KR102443370B1 - Etching solution composition for a silicon nitride layer - Google Patents
Etching solution composition for a silicon nitride layer Download PDFInfo
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- KR102443370B1 KR102443370B1 KR1020150163146A KR20150163146A KR102443370B1 KR 102443370 B1 KR102443370 B1 KR 102443370B1 KR 1020150163146 A KR1020150163146 A KR 1020150163146A KR 20150163146 A KR20150163146 A KR 20150163146A KR 102443370 B1 KR102443370 B1 KR 102443370B1
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- KR
- South Korea
- Prior art keywords
- silicon nitride
- etchant composition
- nitride film
- silicon
- etching
- Prior art date
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 106
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000005530 etching Methods 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 41
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000002210 silicon-based material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 5
- 229920000137 polyphosphoric acid Polymers 0.000 description 5
- -1 silane compound Chemical class 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- PJEXUIKBGBSHBS-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrolidin-2-one Chemical compound OCN1CCCC1=O PJEXUIKBGBSHBS-UHFFFAOYSA-N 0.000 description 1
- HMXFDVVLNOFCHW-UHFFFAOYSA-N 1-butyl-2,2-dimethoxyazasilolidine Chemical compound CCCCN1CCC[Si]1(OC)OC HMXFDVVLNOFCHW-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- BRNBYPNQQNFBEX-UHFFFAOYSA-N 2,2-dimethoxy-1,6,2-diazasilocane Chemical compound CO[Si]1(OC)CCCNCCN1 BRNBYPNQQNFBEX-UHFFFAOYSA-N 0.000 description 1
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HRWADRITRNUCIY-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethanol Chemical compound CC(C)OCCOCCO HRWADRITRNUCIY-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- FETMDPWILVCFLL-UHFFFAOYSA-N 2-[2-(2-propan-2-yloxyethoxy)ethoxy]ethanol Chemical compound CC(C)OCCOCCOCCO FETMDPWILVCFLL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229920000712 poly(acrylamide-co-diallyldimethylammonium chloride) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-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
-
- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
Abstract
본 발명은 인산, 인산을 제외한 비불소계 무기산, 규소계 화합물 및 물을 포함하는 실리콘 질화막 식각액 조성물에 관한 것으로, 실리콘 산화막의 식각은 억제하고, 실리콘 질화막만을 선택하여 식각하는 효과를 지니고 있다.The present invention relates to a silicon nitride film etchant composition comprising phosphoric acid, a non-fluorine-based inorganic acid other than phosphoric acid, a silicon-based compound, and water, and has the effect of suppressing the etching of the silicon oxide film and selecting only the silicon nitride film to etch.
Description
본 발명은 실리콘 질화막 식각액 조성물에 관한 것으로, 보다 자세하게는 인산, 인산을 제외한 비불소계 무기산, 규소계 화합물 및 물을 포함하는 실리콘 질화막 식각액 조성물에 관한 것으로, 실리콘 산화막의 식각은 억제하고, 실리콘 질화막만을 선택하여 식각하는 효과를 지니고 있다.The present invention relates to a silicon nitride etchant composition, and more particularly, to a silicon nitride etchant composition comprising phosphoric acid, a non-fluorine-based inorganic acid other than phosphoric acid, a silicon-based compound, and water. It has the effect of etching by selection.
실리콘 질화막은 반도체 공정에서 대표적인 절연막으로 사용되고 있다. 실리콘 질화막은 실리콘 산화막, 폴리 실리콘막, 실리콘 웨이퍼 표면 등과 접촉하는 구조를 이루고 있으며, CVD(Chemical vapor deposition) 공정에 의해 증착되며, 이는 건식 식각 및 습식 식각을 통해서 제거된다. A silicon nitride film is used as a representative insulating film in a semiconductor process. The silicon nitride film has a structure in contact with a silicon oxide film, a polysilicon film, and the surface of a silicon wafer, and is deposited by a chemical vapor deposition (CVD) process, which is removed through dry etching and wet etching.
건식 식각은 주로 불소계 가스와 비활성 기체 등을 넣고 진공 하에서 진행하는데, 건식 식각을 수행하기 위한 장비가 고가이므로 상업적으로 이용하기에는 한계가 있다. 이에, 건식 식각 보다는 인산을 이용한 습식 식각이 널리 이용되고 있다.Dry etching is mainly performed under vacuum by putting a fluorine-based gas and an inert gas, and there is a limit to commercial use because equipment for performing dry etching is expensive. Accordingly, wet etching using phosphoric acid is widely used rather than dry etching.
순수한 인산을 식각 용액으로 사용하는 습식 식각에 있어, 실리콘 질화막의 식각 속도는 실리콘 산화막의 식각 속도에 비해 약 20 내지 50배 정도 빨라서 어느 정도 선택적인 실리콘 질화막의 제거가 가능하다할 수 있겠으나, 실리콘 질화막의 식각 속도가 높은 편이 아니기 때문에 식각 속도를 높이기 위해는 통상적으로 온도를 높여서 사용해야 한다. 온도를 높여서 식각하는 경우, 실리콘 질화막의 식각 속도와 더불어 실리콘 산화막의 식각 속도도 동반하여 상승하기 때문에 선택비가 떨어지는 문제점이 있다. In wet etching using pure phosphoric acid as an etching solution, the etching rate of the silicon nitride film is about 20 to 50 times faster than the etching rate of the silicon oxide film, so it may be possible to selectively remove the silicon nitride film to some extent. Since the etching rate of the nitride film is not high, it is generally necessary to increase the temperature to increase the etching rate. In the case of etching by increasing the temperature, since the etching rate of the silicon oxide film increases along with the etching rate of the silicon nitride film, there is a problem in that the selectivity is lowered.
