KR20200107139A - Etchant composition - Google Patents
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- KR20200107139A KR20200107139A KR1020190025763A KR20190025763A KR20200107139A KR 20200107139 A KR20200107139 A KR 20200107139A KR 1020190025763 A KR1020190025763 A KR 1020190025763A KR 20190025763 A KR20190025763 A KR 20190025763A KR 20200107139 A KR20200107139 A KR 20200107139A
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- South Korea
- Prior art keywords
- ammonium
- etching composition
- etching
- tetramethylammonium
- weight
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000005530 etching Methods 0.000 claims abstract description 71
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 15
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 2
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 2
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 claims description 2
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 2
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052721 tungsten Inorganic materials 0.000 description 22
- 239000010937 tungsten Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 phosphate anion Chemical class 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LXFUCSMCVAEMCD-UHFFFAOYSA-N acetic acid;nitric acid;phosphoric acid Chemical compound CC(O)=O.O[N+]([O-])=O.OP(O)(O)=O LXFUCSMCVAEMCD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IGMBKNUVZFAHJM-UHFFFAOYSA-I hydrogen sulfate;oxido hydrogen sulfate;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC IGMBKNUVZFAHJM-UHFFFAOYSA-I 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 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
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
본 발명은 식각 조성물, 구체적으로 텅스텐막과 질화막에 대한 고선택적 식각비를 구현할 수 있는 식각 조성물에 관한 것이다.The present invention relates to an etching composition, in particular, to an etching composition capable of implementing a high selective etching ratio for a tungsten layer and a nitride layer.
티탄계 금속인 질화티타늄(TiN)은 반도체 디바이스, 액정 디스플레이, 미세전자제어기술(Micro Electro Mechanical Systems, MEMS) 디바이스, 프린트 배선기판 등에 귀금속이나 알루미늄(Al), 구리(Cu) 배선의 하지층, 캡층으로서 이용된다. 또한, 반도체 디바이스에서는 배리어 메탈, 게이트 메탈로서 사용되는 경우도 있다.Titanium nitride (TiN), a titanium-based metal, is used as a precious metal for semiconductor devices, liquid crystal displays, micro-electromechanical systems (MEMS) devices, printed wiring boards, etc., as well as the underlying layer of aluminum (Al) and copper (Cu) wiring It is used as a cap layer. In addition, in a semiconductor device, it may be used as a barrier metal or a gate metal.
상기 질화티타늄 또는 질화티탄계 금속과 함께 텅스텐 또는 텅스텐계 금속이 액정 디스플레이, 반도체 디바이스의 박막 트랜지스터의 게이트 전극, 배선, 배리어층이나 콘택트홀, 비어홀의 매립 등에 사용된다. 또한, 미세전자제어기술 분야에서는 텅스텐 히터로서도 이용된다.Together with the titanium nitride or titanium nitride-based metal, tungsten or tungsten-based metal is used for the filling of gate electrodes, wirings, barrier layers, contact holes, and via holes of thin film transistors of liquid crystal displays and semiconductor devices. In addition, in the field of microelectronic control technology, it is also used as a tungsten heater.
특히, 질화티타늄 등의 질화 금속막은 배리어층으로 식각액 조성물로부터 에칭을 억제시켜 하부의 재질이 식각되는 것을 막아주는 역할을 하고 있다. 따라서 일반적으로 알려진 식각액으로는 질화티타늄 등의 질화 금속막을 식각시키는 것이 어려워 식각액의 화학적 성질과 연마에 의한 물리적 효과를 더한 화학적 기계적 연마(CMP)방식을 이용하여 제거하는 방법이 일반적이다.In particular, a metal nitride film such as titanium nitride serves as a barrier layer to prevent etching from the etchant composition, thereby preventing the underlying material from being etched. Therefore, it is difficult to etch a metal nitride film such as titanium nitride with a commonly known etchant It is generally a method of removing using a chemical mechanical polishing (CMP) method that adds the chemical properties of the etchant and the physical effect of polishing.
하지만, 상기 화학적 기계적 연마 방식의 경우 공정이 복잡하고, 공정적용에 한계가 있으며, 다른 오염의 발생소지가 많으며, 비용이 일반 습식공정에 비하여 높기 때문에 비효율적이다.However, in the case of the chemical mechanical polishing method, the process is complicated, there is a limit to the application of the process, there are many sources of other contamination, and the cost is higher than that of the general wet process, so it is inefficient.
