- peroxide
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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
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims 6
- 238000005530 etching Methods 0.000 claims abstract description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000002978 peroxides Chemical class 0.000 claims abstract description 21
- -1 N-oxide compounds Chemical class 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052721 tungsten Inorganic materials 0.000 claims description 19
- 239000010937 tungsten Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 60
- 239000010408 film Substances 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 21
- 235000013399 edible fruits Nutrition 0.000 description 14
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 9
- 238000001039 wet etching Methods 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229910004205 SiNX Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 235000015203 fruit juice Nutrition 0.000 description 3
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 3
- 229910003134 ZrOx Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- 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
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Weting (AREA)
Abstract
본 발명은 조성물 총 중량에 대하여, (A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상 75~95 중량%, (B) 과산화물 0.3~10 중량%, (C) 퍼설페이트류 및 하기 화학식 1로 표시되는 N-옥사이드 화합물로 이루어진 군으로부터 선택되는 1종 이상의 보조산화제 0.0005~3 중량%, 및 (D) 잔량의 물을 포함하는 TiN막 식각용 조성물 및 그 식각용 조성물을 이용하는 금속배선의 형성 방법을 제공한다:
[화학식 1]
[Chemical Formula 1]
Description
본 발명은 질화 티탄(TiN) 막의 식각액 조성물 및 그를 이용한 금속배선의 형성 방법에 관한 것이다.The present invention relates to an etchant composition of a titanium nitride (TiN) film and a method of forming a metal wiring using the same.
일반적인 포토리소그래피에 의하여 패턴된 포토레지스트(PR) 마스크는 두께가 두껍고 식각속도가 빠른 특징을 갖는다. 또한 PR 마스크의 사용은 식각 잔유물에 의한 MTJ stack의 측면에 재증착 현상을 유발한다. A photoresist (PR) mask patterned by general photolithography is characterized by a thick thickness and a high etch rate. The use of a PR mask also causes re-deposition on the sides of the MTJ stack due to etching residues.
PR 마스크를 사용하여 식각속도가 느린 식각 대상 금속막의 패턴을 형성하는 경우, PR 마스크의 빠른 식각 속도는 식각속도가 느린 식각 대상 금속막의 식각 선택도를 낮추고 결과적으로 낮은 식각 경사를 야기한다. 그러므로 이러한 PR 마스크의 특징들은 소자의 특성을 저하시키고 고집적화를 방해하는 요인이 되기도 한다. When a PR mask is used to form a pattern of a metal film to be etched at a low etch rate, the rapid etch rate of the PR mask lowers the etch selectivity of the etch target metal film and results in a low etch slope. Therefore, the characteristics of the PR mask deteriorate the characteristics of the device and hinder high integration.
최근 상기와 같은 PR 마스크의 문제를 해결하기 위해서 하드 마스크를 이용하는 기술이 사용되고 있다. 상기 하드 마스크 물질로는 TiN 박막 등이 사용되고 있다. Recently, a technique using a hard mask has been used to solve the problem of the PR mask. As the hard mask material, a TiN thin film or the like is used.
상기 TiN 하드마스크의 식각은 고밀도 플라즈마를 이용하는 유도 결합 플라즈마 반응성 이온 식각 장비(inductively coupled plasma reactive ion etching: ICPRIE) 등을 사용하여 이루어지고 있다. The etching of the TiN hard mask is performed using inductively coupled plasma reactive ion etching (ICPRIE) using high-density plasma.
상기 TiN 하드마스크의 습식 식각 방법으로서 대한민국 특허등록 제1282177호는 과수, 유기산염, 암모니아 및 물을 포함하는 것을 특징으로 하는 티탄계 금속, 텅스텐계 금속, 티탄-텅스텐계 금속 또는 그것들의 질화물의 에칭액을 개시하고 있다. 그러나, 상기 방법 외에 TiN 하드마스크의 습식 식각 방법은 잘 알려져 있지 않다. 특히, 텅스텐을 포함하는 금속막 또는 금속 배선에 대하여 높은 선택도를 갖는 TiN 하드마스크의 습식 식각 방법은 보고된 바 없다. As a wet etching method for the TiN hard mask, Korean Patent Registration No. 1282177 discloses a method for wet etching an etching solution of a titanium-based metal, a tungsten-based metal, a titanium-tungsten-based metal or a nitride thereof . However, the wet etching method of the TiN hard mask is not well known. In particular, a wet etching method of a TiN hard mask having high selectivity for a metal film or metal wiring including tungsten has not been reported.
