KR20210092472A - A molybdenum etchant composition and a pattern formation method using the same - Google Patents
A molybdenum etchant composition and a pattern formation method using the same Download PDFInfo
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- KR20210092472A KR20210092472A KR1020200005910A KR20200005910A KR20210092472A KR 20210092472 A KR20210092472 A KR 20210092472A KR 1020200005910 A KR1020200005910 A KR 1020200005910A KR 20200005910 A KR20200005910 A KR 20200005910A KR 20210092472 A KR20210092472 A KR 20210092472A
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- molybdenum
- etchant composition
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 67
- 239000011733 molybdenum Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000007261 regionalization Effects 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 phosphoric acid compound Chemical class 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000005530 etching Methods 0.000 claims description 53
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 10
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 8
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- COIVORYDLGWALF-UHFFFAOYSA-N azane;methylphosphonic acid Chemical compound [NH4+].CP(O)([O-])=O COIVORYDLGWALF-UHFFFAOYSA-N 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 claims description 2
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 claims description 2
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- FFFKMCBLKWJRJS-UHFFFAOYSA-N C(C)OP(=O)(OCC)OCC.C(C)OP(=O)(OCC)OCC Chemical compound C(C)OP(=O)(OCC)OCC.C(C)OP(=O)(OCC)OCC FFFKMCBLKWJRJS-UHFFFAOYSA-N 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical compound II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 abstract 1
- 229920000153 Povidone-iodine Polymers 0.000 abstract 1
- 229960001621 povidone-iodine Drugs 0.000 abstract 1
- 239000010408 film Substances 0.000 description 94
- 230000000052 comparative effect Effects 0.000 description 38
- 230000008569 process Effects 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 11
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
본 발명은 몰리브데늄 식각액 조성물 및 이를 이용한 패턴 형성 방법에 관한 것이다.The present invention relates to a molybdenum etchant composition and a pattern forming method using the same.
현재까지는 액정 디스플레이와 반도체 디바이스에 구비된 박막 트랜지스터의 게이트 전극, 배선, 배리어층이나 콘택트홀, 비어홀의 매립 등을 형성하기 위해서, 질화티타늄과 함께 텡스텐 또는 텅스턴계 금속이 주로 사용되어 왔다. 하지만, 최근에는 텅스턴계 막에 대한 저항 문제 등이 제기됨에 따라, 텅스턴계 막을 몰리브덴계막이나 루테늄계막으로 대체하여 사용하고 있는 추세이다. Tungsten or tungsten-based metals have been mainly used together with titanium nitride to form gate electrodes, wirings, barrier layers, contact holes, and via holes of thin film transistors provided in liquid crystal displays and semiconductor devices. However, in recent years, as the problem of resistance to the tungsten-based film has been raised, the tungsten-based film has been replaced with a molybdenum-based film or a ruthenium-based film.
예컨데, 반도체 장치, 액정 디스플레이 등의 제조에 있어서, 기판 상에 질화티타늄막 및 몰리브덴막이 적층될 수 있으며 몰리브데늄막이 단독으로 사용될 수 있다. 이러한 반도체 장치, 액정 디스플레이 등에 포함되는 다양한 패턴 형성의 필요에 따라 질화티타늄 및 몰리브덴막에 대한 식각 공정이 수행 될 수 있다. 반도체 장치, 액정 디스플레이 등의 제조 공정은 초미세/초정밀 공정으로, 해당 공정에 적합한 각 막질에 대한 식각 비율이 충족되지 않는 경우, 패턴 붕괴로 인한 회로 성능이 저하되는 문제를 초래한다. 이에, 상기 금속 다층막의 식각 공정에서, 각 식각 공정에서 요구되는 특정의 식각 비율에 맞게 각각의 막이 식각되는 것이 중요하며, 식각 대상 막질 이외에 절연막 등에 손상을 주지 않는 것이 필요하다. For example, in the manufacture of a semiconductor device, a liquid crystal display, etc., a titanium nitride film and a molybdenum film may be laminated on a substrate, and a molybdenum film may be used alone. An etching process for the titanium nitride and molybdenum layers may be performed according to the necessity of forming various patterns included in such semiconductor devices, liquid crystal displays, and the like. The manufacturing process of a semiconductor device, a liquid crystal display, etc. is an ultra-fine/ultra-precision process, and when an etch rate for each film quality suitable for the process is not satisfied, circuit performance is deteriorated due to pattern collapse. Accordingly, in the etching process of the metal multilayer film, it is important that each film is etched according to a specific etching rate required in each etching process, and it is necessary not to damage the insulating film other than the film quality to be etched.
더욱이, 몰리브데늄(Mo)은 식각 과정에서 산화막이 쉽게 생성되어, 식각 특성의 제거가 어려운 문제가 있다. 이에, 몰리브덴의 식각속도를 적절하게 조절하여 산화막 생성을 최소화하면서 표면이 균일한 프로파일을 얻을 수 있는 몰리브데늄막 식각용 조성물이 필요하다.Moreover, molybdenum (Mo) has a problem in that an oxide film is easily generated during the etching process, and thus it is difficult to remove the etching characteristics. Accordingly, there is a need for a molybdenum film etching composition capable of obtaining a uniform surface profile while minimizing oxide film formation by appropriately controlling the molybdenum etching rate.
