KR102576576B1 - Etching composition, method for etching insulating layer of semiconductor devices using the same and method for preparing semiconductor devices - Google Patents
Etching composition, method for etching insulating layer of semiconductor devices using the same and method for preparing semiconductor devices Download PDFInfo
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- KR102576576B1 KR102576576B1 KR1020180170731A KR20180170731A KR102576576B1 KR 102576576 B1 KR102576576 B1 KR 102576576B1 KR 1020180170731 A KR1020180170731 A KR 1020180170731A KR 20180170731 A KR20180170731 A KR 20180170731A KR 102576576 B1 KR102576576 B1 KR 102576576B1
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- etching composition
- etching
- formula
- alkylene
- silane compound
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- 238000005530 etching Methods 0.000 title claims abstract description 125
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims description 41
- 239000004065 semiconductor Substances 0.000 title claims description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 64
- -1 silane compound Chemical class 0.000 claims abstract description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 125000000743 hydrocarbylene group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 150000002431 hydrogen Chemical class 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 5
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 3
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 4
- 229910052698 phosphorus Inorganic materials 0.000 claims 4
- 239000011574 phosphorus Substances 0.000 claims 4
- 239000000126 substance Substances 0.000 claims 2
- 239000010408 film Substances 0.000 description 109
- 150000004767 nitrides Chemical class 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000654 additive Substances 0.000 description 26
- 230000000996 additive effect Effects 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229910052814 silicon oxide Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 229910052581 Si3N4 Inorganic materials 0.000 description 9
- 230000002159 abnormal effect Effects 0.000 description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- 125000006737 (C6-C20) arylalkyl group Chemical group 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001709 polysilazane Polymers 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- JTXUAHIMULPXKY-UHFFFAOYSA-N 3-trihydroxysilylpropan-1-amine Chemical compound NCCC[Si](O)(O)O JTXUAHIMULPXKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005360 phosphosilicate glass Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YNMZZHPSYMOGCI-UHFFFAOYSA-N undecan-3-one Chemical compound CCCCCCCCC(=O)CC YNMZZHPSYMOGCI-UHFFFAOYSA-N 0.000 description 2
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 description 1
- NJWDPSXFIVMIHY-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]-2-oxoacetic acid Chemical compound OCCN(CCO)C(=O)C(O)=O NJWDPSXFIVMIHY-UHFFFAOYSA-N 0.000 description 1
- AFRFYMZFIJPPDD-UHFFFAOYSA-N 2-hydroxy-n,n-bis(2-hydroxyethyl)acetamide Chemical compound OCCN(CCO)C(=O)CO AFRFYMZFIJPPDD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- HQQRKFPNUQQYHT-UHFFFAOYSA-N [SiH4].[P] Chemical class [SiH4].[P] HQQRKFPNUQQYHT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HTPGOQRGCUSPGR-UHFFFAOYSA-N phosphoric acid silane Chemical compound [SiH4].OP(O)(O)=O HTPGOQRGCUSPGR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic 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)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Weting (AREA)
Abstract
본 발명은 식각 조성물을 제공하고자 하는 것으로서, 본 발명의 일 구현예에 따른 식각 조성물은 인산 및 하기 화학식 1로 표시되는 실란화합물을 포함하는 식각 조성물이다.
[화학식 1]
R1 내지 R6는 독립적으로 수소, 하이드로카빌(hydrocarbyl) 또는 비-하이드로카빌(non-hydrocarbyl)이며, R1 내지 R6 중 적어도 하나가 옥소(oxo)이고, Lp는 하이드로카빌렌이고, p는 0 또는 1이며, A는 n가의 라디칼이고, n은 1 내지 4의 정수이다.The present invention is intended to provide an etching composition, and the etching composition according to one embodiment of the present invention is an etching composition containing phosphoric acid and a silane compound represented by Formula 1 below.
[Formula 1]
R 1 to R 6 are independently hydrogen, hydrocarbyl or non-hydrocarbyl, at least one of R 1 to R 6 is oxo, L p is hydrocarbylene, p is 0 or 1, A is an n-valent radical, and n is an integer of 1 to 4.
Description
본 발명은 식각 조성물, 특히 질화막을 선택적으로 제거할 수 있는 고선택비의 식각 조성물에 관한 것이다. The present invention relates to an etching composition, particularly an etching composition with high selectivity that can selectively remove a nitride film.
실리콘 산화막(SiO2) 등의 산화막 및 실리콘 질화막(SiNx) 등의 질화막은 대표적인 절연막으로서, 반도체 제조 공정에서 이들 실리콘 산화막 또는 실리콘 질화막 각각 단독으로, 또는 1층 이상의 막들이 교대로 적층되어 사용된다. 또한, 이러한 산화막 및 질화막은 금속 배선 등의 도전성 패턴을 형성하기 위한 하드마스크로도 이용된다. Oxide films such as silicon oxide (SiO 2 ) and nitride films such as silicon nitride (SiNx) are representative insulating films, and in the semiconductor manufacturing process, these silicon oxide films or silicon nitride films are used alone or with one or more layers alternately stacked. Additionally, these oxide and nitride films are also used as hard masks to form conductive patterns such as metal wiring.
질화막을 제거하기 위한 습식 식각 공정에서는 일반적으로 인산(phosphoric acid)과 탈이온수(deionized water)의 혼합물이 사용되고 있다. 탈이온수는 식각율 감소 및 산화막에 대한 식각 선택성의 변화를 방지하기 위하여 첨가되는 것이나, 공급되는 탈이온수의 양의 미세한 변화에도 질화막 식각 제거 공정에 불량이 발생하는 문제가 있다. 또한, 인산은 강산으로서 부식성을 가지고 있어 취급에 어려움이 있다.In a wet etching process to remove a nitride film, a mixture of phosphoric acid and deionized water is generally used. Deionized water is added to prevent a decrease in the etching rate and a change in etching selectivity for the oxide film, but there is a problem in that even a slight change in the amount of deionized water supplied causes defects in the nitride film etching removal process. Additionally, phosphoric acid is a strong acid and is corrosive, making handling difficult.
이를 해결하기 위한 종래 기술로 인산(H3PO4)에 불산(HF) 또는 질산(HNO3) 등을 포함하는 식각 조성물을 이용하여 질화막을 제거하는 방법이 공지되었으나, 오히려 질화막과 산화막의 식각 선택비를 저해시키는 결과를 초래하였다. 또한, 인산과 규산염, 또는 규산을 포함하는 식각 조성물을 이용하는 기술도 공지되어 있으나, 규산이나 규산염은 기판에 영향을 미칠 수 있는 파티클을 유발하여 오히려 반도체 제조 공정에 적합하지 못한 문제점이 있다.To solve this problem, a method of removing the nitride film using an etching composition containing phosphoric acid (H 3 PO 4 ) and hydrofluoric acid (HF) or nitric acid (HNO 3 ) was known in the prior art, but rather, the method of etching the nitride film and the oxide film was known. It resulted in the inhibition of rain. In addition, there is a known technology using phosphoric acid and silicate, or an etching composition containing silicic acid, but silicic acid or silicate causes particles that can affect the substrate, which has the problem of being unsuitable for the semiconductor manufacturing process.
그러나, 이러한 질화막 제거를 위한 습식 식각 공정에서 인산을 이용하는 경우, 질화막과 산화막의 식각 선택비 저하로 인하여 질화막뿐 아니라 SOD 산화막까지 식각되어 유효 산화막 높이(Effective Field Oxide Height, EFH)를 조절하는 것이 어려워진다. 이에 따라 질화막 제거를 위한 충분한 습식 식각 시간을 확보할 수 없거나, 추가적인 공정을 필요로 하게 되며, 변화를 유발하여 소자 특성에 악영항을 미치게 된다.However, when phosphoric acid is used in the wet etching process to remove the nitride film, not only the nitride film but also the SOD oxide film is etched due to a decrease in the etching selectivity between the nitride film and the oxide film, making it difficult to control the effective field oxide height (EFH). Lose. Accordingly, sufficient wet etching time for removal of the nitride film cannot be secured or additional processes are required, causing changes and adversely affecting device characteristics.
따라서, 반도체 제조 공정에서 산화막에 대하여 질화막을 선택적으로 식각하면서도 파티클 발생과 같은 문제점을 갖지 않는 고선택비의 식각 조성물이 요구되는 실정이다.Therefore, in the semiconductor manufacturing process, there is a need for an etching composition with a high selectivity that selectively etches the nitride film with respect to the oxide film and does not cause problems such as particle generation.