그러므로, TiN 하드마스크의 습식 식각 방법 및 텅스텐을 포함하는 금속막 또는 금속 배선에 대하여 높은 선택도를 갖는 TiN 하드마스크의 습식 식각 방법의 개발이 요구되고 있다.Therefore, development of a wet etching method of a TiN hard mask and a wet etching method of a TiN hard mask having a high selectivity for a metal film or a metal wiring including tungsten is required.
대한민국 특허등록 제1282177호Korea Patent No. 1282177
본 발명은 종래기술의 상기와 같은 문제를 해결하기 위한 것으로서, TiN 막을 효율적으로 습식식각할 수 있는 TiN막 식각용 조성물을 제공하는 것을 목적으로 한다. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a composition for etching a TiN film capable of efficiently wet etching a TiN film.
또한, 본 발명은 텅스텐을 포함하는 금속막 또는 금속 배선에 대하여 높은 선택도를 갖는 TiN막 식각용 조성물을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a composition for etching a TiN film having a high selectivity with respect to a metal film or metal wiring including tungsten.
또한, 본 발명은 반도체의 주요 구성 막질인 SiNx, SiOx, poly Si, HfOx, ZrOx 등의 high-k 재료뿐만 아니라 TEOS, organosilicate glasses(OSG)등의 low-k 재료에 대한 손상 없이 TiN막을 선택적으로 식각할 수 있는 TiN막 식각용 조성물을 제공하는 것을 목적으로 한다.The present invention also provides a method for selectively etching a TiN film without damaging low-k materials such as TEOS and organosilicate glasses (OSG) as well as high-k materials such as SiNx, SiOx, poly Si, HfOx and ZrOx, And to provide a composition for etching a TiN film that can be etched.
또한, 본 발명은 상기와 같은 TiN막 식각용 조성물을 사용하여 금속 배선을 형성하는 방법을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a method for forming a metal wiring using the above composition for etching a TiN film.
본 발명은The present invention
조성물 총 중량에 대하여,With respect to the total weight of the composition,
(A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상 75~95 중량%, (A) 75 to 95% by weight of at least one selected from sulfuric acid and alkylsulfonic acid,
(B) 과산화물 0.3~10 중량%,(B) 0.3 to 10% by weight of peroxide,
(C) 퍼설페이트류 및 하기 화학식 1로 표시되는 N-옥사이드 화합물로 이루어진 군으로부터 선택되는 1종 이상의 보조산화제 0.0005~3 중량%, 및0.0005 to 3% by weight of at least one co-oxidant selected from the group consisting of (C) persulfates and N-oxide compounds represented by the following formula
(D) 잔량의 물을 포함하는 TiN막 식각용 조성물을 제공한다:(D) a residual amount of water.
[화학식 1] [Chemical Formula 1]
상기 식에서,In this formula,
R1 내지 R3는 각각 독립적으로 C1~C4의 알킬기일 수 있으며, R1 to R3 each independently may be an alkyl group of C1 to C4,
R2 및 R3는 서로 결합하여 기 존재하는 질소원자와 C4~C6의 헤테로 고리를 형성할 수 있다.R2 and R3 may combine with each other to form a C4 to C6 hetero ring with the nitrogen atom present.
또한, 본 발명은In addition,
하부 금속막 또는 금속배선으로서 텅스텐(W)을 포함하는 금속막 또는 금속배선을 포함하며, TiN막을 하드마스크로 사용하는 금속배선의 형성 방법에 있어서, A method of forming a metal wiring using a TiN film as a hard mask, the metal film including a metal film or metal wiring including tungsten (W) as a lower metal film or a metal wiring,
상기 텅스텐(W)을 포함하는 금속막 또는 금속배선에 대하여 상기 TiN 하드마스크를 선택적으로 식각하는 단계를 포함하며, 상기 식각단계는 상기 본 발명의 식각액을 사용하여 이루어지는 것을 특징으로 하는 금속배선의 형성 방법을 제공한다.And selectively etching the TiN hard mask with respect to a metal film or metal wiring including the tungsten (W), wherein the etching step is performed using the etching solution of the present invention ≪ / RTI >
본 발명의 TiN막 식각용 조성물은 TiN 막에 대한 효율적인 습식식각을 가능하게 한다.The TiN film etching composition of the present invention enables efficient wet etching of TiN films.
또한, 본 발명의 TiN막 식각용 조성물은 텅스텐을 포함하는 금속막 또는 금속 배선에 대하여 높은 선택도를 갖기 때문에, 텅스텐을 포함하는 금속막 또는 금속 배선이 형성되어 있는 경우에도 TiN막을 선택적으로 식각할 수 있다. In addition, since the composition for etching a TiN film of the present invention has high selectivity for a metal film or metal wiring including tungsten, even when a metal film or metal wiring including tungsten is formed, the TiN film is selectively etched .