한편, 종래에는 대한민국 공개특허공보 제10-2016-0014714호와 같이 질화질화티타늄의 선택적인 에칭을 위한 조성물 및 방법에 관한 기술이 개시되어 있기는 하나, 질화티타늄막과 함께 몰리브덴막이 적층된 금속막에서 몰리브덴막만을 식각하기 위해 사용되는 식각액은 잘 알려져 있지 않다. 또한, 상기 특허문헌에서 개시하는 조성물의 경우에는 식각대상막을 식각하는 과정에서 Al2O3와 같은 절연막 손상을 방지하는 것에 대해서는 구체적으로 개시하고 있지 않다.Meanwhile, in the related art, as disclosed in Korean Patent Application Laid-Open No. 10-2016-0014714, a composition and method for selective etching of titanium nitride have been disclosed, but a metal film in which a molybdenum film is laminated together with a titanium nitride film is disclosed. The etchant used to etch only the molybdenum film is not well known. In addition, in the case of the composition disclosed in the above patent document, preventing damage to the insulating film such as Al 2 O 3 in the process of etching the etch target film is not specifically disclosed.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 몰리브데늄의 금속막 식각시 고식각성능을 나타내고, 절연막에 대한 손상을 방지할 수 있는 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to improve the problems of the prior art, and to provide an etchant composition capable of exhibiting high etching performance when etching a metal film of molybdenum and preventing damage to an insulating film.
상기 목적을 달성하기 위해, 본 발명은 퍼요오드산 유도체, 인산화합물 및 물을 포함하는, 몰리브데늄 식각액 조성물을 제공한다. In order to achieve the above object, the present invention provides a molybdenum etchant composition comprising a periodic acid derivative, a phosphoric acid compound and water.
또한, 기판 상에 몰리브데늄막을 형성하는 단계; 및 상술한 식각액 조성물을 사용하여 상기 몰리브데늄막을 식각하는 단계를 포함하는 패턴 형성 방법을 제공한다.In addition, forming a molybdenum film on the substrate; and etching the molybdenum layer using the above-described etching solution composition.
본 발명의 식각액 조성물은 몰리브데늄 금속막 식각시 고식각성능을 구현할 수 있다. 예컨데, 본 발명의 식각액 조성물을 사용하여 상기 금속막을 식각하면, 몰리브데늄막에 대한 우수한 식각속도를 나타낼 수 있으며, 특히 몰리브데늄막을 특정한 두께로 균일하게 제거하여 우수한 표면조도를 갖게 하는 효과를 제공할 수 있다.The etchant composition of the present invention can realize high etching performance when etching a molybdenum metal film. For example, when the metal film is etched using the etchant composition of the present invention, an excellent etching rate for the molybdenum film can be exhibited, and in particular, the effect of uniformly removing the molybdenum film to a specific thickness to have excellent surface roughness. can provide
또한, 본 발명의 식각액 조성물은 MoO3 산화막을 제거하여 부동태막 형성을 막을 수 있으며, Al2O3와 같은 절연막에 대한 손상을 최소화하여 Al2O3와 몰리브데늄(Mo)간 패턴 붕괴를 방지할 수 있다.In addition, the etchant composition of the present invention can prevent the formation of a passivation film by removing the MoO 3 oxide film, and minimize damage to the insulating film such as Al 2 O 3 to prevent pattern collapse between Al 2 O 3 and molybdenum (Mo). can be prevented
도 1은 본 발명의 일 실시예에 따른 몰리브데늄막이 적층된 구조를 나타내는 도면이다.
도 2 및 도 3은 상기 도 1의 몰리브데늄막을, 각각 본 발명의 비교예 1 및 실시예 4에 따른 식각액 조성물을 이용하여 식각한 후의 결과를 나타내는 이미지이다.
도 4 및 도 5는 도 1의 몰리브데늄막을, 각각 본 발명의 비교예 1 및 실시예 4에 따른 식각액 조성물을 이용하여 식각한 후에 AFM으로 측정한 이미지이다.1 is a view showing a structure in which a molybdenum film is stacked according to an embodiment of the present invention.
2 and 3 are images showing the results of etching the molybdenum film of FIG. 1 using the etching solution compositions according to Comparative Examples 1 and 4 of the present invention, respectively.
4 and 5 are images measured by AFM after etching the molybdenum film of FIG. 1 using the etching solution compositions according to Comparative Examples 1 and 4 of the present invention, respectively.
본 발명은 몰리브데늄막을 식각하기 위한 산화제로서 퍼요오드산 유도체를 포함하면서, 이와 함께 인산화합물 및 물을 포함하는 식각액 조성물 및 이를 이용한 패턴 형성방법에 관한 것이다.The present invention relates to an etchant composition including a periodic acid derivative as an oxidizing agent for etching a molybdenum film, and a phosphoric acid compound and water, and a pattern forming method using the same.