이에, 대한민국 공개특허 제2015-0050278호는 질화티타늄막 및 텅스텐막의 적층체용 식각 조성물, 이를 이용한 식각 방법 및 이로부터 제조된 반도체 소자에 관한 것으로서, (a) 인산 50 내지 80중량%, (b) 질산 5 내지 20중량%, (c) 암모늄계 화합물 0.01 내지 10중량% 및 (d) 잔부량의 용매를 포함하는, 질화티타늄막 및 텅스텐막의 적층체용 식각 조성물에 관한 내용을 개시하고 있다.Accordingly, Korean Patent Application Publication No. 2015-0050278 relates to an etching composition for a laminate of a titanium nitride film and a tungsten film, an etching method using the same, and a semiconductor device manufactured therefrom, (a) 50 to 80% by weight of phosphoric acid, (b) Disclosed is an etching composition for a laminate of a titanium nitride film and a tungsten film comprising 5 to 20% by weight of nitric acid, (c) 0.01 to 10% by weight of an ammonium compound, and (d) a residual amount of a solvent.
그러나, 인산 또는 인산염을 소량이라도 포함하는 경우 인산 또는 인산염에 포함된 포스페이트기가 텅스텐막의 해리 속도를 증가시켜, 이에 따른 후속 증착 공정에서 불량이 다소 발생하는 문제점이 발생하고 있는 실정이다.However, when a small amount of phosphoric acid or phosphate is included, the phosphate group contained in the phosphoric acid or phosphate increases the dissociation rate of the tungsten film, and thus, there is a problem that some defects occur in the subsequent deposition process.
본 발명은 인산 및 인산염을 포함하지 않아 질화티타늄막의 선택적 식각비가 우수한 식각 조성물을 제공하고자 한다.An object of the present invention is to provide an etching composition that does not contain phosphoric acid and phosphate, and thus has an excellent selective etching ratio of a titanium nitride film.
본 발명은 질산; 암모늄염; 및 물을 포함하되, 인산 및 인산염;을 포함하지 않는 식각 조성물을 제공한다.The present invention is nitric acid; Ammonium salt; And water, but phosphoric acid and phosphate; it provides an etching composition that does not contain.
본 발명에 따른 식각 조성물은 인산 및 인산염을 포함하지 않아 텅스텐막 대비 질화티타늄막의 식각속도를 향상시켜 고선택적 식각이 가능한 이점이 있다.Since the etching composition according to the present invention does not contain phosphoric acid and phosphate, there is an advantage in that the etching rate of the titanium nitride layer is improved compared to that of the tungsten layer, thereby enabling highly selective etching.
이하, 본 발명에 대하여 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에서 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 직접 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 개재되는 경우도 포함한다.In the present invention, when a member is positioned "on" another member, this includes not only the case where the member is in direct contact with the other member, but also the case where another member is interposed between the two members.
본 발명에서 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.In the present invention, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise specified.
본 발명의 한 양태는 질산; 암모늄염; 및 물을 포함하되, 인산 및 인산염;을 포함하지 않는 식각 조성물에 관한 것이다.One aspect of the present invention is nitric acid; Ammonium salt; And including water, phosphoric acid and phosphate; relates to an etching composition not containing.
본 발명에 따른 식각 조성물은 질화티타늄막 및 텅스텐막의 고선택적 에칭을 구현할 수 있을 뿐 아니라, 반도체 주요 구성 막질인 SiOx, AlOx, Poly-Si 등의 하부 물질에 대한 데미지 억제(damage free)를 구현할 수 있는 이점이 있다.The etching composition according to the present invention can not only implement highly selective etching of the titanium nitride film and the tungsten film, but also prevent damage to the underlying materials such as SiO x , AlO x , and Poly-Si, which are major components of the semiconductor. There is an advantage that can be implemented.