또한, 본 발명의 TiN막 식각용 조성물은 반도체의 주요 구성 막질인 SiNx, SiOx, poly Si, HfOx, ZrOx 등의 high-k 물질뿐만 아니라 TEOS, organosilicate glasses(OSG)등의 low-k 재료에 대한 손상 없이 TiN막을 선택적으로 식각할 수 있다.In addition, the composition for etching a TiN film of the present invention can be used not only for high-k materials such as SiNx, SiOx, poly Si, HfOx, and ZrOx as main constituent semiconductors, but also for low-k materials such as TEOS and organosilicate glasses The TiN film can be selectively etched without damage.
또한, 본 발명의 TiN막 식각용 조성물은 특히 TiN 하드마스크의 식각시에 매우 유용하게 사용될 수 있다. In addition, the composition for etching a TiN film of the present invention can be particularly usefully used for etching a TiN hard mask.
본 발명은, 조성물 총 중량에 대하여, (A) 황산 및 알킬설폰산(alkyl sulfonic acid) 중에서 선택되는 1종 이상 75~95 중량%, (B) 과산화물 0.3~10 중량%, (C) 퍼설페이트류 및 하기 화학식 1로 표시되는 N-옥사이드 화합물로 이루어진 군으로부터 선택되는 1종 이상의 보조산화제 0.0005~3 중량%, 및 (D) 잔량의 물을 포함하는 TiN막 식각용 조성물에 관한 것이다:(A) at least 75-95 wt% of at least one selected from sulfuric acid and alkyl sulfonic acid, (B) 0.3-10 wt% of peroxide, (C) And 0.0005 to 3% by weight of at least one co-oxidant selected from the group consisting of an N-oxide compound represented by the following formula (1), and (D) the remaining amount of water.
[화학식 1] [Chemical Formula 1]
상기 식에서,In this formula,
R1 내지 R3는 각각 독립적으로 C1~C4의 알킬기일 수 있으며, R1 to R3 each independently may be an alkyl group of C1 to C4,
R2 및 R3는 서로 결합하여 기 존재하는 질소원자와 C4~C6의 헤테로 고리를 형성할 수 있다.R2 and R3 may combine with each other to form a C4 to C6 hetero ring with the nitrogen atom present.
상기 기 존재하는 질소원자 외에 N, O, 및 S 중에서 선택되는 1개의 헤테로 원자를 더 포함할 수 있다. And may further include one heteroatom selected from N, O, and S in addition to the nitrogen atom present in the group.
상기 TiN막은 용도와 관계 없이 TiN으로 이루어진 막을 의미한다. 예컨대, 상기 TiN막은 금속배선을 형성하는 것이거나, TiN 하드마스크로 쓰일 수 있다.The TiN film means a film made of TiN irrespective of use. For example, the TiN film may form a metal wiring or may be used as a TiN hard mask.
상기 TiN막 식각용 조성물은 텅스텐(W)을 포함하는 금속막 또는 금속배선의 존재하에서 TiN막의 선택적 식각을 위하여 유용하게 사용될 수 있다. The composition for etching a TiN film may be useful for selective etching of a TiN film in the presence of a metal film containing tungsten (W) or a metal wiring.
본 발명의 TiN막 식각용 조성물은 텅스텐(W)을 포함하는 금속막 또는 금속배선에 대한 TiN막의 선택 식각비가 7:1 이상인 것을 특징으로 한다. The composition for etching the TiN film of the present invention is characterized in that the selective etching ratio of the TiN film to the metal film containing tungsten (W) or metal wiring is 7: 1 or more.
본 발명의 TiN막 식각용 조성물은 상기 (A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상의 성분과 (B) 과산화물 성분의 중량비가 10:1 ~ 50:1인 것이 바람직하며, 16:1 ~ 35:1인 것이 더욱 바람직하다. 상기 중량비의 범위를 벗어나는 경우, TiN/W 식각 선택비가 7 이상으로 구현될 수 없거나, TiN의 식각 속도가 너무 느려져 공정 시간이 증가하므로 공정 처리량(throughput)에 악영향을 미친다. The composition for etching the TiN film of the present invention preferably has a weight ratio of the at least one component selected from the group consisting of sulfuric acid and alkylsulfonic acid and the peroxide component to the component (B) from 10: 1 to 50: 1, More preferably 35: 1. If the weight ratio is out of the range, the TiN / W etching selection ratio can not be realized to be 7 or more, or the etching speed of the TiN is too slow to increase the processing time, which adversely affects the throughput of the process.
본 발명의 TiN막 식각용 조성물에 있어서, 상기 (A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상의 성분은 TiN 막질과 W 막질의 에칭량과 선택비를 조절하는 기능을 수행한다.In the composition for etching a TiN film of the present invention, at least one component selected from the group consisting of sulfuric acid and alkylsulfonic acid (A) functions to control the etching amount and selectivity of the TiN film and the W film.