본 발명의 식각액 조성물은 몰리브데늄의 금속막 식각시에 몰리브데늄막에 대한 우수한 식각속도를 나타낼 수 있으며, 특히 몰리브데늄막을 특정한 두께로 균일하게 제거하여 우수한 표면조도를 갖게 하는 효과를 제공할 수 있다. 또한, 본 발명의 식각액 조성물을 사용하면, MoO3 산화막을 제거하여 부동태막 형성을 막을 수 있으며, Al2O3와 같은 절연막에 대한 손상을 최소화하여 Al2O3와 몰리브데늄(Mo)간 패턴 붕괴를 방지할 수 있다.The etchant composition of the present invention can exhibit an excellent etching rate for the molybdenum film during etching of the molybdenum metal film, and in particular provides an effect of uniformly removing the molybdenum film to a specific thickness to have excellent surface roughness can do. In addition, the use of the etching liquid composition of the present invention, by removing the MoO 3 oxide film can prevent passivation film formation, Al 2 O for 3 and to minimize damage to the insulating Al 2 O 3 and molybdenum (Mo), such as Pattern collapse can be prevented.
상기 몰리브데늄막은 액정 디스플레이, 반도체 디바이스의 박막 트랜지스터의 게이트 전극, 배선, 배리어층이나 콘택트홀, 비어홀의 매립 등에 사용될 수 있고, 바람직하게는 게이트 전극에 사용될 수 있다.The molybdenum film may be used for a liquid crystal display, a gate electrode of a thin film transistor of a semiconductor device, a wiring, a barrier layer, a contact hole, a via hole, etc., and may be preferably used for a gate electrode.
< 식각액 조성물 >< Etching solution composition >
본 발명의 식각액 조성물은, 퍼요오드산 유도체 및 인산화합물을 포함하며, 용제로써 물을 포함할 수 있다. The etchant composition of the present invention includes a periodic acid derivative and a phosphoric acid compound, and may include water as a solvent.
퍼요오드산 유도체Periodic acid derivatives
본 발명의 식각액 조성물은 산화제로서 퍼요오드산 유도체를 포함하는 것을 특징으로 한다. The etchant composition of the present invention is characterized in that it contains a periodic acid derivative as an oxidizing agent.
상기 퍼요오드산 유도체는 몰리브데늄(Mo)을 산화 및 식각하는 역할을 수행한다.The periodic acid derivative serves to oxidize and etch molybdenum (Mo).
본 발명에서, 퍼요오드산 유도체는 퍼요오드산과, 상기 퍼요오드산에 특정 작용기의 도입, 산화, 환원, 원자의 치환 등을 통해 상기 퍼요오드산으로부터 생성될 수 있는 화합물을 포괄하는 것일 수 있다.In the present invention, the periodic acid derivative may include periodic acid and a compound that can be produced from periodic acid through introduction of a specific functional group to the periodic acid, oxidation, reduction, substitution of atoms, and the like.
본 발명의 식각액 조성물에 포함되는 퍼요오드산 유도체로는, 예를 들면 퍼요오드산, 암모늄 퍼요오데이트, 소듐 퍼요오데이트 및 포타슘 퍼요오데이트 등을 들 수 있다. 상기 예시한 과요오드산 유도체 화합물은 본 발명의 식각액 조성물에 단독 또는 2종 이상이 포함될 수 있다.Periodic acid derivatives included in the etchant composition of the present invention include, for example, periodic acid, ammonium periodate, sodium periodate and potassium periodate. The periodic acid derivative compounds exemplified above may be included alone or in two or more types in the etchant composition of the present invention.
상기 퍼요오드산 유도체는 상용되는 99% 제품을 기준으로 조성물 총 중량에 대하여 0.001 내지 5 중량%로 포함될 수 있으며, 바람직하게는 0.005 내지 1 중량%로 포함될 수 있다. The periodic acid derivative may be included in an amount of 0.001 to 5% by weight, preferably 0.005 to 1% by weight based on the total weight of the composition based on 99% of commercially available products.
본 발명의 식각액 조성물에 퍼요오드산이 상기 함량범위 미만으로 포함되는 경우 식각속도가 느려지는 문제가 발생될 수 있고, 상기 함량범위를 초과하여 포함되는 경우에는 몰리브데늄막이 과도하게 식각 될 우려가 있어 표면이 균일한 프로파일을 얻을 수 없다.If periodic acid is included in the etchant composition of the present invention in less than the above content range, the etching rate may be slowed, and if it is included in excess of the above content range, the molybdenum film may be excessively etched. A profile with a uniform surface cannot be obtained.
한편, 기존의 몰리브데늄막을 제거하는 식각 용액의 경우, 산화제로서 과수 및 질산 조성을 기본으로 하고 있으나, 0.1% 미만의 상대적으로 적은 함량을 사용함에도 몰리브데늄의 식각속도를 제어할 수 없다. 그로 인해, 몰리브데늄막 식각 후 불균일한 표면 프로파일이 얻어지게 된다. 또한, 몰리브데늄은 pH<2 산성에서 MoO3의 산화막을 형성하기 쉬워, 부동태막 생성으로 전기적 결함의 우려가 있다. On the other hand, in the case of the conventional etching solution for removing the molybdenum film, the oxidizing agent is based on peroxide and nitric acid, but the etching rate of molybdenum cannot be controlled even when a relatively small content of less than 0.1% is used. As a result, a non-uniform surface profile is obtained after etching the molybdenum film. In addition, molybdenum tends to form an oxide film of MoO 3 in acidic pH<2, and there is a risk of electrical defects due to the formation of a passivation film.