한편, 종래 식각 조성물에 첨가되는 첨가제인 실란계 첨가제는 용해도가 낮아 적정 용해도가 확보되지 않고, 이로 인해 식각 조성물 내에서 파티클의 석출 및 기판의 이상성장을 야기하는 문제가 있었다. 이러한 파티클은 실리콘 기판에 잔류하여 기판상에 구현되는 소자의 불량을 야기하거나 식각 또는 세정 공정에 사용되는 장비에 잔류하여 장비 고장을 야기하는 문제가 있다.Meanwhile, silane-based additives, which are additives added to conventional etching compositions, have low solubility, so appropriate solubility is not secured, which causes precipitation of particles in the etching composition and abnormal growth of the substrate. These particles remain on the silicon substrate, causing defects in devices implemented on the substrate, or remain in equipment used in etching or cleaning processes, causing equipment failure.
나아가 식각액의 장기 보관 시 질화막과 실리콘 산화막의 식각 속도가 변화하게 되어 선택도가 변화될 수 있다. Furthermore, when the etchant is stored for a long period of time, the etching speed of the nitride film and silicon oxide film may change, resulting in a change in selectivity.
본 발명은 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있으며, 소자 특성에 악영향을 미치는 파티클 발생 등의 문제점을 갖지 않는 고선택비의 식각 조성물을 제공하는데 그 목적이 있다.The purpose of the present invention is to provide an etching composition with high selectivity that can selectively remove the nitride film while minimizing the etching rate of the oxide film and does not have problems such as generation of particles that adversely affect device characteristics.
또한, 본 발명은 저장안정성이 우수한 식각 조성물을 제공하고자 하는데 또 다른 목적이 있다.In addition, another object of the present invention is to provide an etching composition with excellent storage stability.
나아가, 상기 식각 조성물을 이용한 절연막의 식각방법 및 반도체 소자의 제조방법을 제공하고자 한다.Furthermore, it is intended to provide a method of etching an insulating film and a method of manufacturing a semiconductor device using the etching composition.
본 발명은 식각 조성물을 제공하고자 하는 것으로서, 본 발명의 일 구현예에 따르면, 인산 및 하기 화학식 1로 표시되는 실란화합물을 포함하는 식각 조성물을 제공한다.The present invention is intended to provide an etching composition, and according to one embodiment of the present invention, an etching composition containing phosphoric acid and a silane compound represented by the following formula (1) is provided.
[화학식 1][Formula 1]
상기 화학식 1에서, R1 내지 R6는 독립적으로 수소, 하이드로카빌(hydrocarbyl) 또는 비-하이드로카빌(non-hydrocarbyl)이며, R1 내지 R6 중 적어도 하나가 옥소(oxo)이고, Lp는 하이드로카빌렌이며, p는 0 또는 1이고, A는 n가의 라디칼이고, n은 1 내지 4의 정수이다.In Formula 1, R 1 to R 6 are independently hydrogen, hydrocarbyl, or non-hydrocarbyl, at least one of R 1 to R 6 is oxo, and L p is Hydrocarbylene, p is 0 or 1, A is an n-valent radical, and n is an integer from 1 to 4.
상기 R1 내지 R6 중 상기 옥소(oxo)를 제외한 나머지가 수소인 것이 바람직하며, 상기 Lp가 C1-C5의 알킬이고, R1 및 R5 중 적어도 하나가 옥소인 것이 보다 바람직하다.Among R 1 to R 6 , it is preferable that the remainder excluding oxo is hydrogen, where L p is C 1 -C 5 alkyl, and at least one of R 1 and R 5 is more preferably oxo. .
상기 A는 수소, 할로겐, 하이드로카빌렌, 결합부위가 N인 라디칼, 결합부위가 O인 라디칼, 결합부위가 S인 라디칼 또는 결합부위가 P인 라디칼 일 수 있다.The A may be hydrogen, halogen, hydrocarbylene, a radical whose binding site is N, a radical whose binding site is O, a radical whose binding site is S, or a radical whose binding site is P.
상기 A는 C1-C20알킬, C2-C20알케닐 또는 C6-C20아릴일 수 있다.A may be C 1 -C 20 alkyl, C 2 -C 20 alkenyl or C 6 -C 20 aryl.
상기 결합부위가 N인 라디칼은 *-NR11R12, *-NR13-*, *-NR14CONR15-*, *-NR16CSNR17-* 또는 일 수 있으며, 여기서, R11 및 R12는 독립적으로 수소, C1-C20알킬, C1-C20아미노알킬 또는 CONH2이고, R13 내지 R17은 독립적으로 수소 또는 C1-C20알킬이고, L1은 C1-C20알킬렌이다.The radical whose bonding site is N is *-NR 11 R 12 , *-NR 13 -*, *-NR 14 CONR 15 -*, *-NR 16 CSNR 17 -* or may be, where R 11 and R 12 are independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 aminoalkyl, or CONH 2 , and R 13 to R 17 are independently hydrogen or C 1 -C 20 is alkyl, and L 1 is C 1 -C 20 alkylene.
상기 결합부위가 O인 라디칼은 *-O-*일 수 있다.The radical whose binding site is O may be *-O-*.
상기 결합부위가 S인 라디칼은 *-S-*, *-S-S-*, 또는 일 수 있다.The radical whose binding site is S is *-S-*, *-SS-*, or It can be.
상기 결합부위가 P인 라디칼은 , , 또는 일 수 있으며, 여기서, R18 및 R19는 독립적으로, 수소, C1-C20알킬, C6-C20아릴, 또는 (C1-C20)알킬(C1-C20)알콕시이다.The radical whose binding site is P is , , or may be, where R 18 and R 19 are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or (C 1 -C 20 )alkyl(C 1 -C 20 )alkoxy.
상기 화학식 1에서, n은 1이며, Lp는 C1-C5알킬렌이고, p는 0 또는 1이며, A는 수소, 할로겐, 치환 또는 비치환된 C1-C20알킬, 치환 또는 비치환된 C1-C20알케닐, *-NH2, *-NH-(CH2)l-NH2, *-NH-CO-NH2, 또는 *-(CH2)m-C6H5이고, l 및 m은 독립적으로 0 내지 10의 정수일 수 있다.In Formula 1, n is 1, Lp is C 1 -C 5 alkylene, p is 0 or 1, and A is hydrogen, halogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted. C 1 -C 20 alkenyl, *-NH 2 , *-NH-(CH 2 ) l -NH 2 , *-NH-CO-NH 2 , or *-(CH 2 ) m -C 6 H 5 , l and m may independently be integers from 0 to 10.
상기 화학식 1에서, n은 2이며, Lp는 C1-C5알킬렌이고, p는 0 또는 1이며, A는 C1-C20알킬렌, *-NR13-*, *-NR14-CO-NR15-*, *-O-*, *-S-*, *-S-S-*, , , 또는 이고, R13 내지 R15, R18 및 R19는 독립적으로 수소, C1-C20알킬, C6-C20아릴, 또는 (C1-C20)알킬(C1-C20)알콕시일 수 있다.In Formula 1, n is 2, Lp is C 1 -C 5 alkylene, p is 0 or 1, A is C 1 -C 20 alkylene, *-NR 13 -*, *-NR 14 - CO-NR 15 -*, *-O-*, *-S-*, *-SS-*, , , or and R 13 to R 15 , R 18 and R 19 are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or (C 1 -C 20 )alkyl(C 1 -C 20 )alkoxyyl. You can.
상기 화학식 1에서, n은 3이고, Lp는 C1-C5알킬렌이고, p는 0 또는 1이며, A는 또는 일 수 있다.In Formula 1, n is 3, Lp is C 1 -C 5 alkylene, p is 0 or 1, and A is or It can be.
상기 화학식 1에서, n은 4이고, Lp는 C1-C5알킬렌이고, p는 0 또는 1이며, A는 이고, 여기서 L1은 C1-C10알킬렌일 수 있다.In Formula 1, n is 4, Lp is C 1 -C 5 alkylene, p is 0 or 1, and A is , where L 1 may be C 1 -C 10 alkylene.
상기 실란화합물은 하기 구조에서 선택되는 것이 바람직하다.The silane compound is preferably selected from the following structures.