또한, 최근에는 패턴(pattern)의 크기가 줄어들고 미세화 됨에 따라 실리콘 산화막이 미세하게 식각됨으로써 각종 불량 및 패턴 이상이 발생되는 등의 문제가 있다.In addition, in recent years, as the size of the pattern is reduced and miniaturized, the silicon oxide film is finely etched, thereby causing various defects and pattern abnormalities.
따라서, 기존의 인산 식각 용액에 비해 실리콘 질화막의 식각량 및 선택비가 더 높은 새로운 식각 용액의 개발이 필요하다.Therefore, it is necessary to develop a new etching solution having a higher etching amount and selectivity of the silicon nitride layer than the conventional phosphoric acid etching solution.
이러한 노력의 일환으로서, 대한민국 공개특허 제10-2002-0002748호에는 인산을 가열하여 폴리인산을 얻은 후 100℃ 이상에서 식각하여 선택비를 높이는 식각방법이 개시되어 있다. 그러나, 폴리인산의 안정성 및 결정 구조에 따른 선택비 향상에 대한 언급이 전혀 없고, 또한 이를 검증하기가 매우 어렵다. 또한, 상기 공개특허에는 인산에 황산, 산화제를 첨가하여 선택적으로 식각할 수 있는 식각 용액이 개시되어있으나, 황산 첨가의 경우 실리콘 산화막 뿐만 아니라 실리콘 질화막의 식각 속도까지 늦추는 문제점이 있다. As a part of this effort, Korean Patent Laid-Open Publication No. 10-2002-0002748 discloses an etching method for increasing the selectivity by heating phosphoric acid to obtain polyphosphoric acid and then etching at 100° C. or higher. However, there is no mention of improving the selectivity according to the stability and crystal structure of polyphosphoric acid, and it is very difficult to verify this. In addition, the above publication discloses an etching solution capable of selectively etching by adding sulfuric acid and an oxidizing agent to phosphoric acid, but there is a problem in that the etching rate of the silicon nitride layer as well as the silicon oxide layer is slowed when sulfuric acid is added.
일본공개특허 제1994-224176호, 제1997-045660호 및 미국등록특허 제5,310,457호에는 인산에 질산과 불산을 미량 넣어서 고 선택비를 얻었음이 개시되어 있다. 그러나, 불산의 첨가로 인하여 실리콘 산화막의 식각 속도도 더불어 높아지는 문제점이 있으며, 불산의 휘발로 인해 식각액의 조성이 바뀌어서 식각량이 지속적으로 감소되는 문제점이 있다. Japanese Patent Laid-Open Nos. 1994-224176, 1997-045660, and US Patent No. 5,310,457 disclose that a high selectivity was obtained by adding trace amounts of nitric acid and hydrofluoric acid to phosphoric acid. However, there is a problem in that the etching rate of the silicon oxide film is also increased due to the addition of hydrofluoric acid, and the etching amount is continuously reduced because the composition of the etchant is changed due to the volatilization of the hydrofluoric acid.
일본공개특허 제1994-349808호에는 인산에 실리콘 화합물을 넣어서 실리콘 산화막의 식각 속도를 1Å/min 이하로 얻었다고 개시하고 있으나, 실리콘을 과다하게 첨가할 경우 웨이퍼 표면에 이물이 붙는 문제가 있다. Japanese Laid-Open Patent Publication No. 1994-349808 discloses that the etching rate of the silicon oxide film is obtained by adding a silicon compound to phosphoric acid to be 1 Å/min or less, but when silicon is excessively added, there is a problem in that foreign substances are attached to the wafer surface.
대한민국 공개특허 제10-1999-0035773호 및 일본공개특허 제2008-311436호에는 실리콘계 불화물을 첨가하여 실리콘 질화막에 대해 선택적으로 식각할 수 있는 식각 용액이 개시되어 있으나, 실리콘의 과다 첨가로 인하여 웨이퍼 표면에 이물이 붙는 문제점이 있다. Korean Patent Laid-Open No. 10-1999-0035773 and Japanese Patent Laid-Open No. 2008-311436 disclose an etching solution capable of selectively etching a silicon nitride film by adding a silicon-based fluoride, but due to excessive addition of silicon, the wafer surface There is a problem of foreign matter sticking to the .
대한민국 공개특허 제10-2009-0095300호 및 제10-2009-0095327호에는 인산에 알콕시실란 및 옥심실란 화합물을 넣어서 실리콘 산화막의 식각 속도를 1Å/min 이하로 제어하였고, 여기에 불소 화합물을 넣어 질화막 식각 속도를 높였다고 개시하고 있다. 그러나, 통상의 실란 화합물은 물과 접촉 시 이산화규소(SiO2)가 형성되어 웨이퍼 표면에 이물이 붙는 문제가 있고, 끓는점이 대부분 150℃ 이하이므로 150℃ 이상에서 식각할 경우 첨가제의 증발로 인하여 식각 용액의 조성이 바뀌어져 식각 속도가 달라질 수 있다.In Korean Patent Laid-Open Patent Nos. 10-2009-0095300 and 10-2009-0095327, alkoxysilane and oximesilane compounds were added to phosphoric acid to control the etching rate of the silicon oxide film to 1 Å/min or less, and a fluorine compound was added thereto to control the etching rate of the nitride film. It is disclosed that the etching rate is increased. However, conventional silane compounds have a problem in that silicon dioxide (SiO 2 ) is formed when in contact with water and foreign substances are attached to the wafer surface. As the composition of the solution is changed, the etching rate may be changed.
현재까지 보고된 실리콘 질화막의 식각 용액의 제조기술은 크게 4가지로 분류될 수 있다. Techniques for preparing an etching solution for a silicon nitride film reported so far can be broadly classified into four types.