상기 알킬설폰산은 메탄설폰산, 에탄설폰산, 프로판설폰산, 부탄설폰산 등으로부터 선택될 수 있으며, 이들은 1종 단독으로 또는 2종 이상의 조합으로 사용될 수 있다.The alkyl sulfonic acid may be selected from methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and the like, and these may be used singly or in combination of two or more.
상기 (A) 성분들 중 황산이 더욱 바람직하게 사용될 수 있다. Of the above components (A), sulfuric acid may be more preferably used.
상기 (A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상의 성분은 조성물 총 중량에 대하여, 75~95 중량%로 포함되며, 더욱 바람직하게는 80~90 중량%로 포함된다. 상기 성분이 75 중량% 미만으로 포함되면 상대적으로 과산화물 및 물의 함량이 높아지면서 W의 식각속도가 빨라지면서 TiN/W의 식각선택비가 낮아지는 문제가 발생하며, 95 중량%를 초과하면 TiN의 식각속도가 너무 느려져 공정 수율 측면에서 문제가 발생하여 바람직하지 않다. At least one component selected from the group consisting of (A) sulfuric acid and alkylsulfonic acid is contained in an amount of 75 to 95 wt%, more preferably 80 to 90 wt%, based on the total weight of the composition. When the content of the component is less than 75 wt%, the content of peroxide and water is increased, and the etching rate of W is increased and the etching selectivity ratio of TiN / W is lowered. When the content is more than 95 wt% Is too slow to cause a problem in terms of process yield.
본 발명에서 상기 (B) 과산화물은 TiN의 식각속도를 증가시키며, 텅스텐막을 산화시켜 공정 상 필요한 만큼의 텅스텐막의 식각속도를 조절하는 기능을 수행한다.In the present invention, the peroxide (B) increases the etch rate of TiN and oxidizes the tungsten film to control the etching rate of the tungsten film in the process.
상기 과산화물로는 과산화수소(H2O2), tert-부틸하이드로퍼옥사이드, 라우로일 퍼옥사이드, tert-부틸퍼아세테이트, tert-부틸퍼옥시벤조에이트, 2-부탄퍼옥사이드, 메틸에틸케톤 퍼옥사이드, 벤조일 퍼옥사이드, 다이커밀퍼옥사이드 등으로부터 선택될 수 있으며, 이들은 1종 단독으로 또는 2종 이상의 조합으로 사용될 수 있다.As the peroxide, hydrogen peroxide (H 2 O 2 ), tert-butyl hydroperoxide, lauroyl peroxide, tert-butyl peracetate, tert-butyl peroxybenzoate, 2-butane peroxide, methyl ethyl ketone peroxide , Benzoyl peroxide, dicumyl peroxide, etc. These may be used singly or in combination of two or more.
상기 과산화물 중에서 과산화수소가 더욱 바람직하게 사용될 수 있다. Of these peroxides, hydrogen peroxide can be more preferably used.
상기 (B) 과산화물은 조성물 총 중량에 대하여, 0.3~10 중량%로 포함되며, 더욱 바람직하게는 1~5 중량%로 포함된다. 상기 성분이 0.3 중량% 미만으로 포함되면 TiN의 식각속도가 너무 느려져 공정 수율 측면에서 문제가 발생하며, 10 중량%를 초과하면 TiN막의 선택적 식각이 어려워지므로 바람직하지 않다. The peroxide (B) is contained in an amount of 0.3 to 10% by weight, more preferably 1 to 5% by weight based on the total weight of the composition. If the amount of the component is less than 0.3% by weight, the etching rate of TiN becomes too slow to cause a problem in terms of process yield. If it exceeds 10% by weight, selective etching of the TiN film becomes difficult.
본 발명에서 상기 (C) 보조산화제는 과산화물이 TiN 막을 제거시키는데 있어서 보조역할을 수행하는 산화제로서 TiN의 식각성능을 향상시키면서 W의 식각에는 영향을 미치지 않으므로 선택비를 향상시킨다. In the present invention, the (C) co-oxidant improves the selectivity because the peroxide improves the etching performance of TiN and does not affect the etching of W as an oxidizing agent that plays a role in removing the TiN film.
상기 (C) 보조산화제는 조성물 총 중량에 대하여, 0.0005~3 중량%로 포함되며, 더욱 바람직하게는 0.001~1 중량%로 포함된다.The above-mentioned (C) auxiliary oxidizing agent is contained in an amount of 0.0005 to 3% by weight, more preferably 0.001 to 1% by weight based on the total weight of the composition.