질산nitric acid
본 발명에 따른 식각 조성물은 질산을 포함한다. 상기 질산은 무기산이면서, 산화제의 특성을 가지기 때문에 금속의 식각이 가능하다. 요컨대 질화티타늄막의 에칭 속도(etch rate)를 증가시킬 뿐만 아니라, 텅스텐막을 산화시키는 역할을 수행한다. 구체적으로, 상기 텅스텐막을 공정상 필요한 만큼의 에칭 속도를 구현하도록 하는 역할을 수행한다.The etching composition according to the present invention includes nitric acid. Since nitric acid is an inorganic acid and has properties of an oxidizing agent, metal can be etched. In other words, it not only increases the etch rate of the titanium nitride film, but also serves to oxidize the tungsten film. Specifically, the tungsten layer serves to implement an etching rate as necessary for the process.
상기 질산을 포함하는 식각 조성물의 온도가 높아질수록 산화속도가 증가되기 때문에 상기 질산을 포함하는 식각 조성물을 사용하는 공정온도는 50 내지 70℃가 적당하며, 처리 시간은 5분 이내가 적당하다.Since the oxidation rate increases as the temperature of the etching composition containing nitric acid increases, the process temperature for using the etching composition containing nitric acid is preferably 50 to 70°C, and the treatment time is preferably within 5 minutes.
질산의 함량이 높아질수록 질화티타늄막 및 텅스텐막의 고선택비 식각이 가능해지나, 함량이 너무 높은 경우 고온에서의 질산 퓸(fume)이 다소 발생할 수 있다.The higher the nitric acid content, the higher the selectivity etching of the titanium nitride layer and the tungsten layer becomes possible. However, if the content is too high, fume nitrate may be generated at a high temperature.
본 발명의 일 실시형태에 있어서, 상기 질산은 상기 식각 조성물 전체 100 중량%에 대하여 25 내지 75 중량%, 구체적으로 40 내지 70 중량%, 더욱 구체적으로 56 내지 70 중량%로 포함될 수 있다.In one embodiment of the present invention, the nitric acid may be included in an amount of 25 to 75% by weight, specifically 40 to 70% by weight, and more specifically 56 to 70% by weight, based on 100% by weight of the total amount of the etching composition.
상기 질산이 상기 범위 내로 포함되는 경우 텅스텐막의 에칭 속도를 낮추고, 질화티타늄막의 식각효과가 우수하면서도, 식각 속도가 적당하여 상기 질화티타늄막의 식각량의 조절이 용이한 이점이 있어 바람직하다.When the nitric acid is contained within the above range, the etching rate of the tungsten layer is lowered, the etching effect of the titanium nitride layer is excellent, and the etching rate is adequate, so that the etching amount of the titanium nitride layer can be easily adjusted.
암모늄염Ammonium salt
본 발명에 따른 식각 조성물은 암모늄염을 포함한다. 상기 암모늄염은 질산에 의한 텅스텐의 산화 방지 역할을 수행하여 텅스텐의 에칭 속도를 낮추는 역할을 수행할 수 있다. 이에 따라 본 발명에 따른 식각 조성물의 질화티타늄막 및 텅스텐막의 선택비를 높일 수 있는 이점이 있다.The etching composition according to the present invention includes an ammonium salt. The ammonium salt may serve to prevent oxidation of tungsten by nitric acid, thereby lowering an etching rate of tungsten. Accordingly, there is an advantage of increasing the selectivity of the titanium nitride layer and the tungsten layer of the etching composition according to the present invention.
상기 암모늄염은 포스페이트기를 함유하지 않는 것으로서, 본 발명의 또 다른 실시형태에 있어서, 상기 암모늄염은 암모늄 설페이트, 암모늄 퍼옥소모노설페이트, 암모늄 나이트레이트, 암모늄 포메이트, 암모늄 아세테이트, 암모늄 클로라이드, 암모늄 클로레이트, 암모늄 요오데이트, 암모늄 퍼보레이트, 암모늄 퍼클로레이트, 암모늄 퍼요오데이트, 암모늄 퍼설페이트, 암모늄 하이포클로라이드, 테트라메틸암모늄 클로라이드, 테트라메틸암모늄 클로레이트, 테트라메틸암모늄 요오데이트, 테트라메틸암모늄 퍼보레이트, 테트라메틸암모늄 퍼클로레이트, 테트라메틸암모늄 퍼요오데이트, 테트라메틸암모늄 퍼설페이트 및 테트라부틸암모늄 퍼옥소모노설페이트로 이루어진 군에서 선택되는 1 이상일 수 있다. 상기 암모늄염이 상기 군에서 선택되는 1 이상인 경우 전술한 효과가 극대화되기 때문에 바람직하다.The ammonium salt does not contain a phosphate group, and in another embodiment of the present invention, the ammonium salt is ammonium sulfate, ammonium peroxomonosulfate, ammonium nitrate, ammonium formate, ammonium acetate, ammonium chloride, ammonium chlorate, Ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochloride, tetramethylammonium chloride, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium It may be one or more selected from the group consisting of perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, and tetrabutylammonium peroxomonosulfate. When the ammonium salt is at least one selected from the group, it is preferable because the above-described effect is maximized.