첫 번째 기술은 실리콘 질화막의 식각 속도를 높이는 기술로서, 통상 불소계 화합물을 첨가하여 실시하는데 실리콘 산화막의 식각 속도도 함께 높아지므로 미세 공정에 적용하기 어렵다. The first technique is a technique for increasing the etching rate of the silicon nitride layer, which is usually performed by adding a fluorine-based compound.
두 번째 기술은 실리콘 산화막의 식각 속도를 늦추는 기술로서, 첨가제 사용에 의해 대부분이 실리콘 질화막의 식각 속도도 함께 늦추기 때문에 생산성에서 손해를 본다. The second technique is to slow down the etching rate of the silicon oxide layer, and most of them slow down the etching rate of the silicon nitride layer by using an additive, so productivity suffers.
세 번째 기술은 실리콘계 불소화합물을 첨가하는 기술로서, 실리콘 질화막의 식각 속도는 높여주고, 실리콘 산화막의 식각 속도는 낮추어 주고는 있으나 실제 효과를 얻기 위해서는 식각 용액 중의 실리콘 함량이 어느 정도 높아야 한다. 이러할 경우 웨이퍼 표면에 이물이 붙어 식각 용액의 수명이 매우 짧고, 다양한 첨가제를 많이 사용하지 못한다. The third technique is a technique of adding a silicon-based fluorine compound, which increases the etching rate of the silicon nitride layer and lowers the etching rate of the silicon oxide layer. In this case, foreign substances are attached to the wafer surface, so the life of the etching solution is very short, and various additives cannot be used much.
네 번째 기술은 알콕시실란 및 옥심실란 화합물을 첨가하는 기술로서, 실란계 화합물은 물과 반응하여 SiO2를 형성하기 때문에 실란계 화합물의 함량이 높을 경우 세 번째 기술과 마찬가지의 문제가 존재한다.The fourth technique is a technique of adding an alkoxysilane and an oximesilane compound. Since the silane compound reacts with water to form SiO 2 , when the content of the silane compound is high, the same problem as the third technique exists.
따라서, 상기한 단점을 극복하고 실리콘 질화막의 고 식각, 고 선택비를 구현하여 새로운 조성의 식각 용액의 개발이 필요하다.Therefore, it is necessary to develop an etching solution having a new composition by overcoming the above disadvantages and realizing high etching and high selectivity of the silicon nitride layer.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위하여,The present invention in order to solve the problems of the prior art as described above,
실리콘 산화막은 식각하지 않으면서 실리콘 질화막만을 선택적으로 식각하는 실리콘 질화막 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a silicon nitride etchant composition that selectively etches only the silicon nitride layer without etching the silicon oxide layer.
또한, 본 발명은 식각 공정의 안정성을 높이는 것을 목적으로 한다.Another object of the present invention is to increase the stability of the etching process.
또한, 본 발명은 상기 실리콘 질화막 식각액 조성물에 의해 식각된 실리콘 질화막을 포함하는 전자 디바이스를 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an electronic device including a silicon nitride layer etched by the silicon nitride layer etchant composition.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 인산, 인산을 제외한 비불소계 무기산, 규소계 화합물 및 물을 포함하는 실리콘 질화막 식각액 조성물을 제공한다.The present invention provides a silicon nitride etchant composition comprising phosphoric acid, a non-fluorine-based inorganic acid other than phosphoric acid, a silicon-based compound, and water.
또한, 본 발명은 상기 본 발명의 실리콘 질화막 식각액 조성물에 의해 실리콘 질화막을 식각하는 공정을 포함하는 것을 특징으로 하는 전자 디바이스의 제조방법을 제공한다.In addition, the present invention provides a method of manufacturing an electronic device comprising the step of etching a silicon nitride film by the silicon nitride film etchant composition of the present invention.
또한, 본 발명은 상기 본 발명의 제조방법에 의해 제조되는 것을 특징으로 하는 전자 디바이스를 제공한다.In addition, the present invention provides an electronic device, characterized in that manufactured by the manufacturing method of the present invention.
본 발명의 실리콘 질화막 식각액 조성물은 실리콘 질화막만을 식각하고, 실리콘 산화막의 식각을 억제하므로, 실리콘 질화막을 선택적으로 식각할 수 있다.Since the silicon nitride etchant composition of the present invention etches only the silicon nitride layer and suppresses the etching of the silicon oxide layer, the silicon nitride layer can be selectively etched.
또한, 본 발명의 실리콘 질화막 식각액 조성물은 실리콘 질화막 식각 공정의 안정성이 높다.In addition, the silicon nitride etchant composition of the present invention has high stability in the silicon nitride etch process.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
실리콘 질화막은 드램(DRAM) 및 낸드플래시 메모리의 STI(Shallow Trench Isolation) 및 게이트 전극 형성 공정 등 반도체 제조 공정에서 사용된다.Silicon nitride is used in semiconductor manufacturing processes such as shallow trench isolation (STI) and gate electrode forming processes of DRAM and NAND flash memories.
종래에는 실리콘 질화막을 식각하기 위하여 인산을 사용하였다. 그러나 인산은 사용 공정 온도가 높고, 초순수의 함량이 실리콘 질화막 및 실리콘 산화막의 식각률에 영향을 미치기 때문에, 인산에 초순수의 함량을 일정하게 유지하기 위하여 순수를 공급해야 했다. 또한, 인산 자체가 강산이어서 부식성이 있어 취급이 까다로운 문제가 있었다.Conventionally, phosphoric acid was used to etch the silicon nitride layer. However, since phosphoric acid has a high process temperature and the content of ultrapure water affects the etching rates of silicon nitride and silicon oxide layers, pure water had to be supplied to phosphoric acid to keep the content of ultrapure water constant. In addition, since phosphoric acid itself is a strong acid, there is a problem in that it is corrosive and difficult to handle.