상기 보조산화제의 함량이 0.0005 중량% 미만일 경우 TiN Etch 성능을 향상시키기 어려우며, 반대로 3 중량%를 초과할 경우 W 막의 식각성능을 증가시켜 전체적으로 선택비를 감소시킨다. 특히, 퍼설페이트류가 3 중량%를 초과하여 포함될 경우에는 조성물 내에 석출이 발생할 수 있다. If the content of the auxiliary oxidizing agent is less than 0.0005 wt%, it is difficult to improve the TiN Etch performance. On the contrary, when the content of the auxiliary oxidizing agent is more than 3 wt%, the etching performance of the W film is increased to decrease the selectivity ratio as a whole. Particularly, when the persulfate is contained in an amount exceeding 3% by weight, precipitation may occur in the composition.
상기 보조산화제에 있어서, 퍼설페이트류로는 암모늄퍼설페이트(Ammonium persulfate), 소디움퍼설페이트(Sodium persulfate), 포타슘퍼설페이트(potassium persulfate) 등을 들 수 있으며, Examples of the persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, and the like. Examples of the persulfates include ammonium persulfate, sodium persulfate, potassium persulfate,
상기 화학식 1로 표시되는 N-옥사이드 화합물로는 메틸몰포린 N-옥사이드(Methylmorpholine N-oxide), 트리메틸아민 N-옥사이드(Trimethylamine N-oxide) 등을 들 수 있다. Examples of the N-oxide compound represented by Formula 1 include methylmorpholine N-oxide, trimethylamine N-oxide, and the like.
본 발명의 세정제 조성물에서 (D) 물은 특별히 한정되는 것은 아니나, 탈이온수를 사용하는 것이 바람직하며, 물속에 이온이 제거된 정도를 보여주는 물의 비저항 값이 18㏁/㎝ 이상인 탈이온수를 사용하는 것이 더욱 바람직하다.In the detergent composition of the present invention, (D) water is not particularly limited, but it is preferable to use deionized water. It is preferable to use deionized water having a water resistivity of 18 M? / Cm or more More preferable.
본 발명의 TiN 식각용 조성물에는 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 부식방지제, 금속이온 봉쇄제, 계면활성제 등을 들 수 있다. 또한, 상기 첨가제는 이에만 한정되지 않으며, 발명의 효과를 더욱 양호하게 하기 위하여, 이 분야에 공지되어 있는 여러 다른 (E) 첨가제들을 선택하여 사용할 수도 있다.The TiN etching composition of the present invention may contain conventional additives in addition to the above-mentioned components. Examples of the additives include corrosion inhibitors, metal ion sequestrants, surfactants, and the like. In addition, the additive is not limited thereto, and various other additives known in the art may be selected and used in order to further improve the effects of the present invention.
본 발명에서 사용되는 (A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상, (B) 과산화물, (C) 보조산화제, (E) 첨가제 등은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 식각용 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다. The (B) peroxide, (C) the auxiliary oxidizing agent, (E) the additive and the like selected from the group consisting of (A) sulfuric acid and alkylsulfonic acid to be used in the present invention can be produced by a conventionally known method, The etching composition of the invention preferably has purity for semiconductor processing.
본 발명은 또한, 하부 금속막 또는 금속배선으로서 텅스텐(W)을 포함하는 금속막 또는 금속배선을 포함하며, TiN막을 하드마스크로 사용하는 금속배선의 형성 방법에 있어서, The present invention also provides a method of forming a metal wiring using a TiN film as a hard mask, comprising a metal film or metal wiring including tungsten (W) as a lower metal film or metal wiring,
상기 텅스텐(W)을 포함하는 금속막 또는 금속배선에 대하여 상기 TiN 하드마스크를 선택적으로 식각하는 단계를 포함하며, 상기 식각단계는 상기 본 발명의 식각액을 사용하여 이루어지는 것을 특징으로 하는 금속배선의 형성 방법에 관한 것이다.And selectively etching the TiN hard mask with respect to a metal film or metal wiring including the tungsten (W), wherein the etching step is performed using the etching solution of the present invention ≪ / RTI >
상기 TiN 식각용 조성물에 관하여 기술된 내용은 상기 금속배선의 형성 방법에 대하여 그대로 적용될 수 있다.The contents described for the TiN etching composition can be directly applied to the method of forming the metal wiring.