(1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17) (One), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17)
상기 화학식 (1)로 표시되는 실란화합물은 식각 조성물 전체 중량에 대하여 0.001 내지 5중량%로 포함되는 것이 바람직하며, 상기 식각 조성물은 인산 70 내지 90중량%, 화학식 1로 표시되는 실란화합물 0.001 내지 5중량% 및 잔부 물을 포함하는 것일 수 있다.The silane compound represented by the formula (1) is preferably contained in an amount of 0.001 to 5% by weight based on the total weight of the etching composition, and the etching composition contains 70 to 90% by weight of phosphoric acid and 0.001 to 5% by weight of the silane compound represented by the formula (1). It may include weight percent and remaining water.
상기 식각 조성물은 하기 화학식 2로 표시되는 실란 화합물을 더 포함할 수 있다.The etching composition may further include a silane compound represented by the following formula (2).
[화학식 2][Formula 2]
상기 화학식 2에서, R51 내지 R54는 서로 독립적으로 수소, C1-C20의 하이드로카빌, C1-C20의 헤테로하이드로카빌이고, R51 내지 R54는 각각 존재하거나 또는 2개 이상이 헤테로 원소를 통해 서로 연결된 고리형태일 수 있다.In Formula 2, R 51 to R 54 are independently hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 heterohydrocarbyl, and R 51 to R 54 are each present or two or more It may be in the form of a ring connected to each other through a hetero element.
상기 식각 조성물은 암모늄염을 더 포함할 수 있다.The etching composition may further include ammonium salt.
본 발명은 다른 견지로서 상기 식각 조성물을 이용한 절연막의 식각 방법을 제공한다.From another perspective, the present invention provides a method for etching an insulating film using the etching composition.
본 발명은 또 다른 견지로서 상기 절연막의 식각 방법을 포함하는 반도체 소자의 제조방법을 제공한다.As another aspect, the present invention provides a method of manufacturing a semiconductor device including a method of etching the insulating film.
본 발명은 또한, 하기 화학식 1로 표시되는 실란화합물을 제공한다.The present invention also provides a silane compound represented by the following formula (1).
[화학식 1][Formula 1]
R1 및 R2는 옥소이고, R3 내지 R6는 독립적으로 수소, 하이드로카빌 또는 비-하이드로카빌이고, Lp는 C1-C5알킬렌이고, p는 0 또는 1이며, A는 수소, 할로겐, 치환 또는 비치환된 C1-C20알킬, 치환 또는 비치환된 C1-C20알케닐, *-NH2, *-NH-(CH2)l-NH2, *-NH-CO-NH2, 또는 *-(CH2)m-C6H5이고, l 또는 m은 독립적으로 0 내지 10의 정수며, n은 1 내지 4의 정수이다.R 1 and R 2 are oxo, R 3 to R 6 are independently hydrogen, hydrocarbyl or non-hydrocarbyl, Lp is C 1 -C 5 alkylene, p is 0 or 1, A is hydrogen, Halogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkenyl, *-NH 2 , *-NH-(CH 2 ) l -NH 2 , *-NH-CO -NH 2 , or *-(CH 2 ) m -C 6 H 5 , l or m is independently an integer from 0 to 10, and n is an integer from 1 to 4.
상기 화학식 1은 하기 구조로 표현되는 실란화합물일 수 있다.Formula 1 may be a silane compound represented by the following structure.
본 발명은 또한, 하기 화학식 1로 표시되는 실란화합물을 제공한다.The present invention also provides a silane compound represented by the following formula (1).
[화학식 1][Formula 1]
R1 내지 R6는 독립적으로 수소, 하이드로카빌 또는 비-하이드로카빌이고, R1 내지 R6 중 적어도 하나가 옥소이며, Lp는 C1-C5알킬렌이고, p는 0 또는 1이며, A는 C1-C20알킬렌, *-NR13-*, *-NR14-CO-NR15-*, *-O-*, *-S-*, *-S-S-*, , , , , , 또는 이고, R13 내지 R15, R18 및 R19는 독립적으로 수소, C1-C20알킬, C6-C20아릴, 또는 C1-C20알킬C1-C20알콕시이고, L1은 C1-C10알킬렌이며, n은 2 내지 4의 정수이다.R 1 to R 6 are independently hydrogen, hydrocarbyl or non-hydrocarbyl, at least one of R 1 to R 6 is oxo, L p is C 1 -C 5 alkylene, p is 0 or 1, A is C 1 -C 20 alkylene, *-NR 13 -*, *-NR 14 -CO-NR 15 -*, *-O-*, *-S-*, *-SS-*, , , , , , or and R 13 to R 15 , R 18 and R 19 are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or C 1 -C 20 alkylC 1 -C 20 alkoxy, and L 1 is C 1 -C 10 alkylene, and n is an integer of 2 to 4.
상기 화학식 1은 다음 중 어느 하나의 구조로 표현되는 것인 실란화합물일 수 있다.Formula 1 may be a silane compound expressed in any of the following structures.
(6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17) (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17)
본 발명에 따른 식각 조성물은 산화막에 대한 질화막의 식각 선택비가 높다.The etching composition according to the present invention has a high etching selectivity of the nitride film to the oxide film.
또한, 본 발명의 식각 조성물을 이용하면 질화막 제거 시에 산화막의 막질 손상이나 산화막의 식각으로 인한 전기적 특성 저하를 방지하고, 파티클 발생을 방지하여, 소자 특성을 향상시킬 수 있다. In addition, using the etching composition of the present invention, it is possible to prevent damage to the quality of the oxide film or deterioration of electrical properties due to etching of the oxide film when removing the nitride film, prevent particle generation, and improve device characteristics.
도 1 및 도 2는 본 발명의 실시예에 따른 절연막의 식각방법을 예시한 공정 단면도이다.1 and 2 are cross-sectional process views illustrating a method of etching an insulating film according to an embodiment of the present invention.
본 발명은 식각 조성물, 특히 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있는 고선택비를 가지며, 또한, 저장안정성이 우수한 식각 조성물을 제공하고자 한다. The present invention seeks to provide an etching composition, particularly an etching composition that has a high selectivity for selectively removing a nitride film while minimizing the etching rate of the oxide film, and also has excellent storage stability.
본 명세서에서, "하이드로카빌(hydrocarbyl)"은 하이드로카본에서 유래되는 모든 일가(univalent) 치환기를 의미한다. As used herein, “hydrocarbyl” refers to any univalent substituent derived from hydrocarbon.
본 명세서에서, "비-하이드로카빌(non-hydrocarbyl)"은 하이드로카빌이 아닌 치환기를 의미한다.As used herein, “non-hydrocarbyl” refers to a substituent that is not hydrocarbyl.
본 발명의 식각 조성물은 인산, 실란화합물 및 물을 포함한다.The etching composition of the present invention includes phosphoric acid, a silane compound, and water.
상기 인산은 실리콘 질화물과 반응하여 질화물을 식각하는 것으로서, 상기 인산은 하기 식 (1)과 같이 반응하여 실리콘 질화물을 식각한다.The phosphoric acid reacts with silicon nitride to etch the nitride, and the phosphoric acid reacts as shown in the following formula (1) to etch the silicon nitride.
3Si3N4 + 27H2O + 4H3PO4 → 4(NH4)3PO4 + 9SiO2H2O (1)3Si 3 N 4 + 27H 2 O + 4H 3 PO 4 → 4(NH 4 ) 3 PO 4 + 9SiO 2 H 2 O (1)
예를 들어, 상기 인산은 75 내지 85% 농도의 인산을 포함하는 인산 수용액일 수 있다. 상기 인산 수용액에 사용되는 물은 특별히 한정하는 것은 아니지만, 탈이온수를 이용할 수 있다. For example, the phosphoric acid may be an aqueous phosphoric acid solution containing phosphoric acid at a concentration of 75 to 85%. The water used in the phosphoric acid aqueous solution is not particularly limited, but deionized water can be used.
인산은 식각 조성물 전체 중량에 대하여 70 내지 90중량%의 함량으로 포함하는 것이 바람직하다. 70중량% 미만인 경우에는 질화막이 용이하게 제거되지 않는 문제가 있으며, 90%중량을 초과하는 경우에는 질화막에 대한 높은 선택비를 얻을 수 없다. Phosphoric acid is preferably included in an amount of 70 to 90% by weight based on the total weight of the etching composition. If it is less than 70% by weight, there is a problem that the nitride film is not easily removed, and if it exceeds 90% by weight, a high selectivity to the nitride film cannot be obtained.
본 발명의 식각 조성물은 식각액 첨가제로서 실란화합물을 포함한다. 상기 실란화합물은, 예를 들면, 다음 화학식 1로 표시되는 실란화합물일 수 있다. The etching composition of the present invention includes a silane compound as an etchant additive. The silane compound may be, for example, a silane compound represented by the following formula (1).