또한, 실리콘 질화막 및 실리콘 산화막의 식각에 있어서 인산계 식각액 조성물을 장기간 사용하는 경우, 폴리인산이 형성되어 점도가 상승하며, 식각 속도가 저하된다. 뿐만 아니라, 물의 증발로 인하여 인산의 농도가 증가하여 실리콘 산화막의 식각량이 증가하여 실리콘 질화막을 선택적으로 식각하기 어렵다. 더불어, 실리콘의 농도가 포화되어 산화규소로 석출되어 장기간 사용에는 바람직하지 못하다.In addition, when the phosphoric acid-based etchant composition is used for a long period in the etching of the silicon nitride layer and the silicon oxide layer, polyphosphoric acid is formed to increase the viscosity, and the etching rate is decreased. In addition, it is difficult to selectively etch the silicon nitride layer because the etch amount of the silicon oxide layer increases due to the increase of the phosphoric acid concentration due to the evaporation of water. In addition, the concentration of silicon is saturated and precipitated as silicon oxide, which is not preferable for long-term use.
따라서, 본 발명에서는 상기와 같은 문제점을 해결할 수 있는 실리콘 질화막 식각액 조성물을 제공하고자 하였다.Therefore, in the present invention, it was intended to provide a silicon nitride etchant composition capable of solving the above problems.
즉, 본 발명은 인산, 인산을 제외한 비불소계 무기산, 규소계 화합물 및 물을 포함하는 실리콘 질화막 식각액 조성물에 관한 것이다.That is, the present invention relates to a silicon nitride etchant composition comprising phosphoric acid, a non-fluorine-based inorganic acid other than phosphoric acid, a silicon-based compound, and water.
이하, 상기 실리콘 질화막 식각액 조성물을 각 성분별로 자세히 기재하기로 한다.Hereinafter, the silicon nitride etchant composition will be described in detail for each component.
(A)인산(A) phosphoric acid
본 발명의 실리콘 질화막 식각액 조성물에 포함되는 인산(H3PO4)은 실리콘 질화막의 식각율 및 식각 속도를 확보하기 위하여 사용되는 주 성분이다.Phosphoric acid (H 3 PO 4 ) included in the silicon nitride etchant composition of the present invention is a main component used to secure the etch rate and the etch rate of the silicon nitride layer.
상기 인산은 본 발명의 실리콘 질화막 식각액 조성물 총 중량에 대하여 60 내지 95 중량%로 포함되며, 바람직하게는 75 내지 90 중량%로 포함된다.The phosphoric acid is included in an amount of 60 to 95% by weight, preferably 75 to 90% by weight, based on the total weight of the silicon nitride film etchant composition of the present invention.
상기 인산이 60 중량% 미만으로 포함되면 실리콘 질화막의 식각율이 현저하게 저하되며, 95 중량%를 초과하여 포함되면 실리콘 질화막의 식각 속도는 감소하고, 실리콘 산화막의 식각 속도는 증가하게 되어 실리콘 질화막 식각액 조성물의 실리콘 질화막에 대한 선택비가 나빠지게 된다. 또한, 고순도의 인산은 고가이므로 비용적인 측면에서도 바람직하지 않다.When the phosphoric acid is contained in an amount of less than 60 wt%, the etching rate of the silicon nitride film is significantly reduced, and when it is contained in an amount exceeding 95 wt%, the etching rate of the silicon nitride film is decreased, and the etching rate of the silicon oxide film is increased. The selectivity of the composition to the silicon nitride film is deteriorated. In addition, since high-purity phosphoric acid is expensive, it is not preferable in terms of cost.
본 발명에서 선택비란, 실리콘 산화막의 식각 속도 대비 실리콘 질화막의 식각 속도를 의미한다.In the present invention, the selectivity refers to the etching rate of the silicon nitride film compared to the etching rate of the silicon oxide film.
(B)인산을 제외한 비불소계 무기산(B) Non-fluorine-based inorganic acids other than phosphoric acid
본 발명의 실리콘 질화막 식각액 조성물에 포함되는 인산을 제외한 비불소계 무기산은 실리콘 질화막의 식각량을 증가시키며, 폴리인산의 생성을 억제시키는 역할을 한다. The non-fluorine-based inorganic acid, except for phosphoric acid, contained in the silicon nitride film etchant composition of the present invention increases the etching amount of the silicon nitride film and serves to suppress the generation of polyphosphoric acid.
또한, 인산과 상기 인산을 제외한 비불소계 무기산을 함께 사용함으로써 수분의 증발로 인한 실리콘 질화막의 식각량 감소를 방지하여 실리콘 질화막 및 실리콘 산화막의 식각에 있어서, 실리콘 질화막에 대한 선택비를 높이는 역할을 한다.In addition, in the etching of the silicon nitride film and the silicon oxide film, the selectivity to the silicon nitride film is increased by using phosphoric acid and a non-fluorine-based inorganic acid other than the phosphoric acid together to prevent a decrease in the etching amount of the silicon nitride film due to evaporation of moisture. .
또한, 비불소계 무기산은 불소 화합물보다 비등점이 높아 식각 공정의 안정성을 높일 수 있다.In addition, the non-fluorine-based inorganic acid has a higher boiling point than the fluorine compound, and thus the stability of the etching process may be improved.
상기 인산을 제외한 비불소계 무기산은 질산, 황산 및 염산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 바람직하게는 황산을 포함한다.The non-fluorine-based inorganic acid other than phosphoric acid includes at least one selected from the group consisting of nitric acid, sulfuric acid and hydrochloric acid, and preferably includes sulfuric acid.