상기 금속배선의 형성 방법에서 텅스텐을 포함하는 하부 금속막 또는 금속 배선에 대한 상부 TiN 하드마스크의 선택 식각비는 7:1 이상이다. In the method of forming the metal wiring, the selective etching ratio of the upper TiN hard mask to the lower metal film including tungsten or metal wiring is 7: 1 or more.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example 1~10 1 to 10 비교예Comparative Example 1~5 1-5 TiN막TiN film 식각용For etching 조성물의 제조 Preparation of composition
하기 표 1과 같은 성분들을 해당 함량으로 혼합하여 실시예 1~10 및 비교예 1~5의 TiN막 식각용 조성물을 제조하였다. 하기 실시예 및 비교예에서 황산 및 과수로는 96% 황산 및 31% 과수를 사용하였으며, 이들의 함량은 순수 황산 및 과수의 함량(Net 함량)으로 계산하여 하기 표 1에 기재하였다. The compositions for etching the TiN films of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared by mixing the components as shown in Table 1 below. In the following examples and comparative examples, 96% sulfuric acid and 31% fruit juice were used as sulfuric acid and fruit juice, and their contents are shown in the following Table 1 as the content of pure sulfuric acid and fruit juice (net content).
(단위 중량%)(Unit weight%)
[주] [week]
APS: 암모늄퍼설페이트APS: ammonium persulfate
NMMO: N-메틸몰포린 N-옥사이드 화합물NMMO: N-methylmorpholine N-oxide compound
TMAO: 트리메틸아민 N-옥사이드 화합물TMAO: trimethylamine N-oxide compound
MSA: 메탄설폰산 MSA: Methanesulfonic acid
TBHP: tert-부틸하이드로퍼옥사이드TBHP: tert-butyl hydroperoxide
MEKP: 메틸에틸케톤 퍼옥사이드MEKP: methyl ethyl ketone peroxide
TMAH: 테트라메틸암모늄하이드록사이드TMAH: tetramethylammonium hydroxide
시험예Test Example : : 식각특성Etch characteristics 평가 evaluation
TiN, W, SiNx, SiOx, poly Si, HfOx 막질이 형성된 기판을 실시예 1 내지 실시예 10 및 비교예 1 내지 비교예 5 식각용 조성물에 75℃에서, 5분간 침지시켰다. 각 기판의 막질에 대한 식각속도는 Ellipsometer(SE-MG-1000)을 이용하여 막두께의 변화를 측정하여 결정하고 그 결과를 하기 표 2에 나타내었다. 또한 하기에 기재된 수치의 단위는 Å/min이다.Substrates having TiN, W, SiNx, SiOx, poly Si, HfOx films formed thereon were immersed in the etching compositions of Examples 1 to 10 and Comparative Examples 1 to 5 at 75 DEG C for 5 minutes. The etch rate of each substrate was determined by measuring the change in film thickness using an Ellipsometer (SE-MG-1000). The results are shown in Table 2 below. Also, the unit of numerical value described below is A / min.
(단위: Å/min) (Unit: Å / min)
상기 표 2에 의하면, 실시예 1 내지 10의 TiN막 식각용 조성물은 TiN막, W막에 대하여 일정량 이상의 식각속도를 구현하였을 뿐만 아니라, TiN/W의 식각 선택비가 7 이상이었으며, 반도체 주요 막질인 SiNx, SiOx, poly Si, HfOx, 그리고 TEOS 등의 low-k 막의 조성물 처리 전후의 막두께 변화가 없음을 확인할 수 있었다. 특히, 실시예 1, 2, 8 및 10의 경우는 TiN/W의 식각 선택비가 8 이상으로 실시예들 중에서도 우수한 효과를 나타내었다.According to the above Table 2, the compositions for etching the TiN films of Examples 1 to 10 not only achieved an etching rate exceeding a certain amount with respect to the TiN film and the W film, but also had an etch selectivity ratio of TiN / W of 7 or more, It was confirmed that the film thickness of the low-k films such as SiNx, SiOx, poly Si, HfOx, and TEOS did not change before and after the composition treatment. In particular, in the case of Examples 1, 2, 8 and 10, the etching selectivity ratio of TiN / W was not less than 8, showing excellent effects among the examples.
반면, 비교예 1, 비교예3, 비교예 4, 및 비교예 5의 경우 목적하는 TiN/W의 선택비를 구현하지 못하였으며, 특히 비교예1의 경우는 Poly Si 막질에 결함이 확인되었다. 비교예 2의 경우 목적하는 식각특성을 구현하였지만 single tool 적용 시 APS가 석출되어 나오는 문제점이 발생되었다. 비교예 4의 경우 TiN의 식각속도가 너무 느림을 확인할 수 있었다.On the other hand, in Comparative Example 1, Comparative Example 3, Comparative Example 4, and Comparative Example 5, the selectivity ratio of the desired TiN / W was not realized, and in Comparative Example 1, defects were found in the Poly Si film. In the case of Comparative Example 2, although the desired etching characteristics were realized, there was a problem that the APS was precipitated by applying a single tool. In the case of Comparative Example 4, it was confirmed that the etching rate of TiN was too slow.