그러나, 본 발명에 따른 식각액 조성물은 퍼요오드산 유도체를 포함하며, 상기 퍼요오드산 유도체를 상술한 함량범위의 소량으로 2 내지 4의 pH가 되도록 하면서, 몰리브데늄(Mo)막 식각이 가능하다. However, the etchant composition according to the present invention includes a periodic acid derivative, and while the periodic acid derivative is used in a small amount within the above-described content range to a pH of 2 to 4, it is possible to etch a molybdenum (Mo) film. .
본 발명의 퍼요오드산 유도체에 의한 몰리브데늄 막 식각의 일 실시예에 따른 반응 메커니즘은 하기 식 1과 같다. A reaction mechanism according to an embodiment of the molybdenum film etching by the periodic acid derivative of the present invention is as shown in Equation 1 below.
[식 1][Equation 1]
Mo + 3H5IO6 + H2O → MoO3 + 3HIO3 + 7H2O Mo + 3H 5 IO 6 + H 2 O → MoO 3 + 3HIO 3 + 7H 2 O
예를 들면, 상술한 퍼요오드산 유도체를 포함하는 본 발명의 식각액 조성물을 이용하여 몰리브데늄막 식각하면, 산화막이 30Å 미만으로 균일하고 얇게 생성되도록 하여, 부동태막 형성을 막을 수 있다.For example, when the molybdenum film is etched using the etchant composition of the present invention including the periodic acid derivative described above, the oxide film is uniformly and thinly formed to less than 30 Å, thereby preventing the formation of the passivation film.
한편, 식각액 조성물 분야에서, 산화제로서 질산, 과산화수소수, 암모늄아이오데이트 등의 산화제를 사용하는 것도 가능하다. 그러나, 질산은 제조시의 발열로 인한 위험성이 있으며, 암모늄아이오데이트와 같은 산화제는 보관기간에 따라 성분 및 함량에 변화가 생겨 제품의 신뢰성을 저하시킬 수 있다. 또한, 과산화수소의 경우 보호막질인 질화 실리콘에 손상을 가하거나 몰리브데늄의 표면이 거칠어지는 문제가 발생할 수 있다. On the other hand, in the field of the etchant composition, it is also possible to use an oxidizing agent such as nitric acid, hydrogen peroxide, and ammonium iodate as the oxidizing agent. However, there is a risk due to heat generation during manufacture of silver nitrate, and oxidizing agents such as ammonium iodate may have changes in components and contents depending on the storage period, thereby reducing the reliability of the product. In addition, in the case of hydrogen peroxide, a problem of damaging silicon nitride, which is a protective film, or roughening of the surface of molybdenum may occur.
이에 따라, 본 발명의 식각액 조성물은 질산, 과산화수소수, 암모늄아이오데이트 등의 산화제 대신 상술한 과요오드산 유도체를 산화제로 사용하는 것이 가장 바람직하다. Accordingly, in the etchant composition of the present invention, it is most preferable to use the above-described periodic acid derivative as an oxidizing agent instead of an oxidizing agent such as nitric acid, hydrogen peroxide, or ammonium iodate.
또한, 본 발명의 식각액 조성물은 불소화합물을 포함하는 경우, 보호막질인 Al2O3, Si3N4, 및/또는 SiO2에 손상을 줄 수 있어 사용할 수 없다.In addition, when the etchant composition of the present invention contains a fluorine compound, it cannot be used because it may damage Al 2 O 3 , Si 3 N 4 , and/or SiO 2 which is a protective film.
인산 화합물phosphate compound
본 발명에 따른 식각액 조성물은 표면 균일제로서 인산 화합물을 포함하는 것을 특징으로 한다. The etchant composition according to the present invention is characterized in that it contains a phosphoric acid compound as a surface leveling agent.
본 발명에서, 인산 화합물은 몰리브데늄 산화막(MoO3)을 킬레이팅 시켜 제거하는 역할을 수행한다. In the present invention, the phosphoric acid compound serves to chelate and remove the molybdenum oxide film (MoO 3 ).
상기 인산 화합물은 인산계(phosphate), 아인산계(phosphorus), 포스핀계(phosphinate) 및 포스포네이트계(Phosphonate)으로 이루어진 군으로부터 선택되는 1종 이상을 포함한다.The phosphoric acid compound includes at least one selected from the group consisting of phosphate, phosphorus, phosphinate, and phosphonate.
본 발명의 식각액 조성물에 포함되는 인산 화합물로서는, 인산(Phosphoric acid), 아인산(phosphorous acid), 하이포아인산(Hypophosphorous acid), 포스핀산(phosphinic acid), 제2 인산암모늄(ammonium phosphate dibasic), 인산트리에틸(treiethyl phosphate), 암모늄메틸포스포네이트(ammonium methyl phosphonate), N,N,N',N'-에틸렌디아민테트라(메틸렌포스폰산)(N,N,N,N-ethylenediamine tetrakis-(methylenephosphonic acid)), 글리신-N,N-비스(메틸렌 포스폰산) (Glycine-N,N-bis(methylene phosphonic acid), 및 1-하이드록시에탄-1,1-디포스폰산 (1-Hydroxyethane-1,1-diphosphonic acid; HEDPA)등을 들 수 있다. 상기 인산화합물은 1종 이상 포함될 수 있다.Examples of the phosphoric acid compound included in the etchant composition of the present invention include phosphoric acid, phosphorous acid, hypophosphorous acid, phosphinic acid, ammonium phosphate dibasic, and triphosphate. Ethyl (treiethyl phosphate), ammonium methyl phosphonate (ammonium methyl phosphonate), N,N,N',N'-ethylenediaminetetra (methylenephosphonic acid) (N,N,N,N-ethylenediamine tetrakis-(methylenephosphonic acid) )), glycine-N,N-bis(methylene phosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid (1-Hydroxyethane-1, 1-diphosphonic acid (HEDPA), etc. The phosphoric acid compound may be included at least one type.