또한, 상기 인산을 제외한 비불소계 무기산은 본 발명의 실리콘 질화막 식각액 조성물 총 중량에 대하여 1 내지 10 중량%로 포함되며, 바람직하게는 1 내지 5 중량%로 포함된다.In addition, the non-fluorine-based inorganic acid excluding the phosphoric acid is included in an amount of 1 to 10 wt%, preferably 1 to 5 wt%, based on the total weight of the silicon nitride film etchant composition of the present invention.
상기 인산을 제외한 비불소계 무기산이 1 중량% 미만으로 포함되면 실리콘 질화막의 식각량을 증가시키기 어려우며, 10 중량%를 초과하여 포함되면 실리콘 질화막 식각률 향상의 효과가 미미하며, 물의 함량이 줄어들 수 있으므로 실리콘 질화막에 대한 선택비가 불량해질 수 있다.When the non-fluorine-based inorganic acid other than the phosphoric acid is included in less than 1 wt%, it is difficult to increase the etching amount of the silicon nitride film, and when it contains more than 10 wt%, the effect of improving the silicon nitride film etch rate is insignificant, and the water content may be reduced, so silicon The selectivity for the nitride film may be poor.
(C)규소계 화합물(C) Silicon-based compound
본 발명의 실리콘 질화막 식각액 조성물은 규소계 화합물을 포함한다.The silicon nitride film etchant composition of the present invention includes a silicon-based compound.
상기 규소계 화합물은 실리콘 질화막을 선택적으로 식각할 때, 실리콘 산화막의 식각을 최소화 해주는 성분으로, 즉 실리콘 산화막의 식각을 억제하는 역할을 한다.The silicon-based compound is a component that minimizes the etching of the silicon oxide layer when selectively etching the silicon nitride layer, that is, serves to suppress the etching of the silicon oxide layer.
상기 규소계 화합물은 분자 내에 질소를 포함하며, 바람직하게는 하기 화학식 1 내지 4로 이루어진 군으로부터 선택되는 1종 이상을 포함한다.The silicon-based compound includes nitrogen in a molecule, and preferably includes at least one selected from the group consisting of the following Chemical Formulas 1 to 4.
[화학식 1][Formula 1]
H2N-R1-[NH-R2]n-[NH-R3]m-Si(OR4)3 H 2 NR 1 -[NH-R 2 ] n -[NH-R 3 ] m -Si(OR 4 ) 3
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
상기 R1 내지 R3은 각각 독립적으로 탄소수 1 내지 20의 알킬렌기이고,The R 1 to R 3 are each independently an alkylene group having 1 to 20 carbon atoms,
상기 R4는 수소 또는 탄소수 1 내지 20의 알킬기이고,Wherein R 4 is hydrogen or an alkyl group having 1 to 20 carbon atoms,
상기 R5 내지 R12는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고,wherein R 5 to R 12 are each independently an alkyl group having 1 to 10 carbon atoms,
상기 R13은 탄소수 1 내지 10의 알킬렌기이고,Wherein R 13 is an alkylene group having 1 to 10 carbon atoms,
상기 n 및 m은 각각 독립적으로 0 내지 10의 정수이다.Wherein n and m are each independently an integer of 0 to 10.
상기 규소계 화합물은 본 발명의 실리콘 질화막 식각액 조성물 총 중량에 대하여 0.1 내지 3 중량%로 포함되며, 바람직하게는 0.1 내지 2 중량%로 포함된다.The silicon-based compound is included in an amount of 0.1 to 3% by weight, preferably 0.1 to 2% by weight, based on the total weight of the silicon nitride etchant composition of the present invention.
상기 규소계 화합물이 0.1 중량% 미만으로 포함되면 실리콘 산화막의 식각 억제 효과가 저하되고, 3 중량%를 초과하여 포함되면 선택비의 향상 효과가 미미하여 경제성이 저하될 수 있다.When the silicon-based compound is included in an amount of less than 0.1% by weight, the etch-inhibiting effect of the silicon oxide film is reduced, and when it is included in an amount of more than 3% by weight, the effect of improving the selectivity is insignificant, and thus economic efficiency may be reduced.
(D)물(D) water
본 발명의 실리콘 질화막 식각액 조성물은 물을 포함하며, 상기 물은 탈이온수이다.The silicon nitride etchant composition of the present invention includes water, and the water is deionized water.
상기 물은 본 발명의 실리콘 질화막 식각액 조성물 총 중량에 대하여 잔량으로 포함된다.The water is included in the remaining amount based on the total weight of the silicon nitride etchant composition of the present invention.
(E)(E) 극성유기용매Polar organic solvent
본 발명의 실리콘 질화막 식각액 조성물은 극성유기용매를 추가로 포함하여 실리콘 질화막 식각액 조성물의 안정성을 향상시킬 수 있다. 또한, 식각 공정에서 폴리인산이 생성되면 점도가 상승하는데, 극성유기용매를 사용함으로써 실리콘 질화막 식각액 조성물의 점도를 조절할 수 있다.The silicon nitride layer etchant composition of the present invention may further include a polar organic solvent to improve the stability of the silicon nitride layer etchant composition. In addition, when polyphosphoric acid is generated in the etching process, the viscosity increases. By using a polar organic solvent, the viscosity of the silicon nitride etchant composition can be adjusted.
상기 극성유기용매는 고온 공정에 적합한 비등점을 가진 것이라면 그 종류를 특별히 한정하지 않는다.The type of the polar organic solvent is not particularly limited as long as it has a boiling point suitable for a high-temperature process.
그러나 술폭시드류, 글리콜류, 술폰류, 락톤류, 락탐류 및 알코올류로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이 바람직하다.However, it is preferable to include at least one selected from the group consisting of sulfoxides, glycols, sulfones, lactones, lactams and alcohols.