상기 화학식 1에서, R1 내지 R6는 독립적으로 수소, 하이드로카빌(hydrocarbyl) 또는 비-하이드로카빌(non-hydrocarbyl)이고, R1 내지 R6 중 적어도 하나가 옥소일 수 있다. 예를 들어, 상기 하이드로카빌 또는 비-하이드로카빌은, 이에 한정하는 것은 아니지만, 치환 또는 비치환된 C1-C20의 하이드로카빌기, C1-C20의 알콕시기, 카르복시기, 카르보닐기, 니트로기, 트리(C1-C20)알킬실릴기, 포스포릴기 또는 시아노기일 수 있다. R1 내지 R6이 적어도 하나가 옥소일 경우 실란화합물의 인산에 대한 용해도가 높아져 실란화합물에 의한 파티클 생성이나 패턴의 이상성장 등을 방지할 수 있다. 보다 바람직하게는 R1 및 R2 중 적어도 하나가 옥소일 수 있다.In Formula 1, R 1 to R 6 are independently hydrogen, hydrocarbyl, or non-hydrocarbyl, and at least one of R 1 to R 6 may be oxo. For example, the hydrocarbyl or non-hydrocarbyl is, but is not limited to, a substituted or unsubstituted C 1 -C 20 hydrocarbyl group, a C 1 -C 20 alkoxy group, a carboxyl group, a carbonyl group, or a nitro group. , tri(C 1 -C 20 )alkylsilyl group, phosphoryl group, or cyano group. When at least one of R 1 to R 6 is oxo, the solubility of the silane compound in phosphoric acid increases, thereby preventing particle generation or abnormal pattern growth due to the silane compound. More preferably, at least one of R 1 and R 2 may be oxo.
상기 C1-C20의 치환 또는 비치환된 하이드로카빌기는 치환 또는 비치환된 C1-C20의 알킬기, 또는 치환 또는 비치환된 C6-C20의 아릴기일 수 있으며, 여기서 치환은 하이드로카빌기는 할로겐화알킬과 같은 할로겐으로 치환된 하이드로카빌기일 수 있다.The substituted or unsubstituted hydrocarbyl group of C 1 -C 20 may be a substituted or unsubstituted alkyl group of C 1 -C 20 or a substituted or unsubstituted aryl group of C 6 -C 20 , where substitution is hydro The carbyl group may be a hydrocarbyl group substituted with a halogen such as an alkyl halide.
상기 Lp는 하이드로카빌렌이며, p는 0 또는 1일 수 있다. 상기 Lp는 예를 들어, 직접 결합일 수 있고, 또는 C1-C5의 하이드로카빌렌, 예를 들어, C1-C5알킬렌, 구체적으로는 C1-C3알킬렌일 수 있다.The Lp is hydrocarbylene, and p may be 0 or 1. For example, Lp may be a direct bond, or may be C 1 -C 5 hydrocarbylene, for example, C 1 -C 5 alkylene, specifically C 1 -C 3 alkylene.
상기 A는 1 내지 4의 정수인 n가의 라디칼을 나타낸다. 예를 들어, A는 수소, 할로겐, 하이드로카빌렌, 결합부위가 N인 라디칼, 결합부위가 O인 라디칼, 결합부위가 S인 라디칼, 결합부위가 P인 라디칼 등일 수 있다. The A represents an n-valent radical that is an integer of 1 to 4. For example, A may be hydrogen, halogen, hydrocarbylene, a radical with a bonding site of N, a radical with a bonding site of O, a radical with a bonding site of S, a radical with a bonding site of P, etc.
예를 들어, 상기 A는 수소일 수 있으며, F, Cl, Br, I 등의 할로겐일 수 있다. 이때, 상기 n은 1의 정수이다.For example, A may be hydrogen and may be a halogen such as F, Cl, Br, or I. At this time, n is an integer of 1.
상기 하이드로카빌렌으로는 치환 또는 비치환된 C1-C20알킬, C2-C20알케닐 또는 C6-C20아릴일 수 있으며, 보다 구체적으로, 예를 들어, *-CH3, *-(CH2)3, *-(CH2)2CH3, *-(CH2)7CH3, *-CH2CH(CH3)2, *-CHCH2, *-페닐 등일 수 있다. 이때, 상기 n은 1의 정수이다. 나아가, n이 2인 경우로서, *-(CH2)2-*와 같은 치환 또는 비치환된 C2-C20의 알케닐일 수 있다.The hydrocarbylene may be substituted or unsubstituted C 1 -C 20 alkyl, C 2 -C 20 alkenyl, or C 6 -C 20 aryl, and more specifically, for example, *-CH 3 , * It may be -(CH 2 ) 3 , *-(CH 2 ) 2 CH 3 , *-(CH 2 ) 7 CH 3 , *-CH 2 CH(CH 3 ) 2 , *-CHCH 2 , *-phenyl, etc. At this time, n is an integer of 1. Furthermore, when n is 2, it may be substituted or unsubstituted C 2 -C 20 alkenyl such as *-(CH 2 ) 2 -*.
상기 A가 결합부위가 N인 라디칼로는, 예를 들어, n이 1인 경우로서, *-NH2와 같은 비치환된 아민, 또는 *-NH(CH2)2NH2 또는 *-NHCONH2와 같은 치환된 아민 등의 *-NR11R12 등을 들 수 있다. 또한, n이 2인 경우로서, *-NH-*와 같은 *-NR13-*, *-NHCONH-*와 같은 *-NR14CONR15-*, *-NHCSNH-*와 같은 *-NR16CSNR17-* 등을 들 수 있다. 나아가, n이 4인 경우로서는, 를 들 수 있다.The radical where A binds N is, for example, when n is 1, an unsubstituted amine such as *-NH 2 , or *-NH(CH 2 ) 2 NH 2 or *-NHCONH 2 Substituted amines such as *-NR 11 R 12 and the like can be mentioned. Additionally, when n is 2, *-NR 13 -* such as *-NH-*, *-NR 14 CONR 15 -* such as *-NHCONH-*, *-NR 16 such as *-NHCSNH-* CSNR 17 -*, etc. may be mentioned. Furthermore, in the case where n is 4, can be mentioned.
여기서, R11 및 R12는 독립적으로 수소, C1-C20의 알킬, C1-C20의 아미노알킬 또는 CONH2 등일 수 있고, R13 내지 R17은 독립적으로 수소 또는 C1-C20의 알킬일 수 있으며, L1은 C1-C20의 알킬렌일 수 있다.Here, R 11 and R 12 may independently be hydrogen, C 1 -C 20 alkyl, C 1 -C 20 aminoalkyl or CONH 2 , etc., and R 13 to R 17 may independently be hydrogen or C 1 -C 20 It may be an alkyl, and L 1 may be an alkylene of C 1 -C 20 .
상기 A가 결합부위가 O인 라디칼로는 *-O-*일 수 있으며, 이때, n은 2의 정수이다.The radical where A binds to O may be *-O-*, where n is an integer of 2.
상기 결합부위가 S인 라디칼은 *-S-*, *-S-S-*, 또는 일 수 있으며, 이때, n은 2의 정수이다.The radical whose binding site is S is *-S-*, *-SS-*, or It may be, where n is an integer of 2.
한편, 상기 결합부위가 P인 라디칼은 , , 또는 를 들 수 있으며, 이때, n은 2 또는 3의 정수이다. 여기서, R8 및 R9는 독립적으로, 수소, C1-C20의 알킬, C6-C20의 아릴, 또는 (C1-C20)알킬(C1-C20)알콕시일 수 있다.Meanwhile, the radical whose binding site is P is , , or may be mentioned, where n is an integer of 2 or 3. Here, R 8 and R 9 may independently be hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or (C 1 -C 20 )alkyl(C 1 -C 20 )alkoxy.
본 발명에 있어서, n이 1인 경우의 화학식 1의 실란화합물은, 예를 들어, Lp가 직접결합 또는 C1-C5알킬렌이고, A가 치환 또는 비치환의 C1-C20의 알킬, *-NH2, *-NH-(CH2)l-NH2, *-NH-CO-NH2, *-C6H5 또는 *-(CH2)m-C6H5이며, 상기 l 또는 m은 독립적으로 1 내지 10의 정수인 실란 화합물일 수 있다.In the present invention, the silane compound of Formula 1 when n is 1, for example, Lp is a direct bond or C 1 -C 5 alkylene, A is a substituted or unsubstituted C 1 -C 20 alkyl, *-NH 2 , *-NH-(CH 2 ) l -NH 2 , *-NH-CO-NH 2 , *-C 6 H 5 or *-(CH 2 ) m -C 6 H 5 , where l Or m may independently be a silane compound that is an integer of 1 to 10.