본 발명의 식각액 조성물은, 몰리브데늄 산화막(MoO3)를 킬레이팅 시켜 제거율을 높여 식각된 몰리브데늄막의 표면의 균일성을 향상시키기 위한 측면에서, 바람직하게는, 인산(phosphoric acid), 인산트리에틸, 암모늄메틸포스포네이트, 1-하이드록시에탄-1,1-디포스폰산 (1-Hydroxyethane-1,1-diphosphonic acid; HEDPA) 및 제2 인산암모늄(ammonium phosphate dibasic)으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. 상기 인산화합물은 상용되는 100% 제품을 기준으로 조성물 총 중량에 대하여 0.01 내지 10 중량%로 포함될 수 있으며, 바람직하게는 0.1 내지 5 중량%로 포함될 수 있다. The etchant composition of the present invention chelates the molybdenum oxide film (MoO 3 ) to increase the removal rate to improve the uniformity of the surface of the etched molybdenum film, preferably phosphoric acid, phosphoric acid from the group consisting of triethyl, ammonium methylphosphonate, 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) and ammonium phosphate dibasic. It may include one or more selected. The phosphoric acid compound may be included in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on a 100% commercially available product, based on the total weight of the composition.
본 발명의 식각액 조성물에 인산화합물이 상기 함량범위 미만으로 포함되는 경우 몰리브데늄 산화막이 제거되지 않는 문제가 발생될 수 있고, 상기 함량범위를 초과하여 포함되는 경우에는 잔사(residue)로 작용하여 잔류하는 문제점이 있을 수 있다. When the phosphoric acid compound is included in the etchant composition of the present invention below the content range, a problem in that the molybdenum oxide film is not removed may occur. There may be problems with
본 발명의 일 실시예에서, 인산화합물에 의한 몰리브데늄 산화막(MoO3)은 하기 식 2의 반응식과 같이 제거될 수 있다. In an embodiment of the present invention, the molybdenum oxide film (MoO 3 ) by the phosphoric acid compound may be removed as shown in the reaction formula of
[식 2][Equation 2]
12MoO3 + xH2PO4 3- → (PO4)x·12MoO3 3x-+2xH+ 12MoO 3 + xH 2 PO 4 3- → (PO4)x 12MoO 3 3x- +2xH +
상기 식 2에서, x는 MoO3를 킬레이팅시켜 제거하는 인산의 몰 수 이다.In
물water
본 발명의 식각액 조성물에 포함되는 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water included in the etchant composition of the present invention may be deionized water for a semiconductor process, and preferably 18 MΩ/cm or more of the deionized water may be used.
본 발명에서 물은 잔량으로 포함될 수 있으며, 상기 잔량은, 본 발명의 필수 성분 및 그 외 다른 성분들을 더 포함한 총 조성물의 중량이 100 중량%가 되도록 하는 잔량을 의미한다. In the present invention, water may be included as a residual amount, and the residual amount means a residual amount such that the weight of the total composition further including the essential components and other components of the present invention is 100% by weight.
구체적으로, 본 발명은 조성물의 총 중량 대비 85 내지 99.99 중량%로 포함될 수 있다. Specifically, the present invention may be included in 85 to 99.99% by weight based on the total weight of the composition.
< 패턴 형성 방법 >< Pattern formation method >
본 발명은 상술한 식각액 조성물을 이용한 패턴 형성 방법을 제공한다. 본 발명의 패턴 형성 방법은, 본 발명에 따른 식각액 조성물을 사용하는 점을 제외하고는, 공지의 패턴 형성 방법에 따라 패턴을 형성 할 수 있다. The present invention provides a pattern forming method using the above-described etchant composition. The pattern forming method of the present invention may form a pattern according to a known pattern forming method, except that the etchant composition according to the present invention is used.
일 예로, 상기 패턴 형성 방법은, 기판 상에 몰리브데늄막을 형성하는 단계; 및 몰리브데늄막을 전술한 식각액 조성물로 식각하는 단계를 포함할 수 있다. For example, the pattern forming method may include forming a molybdenum film on a substrate; and etching the molybdenum film with the etchant composition described above.
일부 실시예에 있어서, 상기 상에 질화티타늄막을 먼저 형성한 뒤 상기 질화티타늄막 상에 몰리브데늄막을 형성할 수 있다.In some embodiments, a molybdenum layer may be formed on the titanium nitride layer after first forming a titanium nitride layer on the titanium nitride layer.