상기 술폭시드류로는 구체적으로 예를 들어, 디메틸술폭시드(DMSO), 디에틸술폭시드 및 메틸술폭시드 등을 들 수 있다.Specific examples of the sulfoxides include dimethyl sulfoxide (DMSO), diethyl sulfoxide and methyl sulfoxide.
상기 글리콜류로는 구체적으로 예를 들어, 디에틸렌글리콜 메틸 에틸 에테르(MEDG), 에틸렌 글리콜(EG), 프로필렌 글리콜 및 부틸렌 글리콜 등의 알킬렌 글리콜; Specifically, the glycols include, for example, alkylene glycols such as diethylene glycol methyl ethyl ether (MEDG), ethylene glycol (EG), propylene glycol and butylene glycol;
에틸렌글리콜 모노메틸 에테르, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노이소프로필 에테르, 에틸렌글리콜 모노부틸 에테르, 디에틸렌글리콜 모노메틸 에테르, 디에틸렌글리콜 모노에틸 에테르, 디에틸렌글리콜모노이소프로필 에테르, 디에틸렌글리콜 모노부틸 에테르, 트리에틸렌글리콜 모노메틸 에테르, 트리에틸렌글리콜 모노에틸 에테르, 트리에틸렌글리콜 모노이소프로필 에테르, 트리에틸렌글리콜 모노부틸 에테르, 폴리에틸렌글리콜 모노메틸에테르, 폴리에틸렌글리콜 모노부틸 에테르, 프로필렌글리콜 모노메틸 에테르, 디프로필렌글리콜 모노메틸 에테르 및 트리프로필렌글리콜 모노메틸 에테르 등의 알킬렌글리콜 모노알킬에테르; 및Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol Monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether , alkylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether; and
프로필렌글리콜 모노메틸 에테르 아세테이트 등을 들 수 있다.and propylene glycol monomethyl ether acetate.
상기 술폰류로는 구체적으로 예를 들어, 디메틸 술폰, 디에틸 술폰, 비스(2-히드록시에틸)술폰 및 테트라메틸렌 술폰 등을 들 수 있다.Specific examples of the sulfones include dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl)sulfone and tetramethylene sulfone.
상기 락톤류로는 구체적으로 예를 들어, 감마-부티로락톤(GBL) 및 델타-발레로락톤 등을 들 수 있다.Specific examples of the lactones include, for example, gamma-butyrolactone (GBL) and delta-valerolactone.
상기 락탐류로는 구체적으로 예를 들어, N-에틸-2-피롤리돈(NEP), N-프로필-2-피롤리돈, N-히드록 시메틸-2-피롤리돈, N-히드록시에틸-2-피롤리돈 및 N-메틸피롤리디논 등을 들 수 있다.Specifically, the lactams include, for example, N-ethyl-2-pyrrolidone (NEP), N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxy and oxyethyl-2-pyrrolidone and N-methylpyrrolidinone.
상기 알코올류로는 구체적으로 예를 들어, 메탄올(MeOH), 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올, t-부탄올, 펜탄올, 헥산올, 헵탄올, 옥탄올 및 테트라하이드로퍼푸릴 알코올 등을 들 수 있다.Specifically, the alcohols include, for example, methanol (MeOH), ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol and tetrahydrofurfuryl alcohol. can be heard
상기 극성유기용매는 본 발명의 실리콘 질화막 식각액 조성물 총 중량에 대하여 1 내지 20 중량%, 바람직하게는 2 내지 12 중량%로 포함된다.The polar organic solvent is included in an amount of 1 to 20 wt%, preferably 2 to 12 wt%, based on the total weight of the silicon nitride film etchant composition of the present invention.
상기 극성유기용매가 1 중량% 미만으로 포함되면 실리콘 질화막 식각액 조성물의 점도 및 비점 조절이 어려우며, 20 중량%를 초과하여 포함되면 점도 및 비점 조절에 있어서 유의적인 차이를 나타내지 못하므로 경제적이지 못하다.When the polar organic solvent is included in less than 1% by weight, it is difficult to control the viscosity and boiling point of the silicon nitride film etchant composition, and when it is included in excess of 20% by weight, it does not show a significant difference in viscosity and boiling point control, so it is not economical.
또한, 본 발명의 실리콘 질화막 식각액 조성물은 실리콘 질화막 및 실리콘 산화막의 식각속도비가 100:1 이상이며, 바람직하게는 200:1 이상이다.In addition, in the silicon nitride layer etchant composition of the present invention, the etching rate ratio of the silicon nitride layer and the silicon oxide layer is 100:1 or more, preferably 200:1 or more.
즉, 본 발명의 실리콘 질화막 식각액 조성물은 실리콘 산화막에 대한 식각은 억제하고, 실리콘 질화막을 선택적으로 식각할 수 있다.That is, the silicon nitride etchant composition of the present invention can suppress the etching of the silicon oxide layer and selectively etch the silicon nitride layer.
상기 본 발명의 실리콘 질화막 식각액 조성물은 당 업계에 통상적으로 알려진 식각방법에 의하여 수행될 수 있다. 예컨대, 침적, 분무, 또는 침적 및 분무를 이용한 방법 등이 사용될 수 있으며, 이 경우, 식각 조건으로서 온도는 대개 30 내지 80℃, 바람직하게는 50 내지 70℃이고, 침적, 분무, 또는 침적 및 분무 시간은 대개 30초 내지 10분, 바람직하게는 1분 내지 5분이다. 그러나, 이러한 조건은 엄밀하게 적용되지는 않으며, 당업자에 의해 용이하거나 적합한 조건으로 선택될 수 있다.The silicon nitride film etchant composition of the present invention may be performed by an etching method commonly known in the art. For example, dipping, spraying, or a method using immersion and spraying may be used, and in this case, as the etching condition, the temperature is usually 30 to 80° C., preferably 50 to 70° C., and deposition, spraying, or immersion and spraying. The time is usually from 30 seconds to 10 minutes, preferably from 1 minute to 5 minutes. However, these conditions are not strictly applied and may be easily or suitable conditions selected by those skilled in the art.