본 발명의 또 다른 실시형태에 있어서, 상기 암모늄염은 상기 식각 조성물 전체 100 중량%에 대하여 0.01 내지 1 중량%로 포함될 수 있다.In another embodiment of the present invention, the ammonium salt may be included in an amount of 0.01 to 1% by weight based on 100% by weight of the total amount of the etching composition.
본 발명의 또 다른 실시형태에 있어서, 상기 암모늄염은 상기 식각 조성물 전체 100 중량%에 대하여 0.1 내지 1 중량%로 포함될 수 있다.In another embodiment of the present invention, the ammonium salt may be included in an amount of 0.1 to 1% by weight based on 100% by weight of the total amount of the etching composition.
상기 암모늄염이 상기 범위 내로 포함되는 경우 텅스텐의 에칭이 억제되고, 매엽식 세정장치인 싱글 툴(single tool) 처리시 암모늄염이 재결정화되어 파티클에 의한 결함(particle defect)이 발생하는 현상을 억제할 수 있어 바람직하다.When the ammonium salt is included within the above range, the etching of tungsten is suppressed, and the ammonium salt is recrystallized during treatment with a single tool, which is a sheet-fed cleaning device, thereby suppressing the occurrence of particle defects. It is preferable.
물water
본 발명에 따른 식각 조성물은 물을 포함한다.The etching composition according to the present invention contains water.
상기 물은 순수, 초순수, 탈이온수, 증류수 등을 들 수 있으며, 탈이온수(Deionized water)인 것이 바람직하며, 물 속에서 이온이 제거된 정도를 보여주는 물의 비저항값이 18MΩ·㎝ 이상인 탈이온수를 사용하는 것이 보다 바람직하다.The water may be pure water, ultrapure water, deionized water, distilled water, etc., preferably deionized water, and deionized water having a specific resistance value of 18 MΩ·cm or more showing the degree of ion removal from water is used. It is more preferable to do it.
상기 질산이 수용액 상태인 경우, 상기 물은 상기 질산에 일부 또는 전부가 포함된 상태일 수 있으나 이에 한정되지는 않는다.When the nitric acid is in an aqueous solution state, the water may be in a state in which some or all of the nitric acid is included, but is not limited thereto.
상기 물은 상기 식각 조성물 전체 100 중량%에 대하여 잔부로 포함될 수 있다. The water may be included as a balance based on 100% by weight of the total amount of the etching composition.
본 발명에 따른 식각 조성물은 인산 및 인산염;을 포함하지 않는다. 요컨대 본 발명에 따른 식각 조성물은 인산 및/또는 인산염을 포함하지 않는다.The etching composition according to the present invention does not contain phosphoric acid and phosphate. In short, the etching composition according to the present invention does not contain phosphoric acid and/or phosphate.
상기 인산염은 인산 음이온과 동일하게 해석될 수 있는 것으로, 인산의 수소가 알칼리 금속 또는 알칼리 토금속으로 하나 또는 두 개 치환된 염에서 선택되는 것이면 특별히 한정되지 않으며, 제1 인산암모늄(ammonium phosphate monobasic), 제2 인산암모늄(ammonium phosphate dibasic), 제1 인산나트륨(sodium phosphate monobasic), 제2 인산나트륨(sodium phosphate dibasic), 제1 인산칼륨(potassium phosphate monobasic) 또는 제2 인산칼륨(potassium phosphate dibasic)일 수 있으나 이에 한정되지 않으며, 당업계에서 통상적으로 해석되는 용어로서 해석될 수 있다.The phosphate salt is not particularly limited as long as the hydrogen of phosphoric acid is selected from a salt substituted with one or two alkali metals or alkaline earth metals, which can be interpreted in the same manner as the phosphate anion, and the first ammonium phosphate monobasic, Ammonium phosphate dibasic, sodium phosphate monobasic, sodium phosphate dibasic, potassium phosphate monobasic or potassium phosphate dibasic It may be, but is not limited thereto, and may be interpreted as terms commonly interpreted in the art.