Claims (9)
(A) 황산 및 알킬설폰산 중에서 선택되는 1종 이상 75~95 중량%,
(B) 과산화물 0.3~10 중량%,
(C) 퍼설페이트류 및 하기 화학식 1로 표시되는 N-옥사이드 화합물로 이루어진 군으로부터 선택되는 1종 이상의 보조산화제 0.0005~3 중량%, 및
(D) 잔량의 물을 포함하는 TiN막 식각용 조성물:
[화학식 1]
상기 식에서,
R1 내지 R3는 각각 독립적으로 C1~C4의 알킬기일 수 있으며,
R2 및 R3는 서로 결합하여 기 존재하는 질소원자와 C4~C6의 헤테로 고리를 형성할 수 있다. With respect to the total weight of the composition,
(A) 75 to 95% by weight of at least one selected from sulfuric acid and alkylsulfonic acid,
(B) 0.3 to 10% by weight of peroxide,
0.0005 to 3% by weight of at least one co-oxidant selected from the group consisting of (C) persulfates and an N-oxide compound represented by the following formula
(D) Remaining amount of water:
[Chemical Formula 1]
In this formula,
R1 to R3 each independently may be an alkyl group of C1 to C4,
R2 and R3 may combine with each other to form a C4 to C6 hetero ring with the nitrogen atom present.
상기 TiN막 식각용 조성물은 텅스텐(W)을 포함하는 금속막 또는 금속배선의 존재하에서 TiN막의 선택적 식각을 위하여 사용되는 것을 특징으로 하는 TiN 식각용 조성물. The method according to claim 1,
Wherein the composition for etching a TiN film is used for selective etching of a TiN film in the presence of a metal film containing tungsten (W) or a metal wiring.
텅스텐(W)을 포함하는 금속막 또는 금속배선에 대한 TiN막의 선택 식각비가 7:1 이상인 것을 특징으로 하는 TiN 식각용 조성물. The method according to claim 1,
Wherein the selective etching ratio of the TiN film to the metal film containing tungsten (W) or the metal wiring is not less than 7: 1.
상기 (A)성분과 (B)성분의 중량비가 10:1 ~ 50:1인 것을 특징으로 하는 TiN막 식각액 조성물.The method according to claim 1,
Wherein the weight ratio of the component (A) to the component (B) is 10: 1 to 50: 1.
알킬설폰산은 메탄설폰산, 에탄설폰산, 프로판설폰산, 및 부탄설폰산으로 이루어진 군으로부터 선택되는 1종 이상의 것인 것을 특징으로 하는 TiN막 식각액 조성물. The method according to claim 1,
Wherein the alkyl sulfonic acid is at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid.
과산화물은 과산화수소(H2O2), tert-부틸하이드로퍼옥사이드, 라우로일 퍼옥사이드, tert-부틸퍼아세테이트, tert-부틸퍼옥시벤조에이트, 2-부탄퍼옥사이드, 메틸에틸케톤 퍼옥사이드, 벤조일 퍼옥사이드, 및 다이커밀퍼옥사이드로 이루어진 군으로부터 선택되는 1종 이상의 것인 것을 특징으로 하는 TiN막 식각액 조성물. The method according to claim 1,
The peroxide is selected from the group consisting of hydrogen peroxide (H 2 O 2 ), tert-butyl hydroperoxide, lauroyl peroxide, tert-butyl peracetate, tert-butyl peroxybenzoate, 2-butane peroxide, methyl ethyl ketone peroxide, Peroxides, peroxides, peroxides, peroxides, peroxides, peroxides, and peroxides.
상기 화학식 1로 표시되는 N-옥사이드 화합물로는 메틸몰포린 N-옥사이드 화합물 및 트리메틸아민 N-옥사이드 화합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 TiN막 식각액 조성물. The method of claim 1, wherein the persulfates are selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate;
The N-oxide compound represented by Formula 1 is selected from the group consisting of methylmorpholine N-oxide compound and trimethylamine N-oxide compound.