기판은 예를 들면, 실리콘 기판, 게르마늄 기판 또는 실리콘-게르마늄 기판과 같은 반도체 기판을 포함할 수 있다. 실리콘-온-인슐레이터(Silicon-On-Insulator: SOI) 기판 또는 게르마늄-온-인슐레이터(Germanium-On-Insulator: GOI) 기판이 기판으로 사용될 수도 있다. 기판은 InP, GaP, GaAs, GaSb 등과 같은 III-V족 화합물을 포함할 수도 있다.The substrate may include, for example, a semiconductor substrate such as a silicon substrate, a germanium substrate, or a silicon-germanium substrate. A silicon-on-insulator (SOI) substrate or a germanium-on-insulator (GOI) substrate may be used as the substrate. The substrate may include a group III-V compound such as InP, GaP, GaAs, GaSb, or the like.
본 발명은 상술한 식각액 조성물을 사용하여 몰리브데늄막의 금속막을 식각하여 반도체 전극을 형성할 수 있다. In the present invention, a semiconductor electrode may be formed by etching the metal layer of the molybdenum layer using the above-described etching solution composition.
또한, 본 발명에서, 상술한 식각액 조성물을 사용하여 형성 가능한 패턴은, 도전 패턴일 수 있고, 예를 들면, 화상 표시 장치의 패드, 전극 또는 배선으로 활용될 수 있다. In addition, in the present invention, a pattern that can be formed using the above-described etchant composition may be a conductive pattern, for example, may be utilized as a pad, electrode, or wiring of an image display device.
보다 상세하게는, 몰리브데늄 금속막은 소정 패턴으로 식각되어 게이트 전극이 될 수 있다. 질화 티타늄막 및 몰리브데늄막은 전체적으로 식각 대상막일 수 있거나, 부분적으로 식각되는 막일 수 있다.More specifically, the molybdenum metal layer may be etched in a predetermined pattern to become a gate electrode. The titanium nitride film and the molybdenum film may be an etch target film as a whole, or may be partially etched films.
본 발명의 일 실시예에 따르면, 상술한 식각액 조성물을 사용하여 몰리브데늄막 식각시, 전극이 형성될 정도로 몰리브데늄(Mo)이 남아야 하기 때문에 식각속도는 20 내지 40 Å/min 미만, 바람직하게는 10 내지 20 Å 미만, 더욱 바람직하게는 5 내지 10 Å 으로 나타나야 하며, 가장 바람직하게는 5 내지 6 Å으로 나타나야 한다. 본 발명은 상기 식각속도 범위에서, 몰리브데늄막의 표면이 균일한 프로파일을 얻을 수 있다. According to an embodiment of the present invention, when the molybdenum film is etched using the etchant composition described above, the etch rate is less than 20 to 40 Å/min, preferably because molybdenum (Mo) must remain enough to form an electrode. preferably from 10 to less than 20 Angstroms, more preferably from 5 to 10 Angstroms, most preferably from 5 to 6 Angstroms. In the present invention, it is possible to obtain a uniform profile of the surface of the molybdenum film within the etch rate range.
상기 몰리브데늄막의 형성 방법은 특별히 제한되지 않으며, 예를 화학 기상 증착(Chemical Vapor Deposition: CVD) 공정, 플라즈마 강화 화학 기상 증착(Plasma Enhanced Chemical Vapor Deposition: PECVD) 공정, 스퍼터링(sputtering) 공정, 물리 기상 증착(PVD) 공정, 원자층 증착(Atomic Layer Deposition: ALD) 공정 등을 통해 형성될 수 있다. 또한 상기 몰리브데늄막과 함께 질화티타늄막이 형성되는 경우 상기 방법을 통해 형성될 수 있다.The method of forming the molybdenum film is not particularly limited, and for example, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a sputtering process, and a physical It may be formed through a vapor deposition (PVD) process, an atomic layer deposition (ALD) process, or the like. In addition, when a titanium nitride film is formed together with the molybdenum film, it may be formed through the above method.
일 실시예에 있어서, 패턴 형성 방법은 기판과 몰리브데늄막 사이에 절연막을 형성하는 단계를 더 포함할 수 있다. 절연막은 보호 대상막으로, 알루미늄산화막(AlOx)을 포함할 수 있다. 예컨데, 상기 알루미늄산화막(AlOx)은 Al2O3 일 수 있다.In one embodiment, the pattern forming method may further include forming an insulating film between the substrate and the molybdenum film. The insulating layer is a layer to be protected and may include an aluminum oxide layer (AlOx). For example, the aluminum oxide layer (AlOx) may be Al 2 O 3 .
본 발명에 따르면, 상술한 식각액 조성물을 통해 상기 알루미늄산화막은 실질적으로 식각 또는 손상되지 않게 하고, 몰리브데늄막에 대해서만 우수한 식각 특성을 확보할 수 있다. According to the present invention, through the above-described etching solution composition, the aluminum oxide film is substantially not etched or damaged, and excellent etching properties can be secured only with respect to the molybdenum film.
본 발명의 패턴 형성 방법은 전술한 식각액 조성물을 사용하여 정밀하게 반도체 가공된 반도체 소자의 제조에 이용될 수 있으며, 예컨데, 반도체 장치, 액정 디스플레이, MEMS 장치, 프린트 배선 기판 등에 매우 유용하게 적용될 수 있다. 예컨데, 상술한 본 발명의 식각액 조성물을 이용하여 상기 패턴 형성 방법에 따라 식각된 몰리브데늄막 액정 디스플레이, 반도체 디바이스의 박막 트랜지스터의 게이트 전극, 배선, 배리어층이나 콘택트홀, 비어홀의 매립 등에 사용될 수 있고, 바람직하게는 게이트 전극에 사용될 수 있다.The pattern forming method of the present invention can be used for manufacturing a semiconductor device precisely processed using the etchant composition described above, for example, it can be very usefully applied to a semiconductor device, a liquid crystal display, a MEMS device, a printed wiring board, etc. . For example, a molybdenum film liquid crystal display etched according to the pattern formation method using the etchant composition of the present invention described above, a gate electrode of a thin film transistor of a semiconductor device, wiring, barrier layer or contact hole, filling of a via hole, etc. can be used. and preferably used for a gate electrode.