본 발명에 따른 식각 조성물은 상기 인산 및/또는 인산염을 포함하지 않기 때문에 텅스텐막의 식각은 억제하고, 질화티타늄막을 식각함으로써 고선택적 에칭의 구현이 가능하다.Since the etching composition according to the present invention does not contain the phosphoric acid and/or phosphate, etching of the tungsten layer is suppressed, and highly selective etching can be implemented by etching the titanium nitride layer.
본 발명의 또 다른 실시형태에 있어서, 상기 식각 조성물은 질화막 식각 조성물일 수 있다. 요컨대, 본 발명에 따른 식각 조성물은 질화막을 식각할 수 있다.In yet another embodiment of the present invention, the etching composition may be a nitride layer etching composition. In short, the etching composition according to the present invention may etch the nitride layer.
구체적으로, 본 발명에 따른 식각 조성물은 질화티타늄막 및 텅스텐막의 고선택적 에칭의 구현이 가능하다. 더욱 구체적으로, 본 발명에 따른 식각 조성물은 텅스텐막의 식각은 억제하고, 질화티타늄막을 선택적으로 식각 가능한 이점이 있다.Specifically, the etching composition according to the present invention can implement highly selective etching of a titanium nitride film and a tungsten film. More specifically, the etching composition according to the present invention has the advantage of suppressing etching of the tungsten layer and selectively etching the titanium nitride layer.
또한, 반도체의 주요 구성 막질인 SiOx, AlOx, Poly-Si 등의 하부 물질에 대한 데미지를 억제(damage free)할 수 있는 이점이 있다.In addition, there is an advantage of being able to suppress (damage free) damage to lower materials such as SiO x , AlO x , and Poly-Si, which are major constituent films of a semiconductor.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세히 설명한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지는 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다. 또한, 이하에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.Hereinafter, examples will be described in detail to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art. In addition, "%" and "parts" indicating content hereinafter are based on weight unless otherwise noted.
실시예Example 및 And 비교예Comparative example
하기 표 1에 기재된 성분 및 조성에 따라 식각 조성물을 제조하였다. 제조된 조성물을 하기 표 1에 따른 처리 조건을 이용하여 처리하였다.An etching composition was prepared according to the components and compositions shown in Table 1 below. The prepared composition was treated using the treatment conditions according to Table 1 below.
APS : Ammonium Persulfate
AA : Ammonium Acetate
AP : Ammonium PhosphateAS: Ammonium Sulfate
APS: Ammonium Persulfate
AA: Ammonium Acetate
AP: Ammonium Phosphate
실험예Experimental example 1: 에칭 속도(Etch Rate) 평가 1: Etch rate evaluation
W, TiN, SiOx, Poly-si 단막질을 실시예 및 비교예에 따른 식각 조성물에 침지시켰다. 각 조성물에 대한 Etch Rate 평가를 SEM 및 Ellipsometer를 이용하여 평가하여 그 결과를 표 2에 나타내었다. W, TiN, SiO x , Poly-si monolayers were immersed in the etching compositions according to Examples and Comparative Examples. Etch rate evaluation for each composition was evaluated using SEM and Ellipsometer, and the results are shown in Table 2.
실리콘 산화물(SiOx)막 및 Poly-si막에 대한 식각 정도는 아래 평가 기준에 따라 판단한 뒤, 하기 표 2에 나타내었다. The degree of etching for the silicon oxide (SiO x ) film and the poly-si film was determined according to the following evaluation criteria, and then shown in Table 2 below.