또한, 본 발명은 본 발명의 실리콘 질화막 식각액 조성물에 의해 실리콘 질화막을 식각하는 공정을 포함하는 것을 특징으로 하는 전자 디바이스의 제조방법 및 상기 제조방법에 의해 제조된 전자 디바이스를 제공한다.In addition, the present invention provides a method of manufacturing an electronic device comprising the step of etching a silicon nitride film by the silicon nitride film etchant composition of the present invention, and an electronic device manufactured by the method.
본 발명의 실리콘 질화막 식각액 조성물을 이용하여 실리콘 산화막은 식각하지 않으면서 실리콘 질화막만을 선택적으로 식각함으로써, 전자 디바이스의 특성을 보다 향상시킬 수 있다.By selectively etching only the silicon nitride layer without etching the silicon oxide layer using the silicon nitride layer etchant composition of the present invention, the characteristics of the electronic device may be further improved.
이하, 본 발명을 실시예, 비교예 및 실험예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예, 비교예 및 실험예는 본 발명을 예시하기 위한 것으로서, 본 발명은 하기 실시예, 비교예 및 실험예에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있다.Hereinafter, the present invention will be described in more detail using Examples, Comparative Examples and Experimental Examples. However, the following Examples, Comparative Examples and Experimental Examples are intended to illustrate the present invention, and the present invention is not limited by the following Examples, Comparative Examples and Experimental Examples and may be variously modified and changed.
<실리콘 <Silicone 질화막nitride film 식각액etchant 조성물 제조> Composition Preparation>
실시예Example 1 내지 12 및 1 to 12 and 비교예comparative example 1 내지 5. 1 to 5.
하기의 표 1에 기재된 성분과 함량을 혼합하여 실시예 1 내지 12 및 비교예 1 내지 5의 실리콘 질화막 식각액 조성물을 제조하였다.The silicon nitride film etchant compositions of Examples 1 to 12 and Comparative Examples 1 to 5 were prepared by mixing the components and contents shown in Table 1 below.
Polar organic solvent
silicon oxide etch inhibitor
C-1 : N-(2-아미노에틸)-(3-아미노프로필)트리메톡시실란C-1: N-(2-aminoethyl)-(3-aminopropyl)trimethoxysilane
C-2 : 2,2-디메톡시-1,6-디아자-2-실라시클로-옥탄C-2: 2,2-dimethoxy-1,6-diaza-2-silacyclo-octane
C-3 : 2,2-디메톡시-N-n-뷰틸-I-아자-2-실라시클로펜탄C-3: 2,2-dimethoxy-N-n-butyl-I-aza-2-silacyclopentane
C-4 : N-페닐아미노메틸 (트리-메톡시)실란C-4: N-phenylaminomethyl (tri-methoxy)silane
E-1 : 디메틸술폭시드E-1: dimethyl sulfoxide
E-2 : 에틸렌글리콜E-2: Ethylene glycol
E-3 : N-에틸-2-피롤리돈E-3: N-ethyl-2-pyrrolidone
F-1: 폴리(아크릴아미드-코-디알릴디메틸암모늄 클로라이드)F-1: poly(acrylamide-co-diallyldimethylammonium chloride)
F-2: 2-머캅토 벤조티아졸F-2: 2-mercapto benzothiazole
실험예Experimental example 1. 실리콘 1. Silicone 질화막의of nitride film 선택적 optional 식각etching 능력 평가 ability evaluation
상기 실시예 1 내지 12 및 비교예 1 내지 5에서 제조한 실리콘 질화막 식각액 조성물의 실리콘 산화막에 대한 실리콘 질화막의 선택적 식각 능력을 평가하고자 하였다.The selective etching ability of the silicon nitride layer with respect to the silicon oxide layer of the silicon nitride layer etchant composition prepared in Examples 1 to 12 and Comparative Examples 1 to 5 was evaluated.
CVD 방법을 이용하여 반도체 제조 공정과 동일하게 증착하여 실리콘 질화막 웨이퍼 및 실리콘 산화막 웨이퍼를 각각 준비하였다. A silicon nitride film wafer and a silicon oxide film wafer were prepared by depositing in the same manner as in the semiconductor manufacturing process using the CVD method.
식각 전에 주사전자현미경(FESEM, 모델명:SU-8010, 제조사: 히타치)을 이용하여 상기 실리콘 질화막 웨이퍼 및 실리콘 산화막 웨이퍼의 두께를 측정하였다.Before etching, the thickness of the silicon nitride film wafer and the silicon oxide film wafer was measured using a scanning electron microscope (FESEM, model name: SU-8010, manufacturer: Hitachi).
상기 실리콘 질화막 웨이퍼 및 실리콘 산화막 웨이퍼 각각을 140±1℃의 온도로 유지되고 있는 상기 실시예 1 내지 12 및 비교예 1 내지 5의 실리콘 질화막 식각액 조성물에 5분 동안 담궈 식각 공정을 진행하였다.Each of the silicon nitride film wafer and the silicon oxide film wafer was immersed in the silicon nitride etchant composition of Examples 1 to 12 and Comparative Examples 1 to 5 maintained at a temperature of 140±1° C. for 5 minutes to perform an etching process.
식각 완료 후, 초순수로 세정하고, 건조 장치를 이용하여 잔여 식각액 조성물 및 수분을 완전히 건조시켰다.After the etching was completed, it was washed with ultrapure water, and the remaining etchant composition and moisture were completely dried using a drying device.