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. 또한, 이하에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, 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. In addition, "%" and "part" indicating the content hereinafter are based on weight unless otherwise specified.
실시예 및 비교예: 식각액 조성물의 제조Examples and Comparative Examples: Preparation of etchant composition
하기 표 1 에 기재된 조성 및 함량(중량%)으로 실시예 1 내지 15 비교예 1 내지 15 식각액 조성물을 제조하였다.Examples 1 to 15 Comparative Examples 1 to 15 Etchant compositions were prepared with the compositions and contents (wt%) shown in Table 1 below.
2) A2: 인산트리에틸(triethyl phosphate)
3) A3: 암모늄메틸포스포네이트(ammonium methyl phosphonate)
4) A4: 1-Hydroxyethane-1,1-diphosphonic acid(HEDPA)
5) A5: 제2 인산암모늄(ammonium phosphate dibasic)
6) B1: 슬폰산(sulfonic acid)
7) B2: 시트르산(citric acid)
8) B3: 아세트산염(acetic acetate)
9) B4: 암모늄카보네이트(ammonium carbonate)
10) B5: 암모늄 카르복실레이트(ammonium carboxylate)
11) B6: 암모늄 말로네이트(ammonium malonate)1) A1: phosphoric acid
2) A2: triethyl phosphate
3) A3: ammonium methyl phosphonate
4) A4: 1-Hydroxyethane-1,1-diphosphonic acid (HEDPA)
5) A5: ammonium phosphate dibasic
6) B1: sulfonic acid
7) B2: citric acid
8) B3: acetic acid
9) B4: ammonium carbonate
10) B5: ammonium carboxylate
11) B6: ammonium malonate
실험예Experimental example
(1) 몰리브데늄막(Mo) 및 산화알루미늄(Al(1) Molybdenum film (Mo) and aluminum oxide (Al) 22 OO 33 ) 식각속도 평가) Etching rate evaluation
몰리브데늄막(Mo) 및 산화알루미늄(Al2O3)이 각각 증착된 실리콘 웨이퍼를 2 X 2 cm2 크기로 절단하여 시편을 준비하였다. 상기 시편을 실시예 및 비교예의 식각액 조성물에 70℃ 항온조에서 1분간 침지시켰다. 이어서, 시편을 꺼내 물(DIW) 및 IPA(Isopropyl Alcohol)로 세정한 후 N2 가스를 이용하여 건조시켰다. 엘립소미터(Ellipsometer) 및 4-point prove 를 이용하여 식각 후 막의 두께를 측정한 뒤 최초 막 두께 대비 변화값으로 식각 속도를 계산하였다. 그 결과를 하기의 표 2 에 나타내었다.A silicon wafer on which a molybdenum film (Mo) and aluminum oxide (Al 2 O 3 ) were deposited was cut to a size of 2 X 2 cm 2 to prepare a specimen. The specimens were immersed in the etchant compositions of Examples and Comparative Examples in a 70° C. thermostat for 1 minute. Then, the specimen was taken out, washed with water (DIW) and IPA (Isopropyl Alcohol), and then dried using N 2 gas. After measuring the thickness of the film after etching using an ellipsometer and a 4-point probe, the etching rate was calculated as the change value compared to the initial film thickness. The results are shown in Table 2 below.
[몰리브데늄막(Mo) 식각속도 평가기준][Molybdenum film (Mo) etch rate evaluation criteria]
◎: 식각 속도 5 Å/min 이상 10 Å/min 미만◎: Etching rate 5 Å/min or more and less than 10 Å/min
○: 식각 속도 10 Å/min 이상 20 Å/min 미만○: Etching rate 10 Å/min or more and less than 20 Å/min
△: 식각 속도 20 Å/min 이상 40 Å/min 미만△:
×: 식각 안됨 내지 식각 속도 40 Å/min 이상×: not etched to etch rate 40 Å/min or more
[산화알루미늄막(Al2O3) 식각속도 평가기준][Aluminum oxide film (Al 2 O 3 ) etch rate evaluation criteria]
○: 식각 속도 0 내지 2 Å/min 미만○:
△: 식각 속도 2 Å/min 이상 10 Å/min 미만△:
×: 식각 속도 10 Å/min 이상×: Etching rate 10 Å/min or more
(2) 몰리브데늄의 표면 조도 평가(2) Evaluation of surface roughness of molybdenum
상기 식각 속도 평가 시편을 AFM으로 표면 거칠기 변화를 분석하였다.A change in surface roughness of the etching rate evaluation specimen was analyzed by AFM.