<실리콘산화물막 및 알루미늄 산화물막에 대한 식각 정도 평가 기준><Criteria for evaluating the degree of etching for silicon oxide film and aluminum oxide film>
○: 식각속도 1 Å/min 이하○: Etching speed 1 Å/min or less
×: 식각속도 1 Å/min 초과×: Etching speed exceeds 1 Å/min
실험예Experimental example 2: 용해도 평가 2: solubility evaluation
식각 처리 과정 중에서 식각액 조성물의 구성 성분이 석출되어 나오는 지, 식각액 조성물의 용해도를 아래 평가 기준에 따라 판단한 뒤, 하기 표 2에 나타내었다. 탁도는(NTU) HACH사의 2100AN을 이용하여 측정하였다.During the etching process, whether constituents of the etchant composition were precipitated out, and the solubility of the etchant composition was determined according to the following evaluation criteria, and then shown in Table 2 below. Turbidity (NTU) was measured using 2100AN of HACH.
<용해도 평가 기준><Solubility evaluation criteria>
○: 탁도측정결과 NTU(Nephelometric Turbidity Unit)가 1 이하○: As a result of turbidity measurement, NTU (Nephelometric Turbidity Unit) is less than 1
×: 탁도측정결과 NTU(Nephelometric Turbidity Unit)가 1 초과×: As a result of turbidity measurement, NTU (Nephelometric Turbidity Unit) exceeds 1
(E/R, Å/min)TiN
(E/R, Å/min)
(E/R, Å/min)W
(E/R, Å/min)
(식각비)TiN/W
(Etching cost)
상기 표 2를 보면 알 수 있듯이, 본 발명에 따른 식각 조성물을 이용한 실시예의 경우 질화텅스텐막 및 텅스텐막에 대한 식각 선택비가 우수한 것을 알 수 있다.As can be seen from Table 2, it can be seen that in the case of the embodiment using the etching composition according to the present invention, the etching selectivity for the tungsten nitride film and the tungsten film is excellent.
Claims (6)
인산 및 인산염;을 포함하지 않는 식각 조성물.nitric acid; Ammonium salt; And water,
An etching composition that does not contain phosphoric acid and phosphate.
상기 질산은 상기 식각 조성물 전체 100 중량%에 대하여 40 내지 75 중량%로 포함되는 것인 식각 조성물.The method of claim 1,
The etching composition that the nitrate is contained in an amount of 40 to 75% by weight based on 100% by weight of the total amount of the etching composition.
상기 암모늄염은 상기 식각 조성물 전체 100 중량%에 대하여 0.01 내지 1 중량%로 포함되는 것인 식각 조성물.The method of claim 1,
The etching composition that the ammonium salt is contained in an amount of 0.01 to 1% by weight based on 100% by weight of the total amount of the etching composition.
상기 암모늄염은 상기 식각 조성물 전체 100 중량%에 대하여 0.1 내지 1 중량%로 포함되는 것인 식각 조성물.The method of claim 3,
The etching composition that the ammonium salt is contained in an amount of 0.1 to 1% by weight based on 100% by weight of the total amount of the etching composition.
상기 암모늄염은 암모늄 설페이트, 암모늄 퍼옥소모노설페이트, 암모늄 나이트레이트, 암모늄포메이트, 암모늄 아세테이트, 암모늄 클로라이드, 암모늄 클로레이트, 암모늄 요오데이트, 암모늄 퍼보레이트, 암모늄 퍼클로레이트, 암모늄 퍼요오데이트, 암모늄 퍼설페이트, 암모늄 하이포클로라이드, 테트라메틸암모늄 클로라이드, 테트라메틸암모늄 클로레이트, 테트라메틸암모늄 요오데이트, 테트라메틸암모늄 퍼보레이트, 테트라메틸암모늄 퍼클로레이트, 테트라메틸암모늄 퍼요오데이트, 테트라메틸암모늄 퍼설페이트 및 테트라부틸암모늄 퍼옥소모노설페이트로 이루어진 군에서 선택되는 1 이상인 것인 식각 조성물.The method of claim 1,
The ammonium salt is ammonium sulfate, ammonium peroxomonosulfate, ammonium nitrate, ammonium formate, ammonium acetate, ammonium chloride, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, Ammonium hypochloride, tetramethylammonium chloride, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate and tetrabutylammonium peroxo Etching composition that is at least one selected from the group consisting of monosulfate.
상기 식각 조성물은 질화막 식각 조성물인 것인 식각 조성물.The method of claim 1,
The etching composition is a nitride film etching composition.
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