또한, n이 2인 경우의 화학식 1의 실란화합물로는, 예를 들어, Lp가 직접결합 또는 C1-C5의 알킬렌이고, A가 C1-C20의 알킬렌이며, *-NH-* 또는 *-C(O)-*인 실란화합물일 수 있다.In addition, as a silane compound of Formula 1 when n is 2, for example, Lp is a direct bond or C 1 -C 5 alkylene, A is C 1 -C 20 alkylene, *-NH It may be a silane compound of -* or *-C(O)-*.
또한, n은 3인 경우의 화학식 1의 실란화합물로는, 예를 들어, Lp는 직접결합 또는 C1-C3 알킬렌이고, A가 또는 인 실란 화합물을 들 수 있다.In addition, in the silane compound of Formula 1 where n is 3, for example, Lp is a direct bond or C1-C3 alkylene, and A is or Phosphorus silane compounds can be mentioned.
나아가, n이 4인 경우의 화학식 1의 실란화합물은, 예를 들어, Lp가 직접결합 또는 C1-C3의 알킬렌이고, A가 이며, 여기서 L1이 C1-C10의 알킬렌인 실란화합물일 수 있다.Furthermore, in the silane compound of Formula 1 when n is 4, for example, Lp is a direct bond or C 1 -C 3 alkylene, and A is , where L 1 may be a silane compound of C 1 -C 10 alkylene.
화학식 1로 표시되는 실란화합물로는, 보다 구체적으로 예를 들면, 다음과 같은 구조식 1 내지 17로 표시되는 실란화합물 중 어느 하나일 수 있다.More specifically, the silane compound represented by Formula 1 may be any one of the silane compounds represented by the following structural formulas 1 to 17.
(1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17) (One), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17)
상기와 같은 실란화합물에 포함된 산소들은 산화막의 표면에 결합하여 산화막을 보호하며, 실란화합물에 포함된 산소들은 산화막의 표면에 수소 결합할 수 있어, 식각 조성물 내에서 질화물이 식각되는 동안 산화막이 식각되는 것을 최소화할 수 있다. 또한 R1 내지 R6의 적어도 하나가 옥소일 경우 실란화합물의 인산에 대한 용해도가 높아져 실란화합물에 의한 파티클 생성이나 패턴의 이상성장 등을 방지할 수 있다.The oxygen contained in the above silane compound protects the oxide film by bonding to the surface of the oxide film, and the oxygen contained in the silane compound can hydrogen bond to the surface of the oxide film, thereby etching the oxide film while the nitride is etched in the etching composition. This can be minimized. In addition, when at least one of R 1 to R 6 is iodine, the solubility of the silane compound in phosphoric acid is increased, thereby preventing generation of particles or abnormal pattern growth due to the silane compound.
또한, 상기와 같은 실란화합물은 고리모양의 실란화합물로서, 식각 조성물 내에서 가장 안정적인 형태로 존재할 수 있으며, 따라서, 통상적으로 사용되던 단사슬 모양의 실리콘 첨가제에 비하여 식각 선택비를 현저히 상승시킬 수 있다. 나아가, 상기와 같은 고리 모양의 화합물을 포함함으로써 식각 조성물 내의 활성 실리콘계 첨가제의 구조 안정성이 향상되어, 실리콘 산화막의 식각 속도를 또한 지속적으로 유지할 수 있다.In addition, the above silane compound is a cyclic silane compound and can exist in the most stable form in the etching composition, and therefore can significantly increase the etching selectivity compared to the commonly used short-chain silicon additive. . Furthermore, by including the above-mentioned cyclic compound, the structural stability of the active silicon-based additive in the etching composition is improved, and the etching rate of the silicon oxide film can be continuously maintained.
본 발명에서 제안하는 바와 같은 실란화합물은 식각 조성물에 소량으로 첨가하더라도 실리콘 산화막을 효과적으로 보호할 수 있어 산화막에 대한 질화물의 식각 선택성을 증가시킬 수 있다. 상기 실란화합물은 식각 조성물 전체 중량에 대하여 0.001 내지 5중량%의 함량으로 첨가할 수 있다. 상기 실란화합물의 함량이 0.001중량% 미만으로 사용하는 경우에는 산화막에 대한 질화물의 고선택성 효과를 얻기 어려우며, 5중량%를 초과하는 경우에는 실란화합물이 겔화될 수 있는바 바람직하지 않다. 상기 실란화합물은 예를 들면, 0.001, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1, 0.15 또는 0.2중량% 이상이고, 5, 4.5, 4, 3.5, 3, 2.5, 2 또는 1중량% 이하인 범위 내의 함량으로 식각 조성물에 포함할 수 있다. The silane compound proposed in the present invention can effectively protect the silicon oxide film even when added in a small amount to the etching composition, thereby increasing the etching selectivity of nitride over the oxide film. The silane compound can be added in an amount of 0.001 to 5% by weight based on the total weight of the etching composition. If the silane compound is used in an amount of less than 0.001% by weight, it is difficult to obtain a high selectivity effect of the nitride for the oxide film, and if it is more than 5% by weight, the silane compound may gel, which is not desirable. For example, the silane compound is 0.001, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1, 0.15, or 0.2% by weight or more, and is 5, 4.5, 4, 3.5, 3, 2.5, 2, or 1% by weight or less. It can be included in the etching composition in an amount within the range.
식각 조성물에 대한 첨가제로 종래 사용되는 실란 화합물은 용해도가 낮은 특징이 있다. 식각 조성물에서 적정 용해도가 확보되지 않은 실란계 첨가제를 사용하거나 또는 조성비가 적정 수준으로 조정되지 않는 경우에는 식각 조성물 내에서 실리콘계 파티클 석출과 이상성장을 야기한다. 이러한 파티클은 실리콘 기판에 잔류하여 기판 상에 구현되는 소자의 불량을 야기하거나 식각 또는 세정 공정에 사용되는 장비(예를 들어, 필터)에 잔류하여 장비 고장을 야기할 수 있다. Silane compounds conventionally used as additives for etching compositions are characterized by low solubility. If a silane-based additive that does not have adequate solubility is used in the etching composition or the composition ratio is not adjusted to an appropriate level, precipitation and abnormal growth of silicon-based particles occur within the etching composition. These particles may remain on the silicon substrate, causing defects in devices implemented on the substrate, or may remain in equipment (eg, filters) used in the etching or cleaning process, causing equipment failure.
그러나, 본 발명의 식각 조성물은 상기와 같은 실란화합물에 의해 산화물에 대한 식각을 억제함으로써 질화물에 대한 선택도를 향상시키면서, 실리카 생성을 억제하여 파티클 생성 억제 및 저장안정성을 향상시키는 효과를 얻을 수 있다. However, the etching composition of the present invention suppresses etching of oxides using the silane compound as described above, thereby improving selectivity to nitrides and suppressing silica production, thereby suppressing particle production and improving storage stability. .
한편, 상기 식 1에서 SiO2H2O는 통상적으로 산화막의 표면에 석출되어 산화막의 두께를 증가시킬 수 있는 이상 성장 현상을 나타낼 수 있다. 특히, 식각 조성물 내에서 질화물의 식각 공정이 누적되어 진행되는 경우, 식각 조성물 내의 SiO2H2O의 농도가 증가될 수 있으며, 이러한 SiO2H2O의 농도 증가는 이상 성장의 발생 정도가 증가할 수 있다. 즉, 초기 식각 조성물에서는 SiO2H2O에 의한 이상 성장이 발생하지 않더라도, 누적 공정 횟수가 증가할수록 이상 성장이 발생 빈도가 증가할 수 있다. 그러나, 본 발명에 따른 실란화합물을 포함하는 경우에는 이와 같은 이상성장의 현상 발생을 억제할 수 있다.On the other hand, SiO 2 H 2 O in Equation 1 is usually precipitated on the surface of the oxide film and may exhibit an abnormal growth phenomenon that can increase the thickness of the oxide film. In particular, when the etching process of nitride is accumulated in the etching composition, the concentration of SiO 2 H 2 O in the etching composition may increase, and the increase in the concentration of SiO 2 H 2 O increases the degree of abnormal growth. can do. That is, even if abnormal growth due to SiO 2 H 2 O does not occur in the initial etching composition, the frequency of abnormal growth may increase as the number of cumulative processes increases. However, when the silane compound according to the present invention is included, the occurrence of such abnormal growth can be suppressed.