이때 평가 기준은 아래와 같으며 그 결과를 하기 표 2 및 도 4 및 도 5에 나타내었다. 구체적으로, 각각 비교예 1에 따른 식각액 조성물을 이용하여 식각한 후에 AFM으로 측정한 이미지를 도 4에, 실시예 4에 따른 식각액 조성물을 이용하여 식각한 후에 AFM으로 측정한 이미지를 도 5에 나타내었다.In this case, the evaluation criteria are as follows, and the results are shown in Table 2 and FIGS. 4 and 5 below. Specifically, the image measured by AFM after etching using the etchant composition according to Comparative Example 1 is shown in FIG. 4, and the image measured by AFM after etching using the etchant composition according to Example 4 is shown in FIG. It was.
<평가 기준><Evaluation criteria>
◎: RMS(Root Mean Square) 50 Å 미만◎: RMS (Root Mean Square) less than 50 Å
○: RMS 50 Å 이상 내지 70 Å 미만○: RMS 50 Å or more to less than 70 Å
△: RMS 70 Å 이상 내지 90 Å 미만△: RMS 70 Å or more to less than 90 Å
Х: RMS 90 Å 이상Х: RMS 90 Å or more
(3) 산화막 생성량 비교(TEM)(3) Comparison of oxide film production (TEM)
상기 식각 속도 평가 시편을 ＴＥＭ으로 측정하여，산화막의 두께를 표기하였다． 시편의 단면 이미지에서 몰리브데늄막 위에 생성된 산화막의 두께는 명암차로 나타내었다． 이때 평가 기준은 아래와 같으며 그 결과를 하기 표 2 및 도 2 및 ３에 나타내었다. 구체적으로, 각각 비교예 1에 따른 식각액 조성물을 이용하여 식각한 후에 ＴＥＭ으로 측정한 이미지를 도 2에, 실시예 4에 따른 식각액 조성물을 이용하여 식각한 후에 ＴＥＭ으로 측정한 이미지를 도 3에 나타내었다.The etch rate evaluation specimen was measured with TEM, and the thickness of the oxide film was marked with . In the cross-sectional image of the specimen, the thickness of the oxide film formed on the molybdenum film is indicated by the contrast. At this time, the evaluation criteria are as follows, and the results are shown in Table 2 and FIGS. 2 and 3 below. Specifically, after etching using the etchant composition according to Comparative Example 1, respectively, an image measured by TEM is shown in FIG. 2, and an image measured by TEM after etching using the etchant composition according to Example 4 is shown in FIG. 3 It was.
<평가 기준><Evaluation criteria>
○ : 30 Å 미만○: less than 30 Å
Х : 30 Å 이상Х: more than 30 Å
(Å/min)Mo etch rate
(Å/min)
(Å/min)Al 2 O 3 Etching rate
(Å/min)
(Å)surface roughness
(Å)
(Å)Oxide film production
(Å)
상기 표 2를 참조하면, 본원 실시예에 따른 식각액 조성물을 사용하는 경우, 몰리브데늄막 식각시 양호한 수준 또는 그 이상의 식각속도를 나타내며, 산화막이 30Å 미만으로 균일하고 얇게 생성되도록 할 수 있다. 또한, 본 발명의 실시예에 따른 식각액 조성물을 사용하면 우수한 표면 조도를 갖고, 산화알루미늄막과 같은 절역막 손상을 방지하면서 몰리브데늄막을 식각할 수 있음을 확인할 수 있었다.이와 비교하여, 비교예 1 내지 15에 따른 식각액 조성물을 이용하여 몰리브데늄막을 식각하는 경우에는 몰리브데늄막 식각이 충분히 이루어지지 않거나, 산화막이 목적하는 수준 이상으로 생성될 수 있고, 표면 조도나 Al2O3와 같은 절연막에 대한 손상에 있어서도 실시예에 따른 식각액 조성물 대비 현저히 저하된 효과를 나타내었다. Referring to Table 2, when the etchant composition according to the embodiment of the present application is used, the etching rate of the molybdenum film is etched at a good level or higher, and the oxide film can be formed uniformly and thinly to less than 30 Å. In addition, it was confirmed that using the etchant composition according to an embodiment of the present invention has excellent surface roughness and can etch the molybdenum film while preventing damage to the cut film such as the aluminum oxide film. In comparison, Comparative Example When the molybdenum film is etched using the etchant composition according to 1 to 15, the molybdenum film is not etched sufficiently, or an oxide film may be generated at a desired level or more, and surface roughness or Al 2 O 3 In the case of damage to the insulating film, the effect was significantly reduced compared to the etchant composition according to the embodiment.
Claims (8)
조성물 총 중량에 대하여,
퍼요오드산 유도체 0.001 내지 5중량%;
인산 화합물 0.01 내지 10중량%; 및
잔량의 물을 포함하는, 몰리브데늄 식각액 조성물.The method according to claim 1,
with respect to the total weight of the composition,
0.001 to 5% by weight of a periodic acid derivative;
0.01 to 10% by weight of a phosphoric acid compound; and
A molybdenum etchant composition comprising the remaining amount of water.
청구항 1 내지 7 중 어느 한 항의 식각액 조성물을 사용하여 상기 몰리브데늄막을 식각하는 단계;를 포함하는 패턴 형성 방법.forming a molybdenum film on a substrate; and
A method of forming a pattern comprising a; etching the molybdenum layer using the etchant composition of any one of claims 1 to 7.
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