건조된 실리콘 질화막 웨이퍼 및 실리콘 산화막 웨이퍼를 주사전자현미경(FESEM, 모델명:SU-8010, 제조사: 히타치)을 이용하여 두께를 측정하였다.The thickness of the dried silicon nitride film wafer and silicon oxide film wafer was measured using a scanning electron microscope (FESEM, model name: SU-8010, manufacturer: Hitachi).
식각 전, 후의 두께로 식각량 및 식각 속도를 측정하였고, 실리콘 질화막 웨이퍼의 식각 속도와 실리콘 산화막 웨이퍼의 식각 속도 비에 의해 선택비를 계산하였다.The etching amount and the etching rate were measured by the thickness before and after the etching, and the selectivity was calculated by the ratio of the etching rate of the silicon nitride wafer to the etching rate of the silicon oxide wafer.
식각 선택비 평가 기준은 하기와 같고, 결과를 하기 표 2에 나타내었다.The etch selectivity evaluation criteria are as follows, and the results are shown in Table 2 below.
<식각 선택비 평가 기준><Estimation criteria for etch selectivity>
◎ : 선택비가 200 이상 ◎: selection ratio of 200 or more
○ : 선택비가 100 이상 200 미만○: selection ratio 100 or more but less than 200
△ : 선택비가 100 미만△: selection ratio less than 100
X : 선택비가 거의 0에 가까움X: the selectivity ratio is close to zero
상기 표 2의 결과에서, 본 발명의 실리콘 질화막 식각액 조성물인 실시예 1 내지 12는 실리콘 산화막을 거의 식각하지 않고, 실리콘 질화막을 선택적으로 식각하며, 선택비도 매우 우수한 결과를 보였다.From the results of Table 2, Examples 1 to 12, which are the silicon nitride etchant compositions of the present invention, hardly etched the silicon oxide film, selectively etched the silicon nitride film, and showed very good selectivity.
즉, 실리콘 산화막의 식각을 억제하는 역할을 하는 규소계 화합물을 포함함으로써, 실리콘 질화막의 선택비를 높일 수 있다는 것을 알 수 있었다.That is, it was found that the selectivity of the silicon nitride film could be increased by including the silicon-based compound serving to suppress the etching of the silicon oxide film.
반면, 인산을 포함하지 않는 비교예 1 및 인산을 제외한 비불소계 무기산을 포함하지 않는 비교예 2의 실리콘 질화막 식각액 조성물은 실리콘 질화막 및 실리콘 산화막의 식각 속도가 매우 느렸으며, 선택비 또한 불량하였다.On the other hand, the silicon nitride film etchant composition of Comparative Example 1 not containing phosphoric acid and Comparative Example 2 not containing the non-fluorine-based inorganic acid except phosphoric acid had very slow etching rates of the silicon nitride film and the silicon oxide film, and the selectivity was also poor.
규소계 화합물을 포함하지 않는 비교예 3의 실리콘 질화막 식각액 조성물은 실리콘 질화막 및 실리콘 산화막의 식각 속도가 매우 느렸으며, 선택비 또한 불량하였다.In the silicon nitride layer etchant composition of Comparative Example 3, which does not include a silicon-based compound, the etching rates of the silicon nitride layer and the silicon oxide layer were very slow, and the selectivity was also poor.
규소계 화합물 대신 실리콘 산화막의 식각을 억제시킬 수 있는 성분을 포함한 비교예 4 및 5의 실리콘 질화막 식각액 조성물은 실리콘 질화막의 식각 속도는 실시예와 비슷하였으나, 실리콘 산화막의 식각 속도가 높아 선택비가 불량한 결과를 보였다.The silicon nitride etchant compositions of Comparative Examples 4 and 5 containing a component capable of inhibiting the etching of the silicon oxide film instead of the silicon-based compound had similar etch rates to those of Examples, but the etch rate of the silicon oxide film was high, resulting in poor selectivity showed
따라서, 본 발명의 실리콘 질화막 식각액 조성물은 실리콘 산화막의 식각을 억제시킬 수 있어 실리콘 질화막을 선택적으로 식각할 수 있다.Therefore, the silicon nitride etchant composition of the present invention can suppress the etching of the silicon oxide layer, and thus the silicon nitride layer can be selectively etched.
Claims (10)
상기 규소계 화합물은 하기 화학식 1 내지 4로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물.
[화학식 1]
H2N-R1-[NH-R2]n-[NH-R3]m-Si(OR4)3
[화학식 2]
[화학식 3]
[화학식 4]
상기 R1 내지 R3은 각각 독립적으로 탄소수 1 내지 20의 알킬렌기이고,
상기 R4는 탄소수 1 내지 20의 알킬기이고,
상기 R5 내지 R12는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고,
상기 R13은 탄소수 1 내지 10의 알킬렌기이고,
상기 n 및 m은 각각 독립적으로 0 내지 10의 정수이다.A silicon nitride film etchant composition comprising phosphoric acid, a non-fluorine-based inorganic acid other than phosphoric acid, a silicon-based compound, and water,
The silicon-based compound is a silicon nitride film etchant composition comprising at least one selected from the group consisting of the following Chemical Formulas 1 to 4.
[Formula 1]
H 2 NR 1 -[NH-R 2 ] n -[NH-R 3 ] m -Si(OR 4 ) 3
[Formula 2]
[Formula 3]
[Formula 4]
The R 1 to R 3 are each independently an alkylene group having 1 to 20 carbon atoms,
Wherein R 4 is an alkyl group having 1 to 20 carbon atoms,
wherein R 5 to R 12 are each independently an alkyl group having 1 to 10 carbon atoms,
Wherein R 13 is an alkylene group having 1 to 10 carbon atoms,
Wherein n and m are each independently an integer of 0 to 10.
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