본 발명의 식각 조성물에 있어서, 잔부는 용매이다. 상기 용매는 특별히 한정하지 않으나, 물일 수 있다. In the etching composition of the present invention, the remainder is a solvent. The solvent is not particularly limited, but may be water.
본 발명의 식각 조성물은 다음의 화학식 2로 표시되는 실란화합물을 더 포함할 수 있다.The etching composition of the present invention may further include a silane compound represented by the following formula (2).
상기 화학식 2에서, R51 내지 R54는 서로 독립적으로 수소, C1-C20의 하이드로카빌, C1-C20의 헤테로하이드로카빌이고, R51 내지 R54는 각각 존재하거나 또는 2개 이상이 헤테로 원소를 통해 서로 연결된 고리형태이다. 예를 들어, 수소, C1-C20알킬 또는 C1-C20헤테로알킬 등일 수 있다. 이때, 상기 헤테로 원소는 특별히 한정하지 않으나, 예를 들면, N, S, O, P 등일 수 있다.In Formula 2, R 51 to R 54 are each independently hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 heterohydrocarbyl, and R 51 to R 54 are each present or two or more It is in the form of rings connected to each other through hetero elements. For example, it may be hydrogen, C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, etc. At this time, the hetero element is not particularly limited, but may be, for example, N, S, O, P, etc.
상기 화학식 2로 표시되는 실란화합물은 전체 식각 조성물 중량에 대하여 0.005 내지 1중량%의 함량으로 포함할 수 있다.The silane compound represented by Formula 2 may be included in an amount of 0.005 to 1% by weight based on the total weight of the etching composition.
나아가, 본 발명의 식각 조성물에는 암모늄염을 또한 첨가할 수 있다. 암모늄염은 식각 조성물의 겔화를 방지할 수 있으며, 전체 중량에 대해 0.001 내지 10중량%의 함량으로 첨가할 수 있다. 0.001중량% 미만으로 첨가하면 겔화를 저하시키는 물성 개선효과가 미미하며, 10중량%를 초과하여 첨가하면 암모늄염이 겔화의 원인이 될 수 있다.Furthermore, ammonium salt can also be added to the etching composition of the present invention. Ammonium salt can prevent gelation of the etching composition and can be added in an amount of 0.001 to 10% by weight based on the total weight. If added in less than 0.001% by weight, the effect of improving physical properties in reducing gelation is minimal, and if added in excess of 10% by weight, ammonium salt may cause gelation.
상기 암모늄염으로는 암모늄 이온을 갖는 화합물로서, 본 발명이 속하는 분야에서 통상적으로 사용되는 것을 본 발명에서도 적합하게 사용할 수 있다. 이러한 암모늄염으로는 이에 한정하는 것은 아니지만, 예를 들어, 암모니아수, 암모늄클로라이드, 암모늄 아세트산, 암모늄인산염, 암모늄과옥시이황산염, 암모늄황산염, 암모늄불산염 등을 들 수 있으며, 이들 중 어느 하나를 단독으로 사용할 수 있음은 물론, 2 이상을 혼합하여 사용할 수도 있다.The ammonium salt is a compound having an ammonium ion, and those commonly used in the field to which the present invention pertains can also be suitably used in the present invention. Such ammonium salts are not limited thereto, but include, for example, ammonia water, ammonium chloride, ammonium acetic acid, ammonium phosphate, ammonium peroxydisulfate, ammonium sulfate, and ammonium hydrofluoric acid. Any one of these may be used alone. Of course, it is possible to use a mixture of two or more.
나아가, 본 발명의 식각 조성물은 식각 성능을 더욱 향상시키기 위해, 본 기술분야에서 통상적으로 사용되는 임의의 첨가제를 더 포함할 수 있다. 첨가제로는 계면활성제, 금속이온 봉쇄제, 부식방지제 등을 들 수 있다.Furthermore, the etching composition of the present invention may further include any additives commonly used in the art to further improve etching performance. Additives include surfactants, metal ion sequestrants, and corrosion inhibitors.
본 발명의 식각 조성물은 산화막과 질화막을 포함하는 반도체 소자로부터 질화막을 선택적으로 식각 제거하기 위해 사용되는 것으로서, 상기 질화막은 실리콘 질화막, 예컨대, SiN 막, SiON 막 등을 포함할 수 있다.The etching composition of the present invention is used to selectively etch and remove a nitride film from a semiconductor device including an oxide film and a nitride film, and the nitride film may include a silicon nitride film, for example, a SiN film, a SiON film, etc.
또한, 산화막은 실리콘 산화막, 예컨대 SOD(Spin On Dielectric)막, HDP(High Density Plasma)막, 열산화(thermal oxide)막, BPSG(Borophosphate Silicate Glass)막, PSG(Phospho Silicate Glass)막, BSG(Boro Silicate Glass)막, PSZ(Polysilazane)막, FSG(Fluorinated Silicate Glass)막, LPTEOS(Low Pressure Tetra Ethyl Ortho Silicate)막, PETEOS(Plasma Enhanced Tetra Ethyl Ortho Silicate)막, HTO(High Temperature Oxide)막, MTO(Medium Temperature Oxide)막, USG(Undopped Silicate Glass)막, SOG(Spin On Glass)막, APL(Advanced Planarization Layer)막, ALD(Atomic Layer Deposition)막, PE-산화막(Plasma Enhanced oxide), O3-TEOS(O3-Tetra Ethyl Ortho Silicate)막 및 그 조합으로 이루어진 군으로부터 선택되는 적어도 일 이상의 막일 수 있다.In addition, the oxide film may be a silicon oxide film, such as a Spin On Dielectric (SOD) film, a High Density Plasma (HDP) film, a thermal oxide film, a Borophosphate Silicate Glass (BPSG) film, a Phospho Silicate Glass (PSG) film, or a BSG ( Boro Silicate Glass (PSZ) film, PSZ (Polysilazane) film, FSG (Fluorinated Silicate Glass) film, LPTEOS (Low Pressure Tetra Ethyl Ortho Silicate) film, PETEOS (Plasma Enhanced Tetra Ethyl Ortho Silicate) film, HTO (High Temperature Oxide) film, MTO (Medium Temperature Oxide) film, USG (Undopped Silicate Glass) film, SOG (Spin On Glass) film, APL (Advanced Planarization Layer) film, ALD (Atomic Layer Deposition) film, PE-oxide film (Plasma Enhanced oxide), O3 -It may be at least one film selected from the group consisting of a TEOS (O3-Tetra Ethyl Ortho Silicate) film and a combination thereof.
본 발명의 식각 조성물을 이용하는 식각 공정은 습식 식각 방법, 예컨대 침지시키는 방법, 분사하는 방법 등에 의하여 이루어질 수 있다.The etching process using the etching composition of the present invention may be performed by a wet etching method, such as an immersion method or a spraying method.
본 발명의 식각 조성물을 사용하는 식각공정의 예를 도 1 및 도 2에 개략적으로 나타내었다. 도 1 및 도 2는, 일례로, 플래시 메모리 소자의 소자 분리 공정을 나타내는 공정 단면도이다. An example of an etching process using the etching composition of the present invention is schematically shown in Figures 1 and 2. 1 and 2 are cross-sectional views showing, as an example, a device separation process for a flash memory device.
먼저, 도 1에 도시된 바와 같이, 기판(10) 상에 터널산화막(11), 폴리실리콘막(12), 버퍼산화막(13) 및 패드질화막(14)을 차례로 형성한 후, 폴리실리콘막(12), 버퍼산화막(13) 및 패드질화막(14)을 선택적으로 식각하여 트렌치를 형성한다. 이어서, 트렌치를 갭필할 때까지 SOD 산화막(15)을 형성한 후, 패드질화막(14)을 연마정지막으로 하여 SOD 산화막(15)에 대해 CMP 공정을 실시한다.First, as shown in FIG. 1, a tunnel oxide film 11, a polysilicon film 12, a buffer oxide film 13, and a pad nitride film 14 are sequentially formed on the substrate 10, and then a polysilicon film ( 12), the buffer oxide film 13 and the pad nitride film 14 are selectively etched to form a trench. Next, the SOD oxide film 15 is formed until the trench is gap-filled, and then a CMP process is performed on the SOD oxide film 15 using the pad nitride film 14 as a polishing stop film.