상기 텅스텐(W)을 포함하는 금속막 또는 금속배선에 대하여 상기 TiN 하드마스크를 선택적으로 식각하는 단계를 포함하며, 상기 식각단계는 청구항 1 내지 청구항 8 중 어느 한 항의 식각액을 사용하여 이루어지는 것을 특징으로 하는 금속배선의 형성 방법.A method of forming a metal wiring using a TiN film as a hard mask, the metal film including a metal film or metal wiring including tungsten (W) as a lower metal film or a metal wiring,
And selectively etching the TiN hard mask with respect to a metal film or metal wiring including the tungsten (W), wherein the etching step is performed using the etching solution of any one of claims 1 to 8 Of the metal wiring.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210025409A (en) * | 2019-08-27 | 2021-03-09 | 엘티씨에이엠 주식회사 | ETCHING COMPOSITION WITH HIGH SELECTIVITY TO TiN LAYER USING HYDROGEN PEROXIDE |
| CN114350365A (en) * | 2021-12-07 | 2022-04-15 | 湖北兴福电子材料有限公司 | Etching solution for stably etching titanium nitride |
| US11390805B2 (en) | 2020-02-05 | 2022-07-19 | Samsung Electronics Co., Ltd. | Etching composition and method for manufacturing semiconductor device using the same |
| US11427759B2 (en) | 2019-10-17 | 2022-08-30 | Samsung Electronics Co., Ltd. | Etchant compositions for metal-containing films and methods of manufacturing integrated circuit devices using the etchant compositions |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009044129A (en) * | 2007-07-13 | 2009-02-26 | Tokyo Ohka Kogyo Co Ltd | Titanium nitride-stripping liquid, and method for stripping titanium nitride coating film |
| KR20130049507A (en) * | 2011-11-04 | 2013-05-14 | 동우 화인켐 주식회사 | Etching solution composition for a titanium nitride layer and method for etching the titanium nitride layer using the same |
| KR101282177B1 (en) | 2008-09-09 | 2013-07-04 | 쇼와 덴코 가부시키가이샤 | Etchant for titanium-based metal, tungsten-based metal, titanium-tungsten-based metal or nitrides thereof |
| WO2015031620A1 (en) * | 2013-08-30 | 2015-03-05 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
| KR20150029827A (en) * | 2013-09-10 | 2015-03-19 | 동우 화인켐 주식회사 | ETCHANT COMPOSITION FOR NICKEL-BASED METAL LAYER AND TiN |
| KR20150050278A (en) * | 2013-10-31 | 2015-05-08 | 솔브레인 주식회사 | Composition for etching titanium nitrate layer-tungsten layer containing laminate, method for etching using the same and semiconductor device manufactured by using the same |
| KR20150071790A (en) * | 2013-12-18 | 2015-06-29 | 동우 화인켐 주식회사 | Etching solution composition for a metal nitride layer |
| KR20150126637A (en) * | 2013-03-04 | 2015-11-12 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Compositions and methods for selectively etching titanium nitride |
-
2016
- 2016-01-12 KR KR1020160003831A patent/KR102415954B1/en active IP Right Grant
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009044129A (en) * | 2007-07-13 | 2009-02-26 | Tokyo Ohka Kogyo Co Ltd | Titanium nitride-stripping liquid, and method for stripping titanium nitride coating film |
| KR101282177B1 (en) | 2008-09-09 | 2013-07-04 | 쇼와 덴코 가부시키가이샤 | Etchant for titanium-based metal, tungsten-based metal, titanium-tungsten-based metal or nitrides thereof |
| KR20130049507A (en) * | 2011-11-04 | 2013-05-14 | 동우 화인켐 주식회사 | Etching solution composition for a titanium nitride layer and method for etching the titanium nitride layer using the same |
| KR20150126637A (en) * | 2013-03-04 | 2015-11-12 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Compositions and methods for selectively etching titanium nitride |
| WO2015031620A1 (en) * | 2013-08-30 | 2015-03-05 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
| KR20150029827A (en) * | 2013-09-10 | 2015-03-19 | 동우 화인켐 주식회사 | ETCHANT COMPOSITION FOR NICKEL-BASED METAL LAYER AND TiN |
| KR20150050278A (en) * | 2013-10-31 | 2015-05-08 | 솔브레인 주식회사 | Composition for etching titanium nitrate layer-tungsten layer containing laminate, method for etching using the same and semiconductor device manufactured by using the same |
| KR20150071790A (en) * | 2013-12-18 | 2015-06-29 | 동우 화인켐 주식회사 | Etching solution composition for a metal nitride layer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210025409A (en) * | 2019-08-27 | 2021-03-09 | 엘티씨에이엠 주식회사 | ETCHING COMPOSITION WITH HIGH SELECTIVITY TO TiN LAYER USING HYDROGEN PEROXIDE |
| US11427759B2 (en) | 2019-10-17 | 2022-08-30 | Samsung Electronics Co., Ltd. | Etchant compositions for metal-containing films and methods of manufacturing integrated circuit devices using the etchant compositions |
| US11390805B2 (en) | 2020-02-05 | 2022-07-19 | Samsung Electronics Co., Ltd. | Etching composition and method for manufacturing semiconductor device using the same |
| CN114350365A (en) * | 2021-12-07 | 2022-04-15 | 湖北兴福电子材料有限公司 | Etching solution for stably etching titanium nitride |
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