다음으로, 도 2에 도시된 바와 같이, 전술한 본 발명에 따른 식각 조성물을 이용한 습식 식각에 의하여 패드질화막(14)을 제거한 후, 세정 공정에 의하여 버퍼산화막(13)을 제거한다. 이로써, 필드 영역에 소자분리막(15A)이 형성된다. Next, as shown in FIG. 2, the pad nitride film 14 is removed by wet etching using the etching composition according to the present invention described above, and then the buffer oxide film 13 is removed through a cleaning process. As a result, the device isolation film 15A is formed in the field region.
식각 공정시 공정 온도는 50 내지 300℃의 범위, 바람직하게는 100 내지 200℃의 범위, 보다 바람직하게는 156℃ 내지 163℃의 범위일 수 있으며, 적정 온도는 다른 공정과 기타 요인을 고려하여 필요에 따라 변경될 수 있다.During the etching process, the process temperature may range from 50 to 300°C, preferably from 100 to 200°C, and more preferably from 156°C to 163°C. The appropriate temperature is necessary in consideration of other processes and other factors. It may change depending on.
이와 같이 본 발명의 식각 조성물을 이용하여 수행되는 식각 공정을 포함하는 반도체 소자의 제조방법에 따르면, 질화막과 산화막이 교대로 적층되거나 혼재되어 있는 경우 질화막에 대한 선택적 식각이 가능하다. 또한, 종래 식각 공정에서 문제되었던 파티클 발생을 방지하여 식각 공정의 안정성 및 신뢰성을 확보할 수 있다.According to the method of manufacturing a semiconductor device including an etching process performed using the etching composition of the present invention, selective etching of the nitride film is possible when the nitride film and the oxide film are alternately stacked or mixed. In addition, the stability and reliability of the etching process can be secured by preventing the generation of particles, which was a problem in the conventional etching process.
따라서, 이러한 방법은 반도체 소자 제조공정에 있어서 산화막에 대하여 질화막의 선택적 식각이 필요한 여러 과정에 효율적으로 적용될 수 있다.Therefore, this method can be efficiently applied to various processes that require selective etching of the nitride film with respect to the oxide film in the semiconductor device manufacturing process.
실시예Example
이하, 본 발명을 실시예를 들어 보다 구체적으로 설명한다. 이하의 실시예는 본 발명의 일 예에 대한 것으로서, 이에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. The following example is an example of the present invention, and the present invention is not limited thereto.
합성예 1Synthesis Example 1
100㎖ 둥근바닥 플라스크에 N,N-비스(2-히드록시에틸)글리신 16.3g과 클로로메틸트리메톡시실란 17.0g, 톨루엔 30㎖를 넣은 후 130℃로 승온하여 24시간 교반하였다. 16.3 g of N,N-bis(2-hydroxyethyl)glycine, 17.0 g of chloromethyltrimethoxysilane, and 30 ml of toluene were added to a 100 ml round bottom flask, then the temperature was raised to 130°C and stirred for 24 hours.
이후 감압 조건에서 메탄올을 제거하며 2시간 추가 교반하고, 상온으로 냉각 후 여과하여 흰색 고체를 얻었다. Afterwards, methanol was removed under reduced pressure and stirred for an additional 2 hours, cooled to room temperature, and filtered to obtain a white solid.
상기 얻어진 흰색 고체를 톨루엔 리슬러리(re-slurry)를 통해 정제된 실란 첨가제 1[1-(클로로메틸)-2,8,9-트리옥사-5-아자-1-실라바이시클로[3,3,3]운데칸-3-온] 9.9g을 합성하였다.The obtained white solid was purified through toluene re-slurry with the silane additive 1[1-(chloromethyl)-2,8,9-trioxa-5-aza-1-silabicyclo[3,3. ,3]undecan-3-one] 9.9g was synthesized.
1H-NMR(CDCl3) 3.81(s, 2H), 3.78~3.71(m, 2H), 3.62~3.25(m, 2H), 3.05(s, 2H), 3.02~2.91(m, 4H) 1 H-NMR (CDCl 3 ) 3.81(s, 2H), 3.78~3.71(m, 2H), 3.62~3.25(m, 2H), 3.05(s, 2H), 3.02~2.91(m, 4H)
합성예 2Synthesis Example 2
100㎖ 둥근바닥 플라스크에 2-히드록시-N,N-비스(2-히드록시에틸)아세트아마이드 16.3g과 메틸트리메톡시실란 13.6g 및 톨루엔 30㎖를 넣은 후 130℃로 승온하여 24시간 교반하였다. Add 16.3 g of 2-hydroxy-N,N-bis(2-hydroxyethyl)acetamide, 13.6 g of methyltrimethoxysilane, and 30 mL of toluene to a 100 mL round bottom flask, then raise the temperature to 130°C and stir for 24 hours. did.
이후 감압 조건에서 메탄올을 제거하며 2시간 추가 교반하고, 상온으로 냉각 후 여과하여 흰색 고체를 얻었다. Afterwards, methanol was removed under reduced pressure and stirred for an additional 2 hours, cooled to room temperature, and filtered to obtain a white solid.
상기 얻어진 흰색 고체를 톨루엔 리슬러리를 통해 정제된 실란 첨가제 2[1-메틸-2,8,9-트리옥사-5-아자-1-실라바이시클로[3,3,3]운데칸-4-온] 8.3g을 합성하였다.The obtained white solid was treated with the silane additive 2[1-methyl-2,8,9-trioxa-5-aza-1-silabicyclo[3,3,3]undecan-4- purified through toluene reslurry. On] 8.3g was synthesized.
1H-NMR(CDCl3) 4.46(s, 2H), 3.92~3.86(m, 2H), 3.83~3.76(m, 2H), 3.67~3.59(m, 2H), 3.45~3.35(m, 2H), 0.47(s, 3H) 1 H-NMR (CDCl 3 ) 4.46 (s, 2H), 3.92 to 3.86 (m, 2H), 3.83 to 3.76 (m, 2H), 3.67 to 3.59 (m, 2H), 3.45 to 3.35 (m, 2H) , 0.47(s, 3H)
합성예 3Synthesis Example 3
100㎖ 둥근바닥 플라스크에 2-[비스(2-히드록시에틸)아미노]-2-옥소-아세트산 17.7g과 메틸트리메톡시실란 13.6g, 톨루엔 30㎖를 넣은 후 130℃로 승온하여 24시간 교반하였다. Add 17.7 g of 2-[bis(2-hydroxyethyl)amino]-2-oxo-acetic acid, 13.6 g of methyltrimethoxysilane, and 30 ml of toluene to a 100 ml round bottom flask, then raise the temperature to 130°C and stir for 24 hours. did.
이후 감압 조건에서 메탄올을 제거하며 2시간 추가 교반하고, 상온으로 냉각 후 여과하여 흰색 고체를 얻었다. Afterwards, methanol was removed under reduced pressure and stirred for an additional 2 hours, cooled to room temperature, and filtered to obtain a white solid.
상기 얻어진 흰색 고체를 톨루엔 리슬러리를 통해 정제된 실란 첨가제 3[1-메틸-2,8,9-트리옥사-5-아자-1-실라바이시클로[3,3,3]운데칸-3,4-디온] 4.9g을 합성하였다.The obtained white solid was mixed with the silane additive 3[1-methyl-2,8,9-trioxa-5-aza-1-silabicyclo[3,3,3]undecane-3, purified through toluene reslurry. 4-dione] 4.9g was synthesized.
1H-NMR(CDCl3) 4.22~4.12(m, 2H), 4.10~4.02(m, 1H), 4.00~3.94(m, 1H), 3.94~9.83(m, 2H), 3.70~3.61(m, 1H), 3.31~3.18(m, 1H), 0.45(s, 3H) 1H -NMR (CDCl 3 ) 4.22~4.12(m, 2H), 4.10~4.02(m, 1H), 4.00~3.94(m, 1H), 3.94~9.83(m, 2H), 3.70~3.61(m, 1H), 3.31~3.18(m, 1H), 0.45(s, 3H)
합성예 4Synthesis Example 4
100㎖ 둥근바닥 플라스크에 N-(카르복시메틸)-N-(2-히드록시에틸)글리신 17.7g과 비닐트리메톡시실란 14.8g, 톨루엔 30㎖를 넣은 후 130℃로 승온하여 24시간 교반하였다. 17.7 g of N-(carboxymethyl)-N-(2-hydroxyethyl)glycine, 14.8 g of vinyltrimethoxysilane, and 30 ml of toluene were added to a 100 ml round bottom flask, then the temperature was raised to 130°C and stirred for 24 hours.
이후 감압 조건에서 메탄올을 제거하며 2시간 추가 교반하고, 상온으로 냉각 후 여과하여 흰색 고체를 얻었다. Afterwards, methanol was removed under reduced pressure and stirred for an additional 2 hours, cooled to room temperature, and filtered to obtain a white solid.
상기 얻어진 흰색 고체를 톨루엔 리슬러리를 통해 정제된 실란 첨가제 4[1-에테닐-2,8,9-트리옥사-5-아자-1-실라바이시클로[3,3,3]운데칸-3,7-디온] 7.8g을 합성하였다.The obtained white solid was purified through toluene reslurry with the silane additive 4[1-ethenyl-2,8,9-trioxa-5-aza-1-silabicyclo[3,3,3]undecane-3. ,7-dione] 7.8g was synthesized.
1H-NMR(CDCl3) 7.65(dd, J1=9.5 Hz, J2=16.0 Hz, 1H), 5.13(dd, J1=9.5 Hz, J2=1.6 Hz, 1H), 5.01(dd, J1=16.0 Hz, J2=1.6 Hz, 1H), 3.95(d, J=18.1 Hz, 1H), 3.90~3.76(m, 2H), 3.66(d, J=17.0 Hz, 1H), 3.53(d, d, J=17.0 Hz, 1H), 3.31~3.18(m, 1H), 3.04~2.95(m, 1H), 2.97~2.83(m, 1H) 1 H-NMR(CDCl 3 ) 7.65(dd, J1= 9.5 Hz, J2= 16.0 Hz, 1H), 5.13(dd, J1= 9.5 Hz, J2= 1.6 Hz, 1H), 5.01(dd, J1= 16.0 Hz, J2= 1.6 Hz, 1H), 3.95(d, J= 18.1 Hz, 1H), 3.90~3.76(m, 2H), 3.66(d, J= 17.0 Hz, 1H), 3.53(d, d, J= 17.0 Hz, 1H), 3.31~3.18(m, 1H), 3.04~2.95(m, 1H), 2.97~2.83(m, 1H)
합성예 5Synthesis Example 5
100㎖ 둥근바닥 플라스크에 N,N-비스(카르복시메틸)글리신 19.1g과 메틸트리메톡시실란 13.6g, 톨루엔 30㎖를 넣은 후 130℃로 승온하여 24시간 교반하였다. After putting 19.1 g of N,N -bis(carboxymethyl)glycine, 13.6 g of methyltrimethoxysilane, and 30 ml of toluene in a 100 ml round bottom flask, the mixture was heated to 130°C and stirred for 24 hours.
이후 감압 조건에서 메탄올을 제거하며 2시간 추가 교반하고, 상온으로 냉각 후 여과하여 흰색 고체를 얻었다. Afterwards, methanol was removed under reduced pressure and stirred for an additional 2 hours, cooled to room temperature, and filtered to obtain a white solid.
상기 얻어진 흰색 고체를 톨루엔 리슬러리를 통해 정제된 실란 첨가제 5[1-메틸-2,8,9-트리옥사-5-아자-1-실라바이시클로[3,3,3]운데칸-3,7,10-트리온] 2.4g을 합성하였다.The obtained white solid was mixed with the silane additive 5[1-methyl-2,8,9-trioxa-5-aza-1-silabicyclo[3,3,3]undecane-3, purified through toluene reslurry. 7,10-trione] 2.4g was synthesized.
1H-NMR(CDCl3) 3.86~3.7(m, 6H), 0.56(s, 3H) 1 H-NMR(CDCl 3 ) 3.86~3.7(m, 6H), 0.56(s, 3H)
실시예 1Example 1
반도체 웨이퍼 위에 500Å(옹스트롱)의 두께로 증착된 실리콘 산화막(SiOx)과 5000Å 두께의 실리콘 질화막(SiN)이 형성된 기판을 준비하였다.A substrate with a silicon oxide film (SiOx) deposited to a thickness of 500 Å (angstrom) and a silicon nitride film (SiN) to a thickness of 5000 Å were formed on a semiconductor wafer.
표 1에 나타낸 것과 같이, 85% 인산 99.5중량%, 실란 첨가제 1을 0.5중량% 첨가하여 100중량%가 되도록 혼합하여 식각 조성물을 제조하였다. As shown in Table 1, an etching composition was prepared by adding 99.5% by weight of 85% phosphoric acid and 0.5% by weight of silane additive 1 and mixing to 100% by weight.
상기 식각 조성물을 둥근 플라스크에 넣고 60분간 가열하여 158℃로 상승시킨 뒤, 상기 실리콘 웨이퍼를 720초, 6000초 동안 침지시켜 식각공정을 수행하였다. The etching composition was placed in a round flask and heated for 60 minutes to raise the temperature to 158°C, and then the silicon wafer was immersed for 720 seconds and 6000 seconds to perform an etching process.
패턴이 형성된 실리콘 웨이퍼 표면을 선택적으로 식각한 후, 실리콘 산화막과 질화막의 식각 전/후 막질의 두께를 박막 두께 측정 장비(NANO VIEW, SEMG-1000)인 엘립소미트리를 이용하여 측정하고, 이로부터 실리콘 산화막의 식각속도(SiN E/R, Å/min)와 질화막의 식각속도(SiN E/R, Å/min) 및 선택비를 계산하였다. 그 결과를 표 1에 나타내었다.After selectively etching the patterned silicon wafer surface, the thickness of the silicon oxide and nitride films before and after etching is measured using ellipsometry, a thin film thickness measurement equipment (NANO VIEW, SEMG-1000), and from this, The etch rate of the silicon oxide film (SiN E/R, Å/min) and the etch rate of the nitride film (SiN E/R, Å/min) and selectivity were calculated. The results are shown in Table 1.
선택비는 산화막 식각 속도에 대한 질화막 식각 속도의 비를 나타내며, 초기값과 식각 처리 후의 막 두께의 차이를 식각 시간(분)으로 나누어 산출한 값이다.The selectivity ratio represents the ratio of the nitride film etching rate to the oxide film etching rate, and is a value calculated by dividing the difference between the initial value and the film thickness after etching by the etching time (minutes).
실시예 2 내지 5Examples 2 to 5
실란 첨가제 2 내지 5를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 식각공정을 수행하여, 실리콘 산화막의 식각속도와 질화막의 식각속도 및 선택비를 계산하고, 그 결과를 표 1에 나타내었다.The etching process was performed in the same manner as in Example 1 except that silane additives 2 to 5 were used, and the etching rate of the silicon oxide film and the etching rate and selectivity of the nitride film were calculated, and the results are shown in Table 1.
비교예 1Comparative Example 1
첨가제로서 3-Aminopropylsilanetriol을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 식각공정을 수행하여, 실리콘 산화막의 식각속도와 질화막의 식각속도 및 선택비를 계산하고, 그 결과를 표 1에 나타내었다.The etching process was performed in the same manner as in Example 1 except that 3-Aminopropylsilanetriol was used as an additive, and the etching rate of the silicon oxide film and the etching rate and selectivity of the nitride film were calculated, and the results are shown in Table 1.
(℃)process temperature
(℃)
(Å/min)SiN E/R
(Å/min)
(Å/min)SiO E/R
(Å/min)
표 1로부터 알 수 있는 바와 같이, 식각 조성물의 첨가제로서 실란 첨가제 1 내지 5의 고리모양의 실란 화합물을 식각 조성물에 적용하였을 때, 비교예 1에 비하여 식각 선택비가 현저하게 높게 나타남을 알 수 있다. 또한, 실리콘 질화막의 식각 속도(SiN E/R)의 면에서도, 비교예 1의 식각 조성물에 비해 현저히 우수한 효과를 나타내어 실리콘 질화막의 식각 공정에 최적화된 식각 조성물을 제공할 수 있음을 확인하였다. As can be seen from Table 1, when the cyclic silane compounds of silane additives 1 to 5 were applied to the etching composition as an additive to the etching composition, the etching selectivity was significantly higher than that of Comparative Example 1. In addition, in terms of the etching rate (SiN E/R) of the silicon nitride film, it showed a significantly superior effect compared to the etching composition of Comparative Example 1, confirming that an etching composition optimized for the etching process of the silicon nitride film can be provided.
이러한 결과로부터 본 발명에서 제안하는 실란 화합물을 첨가제로 사용하는 경우, 활성 실리콘계 구조 안정성이 비교예 1의 단사슬 구조의 실란화합물에 비하여 향상되는 결과를 제공함을 알 수 있었다. From these results, it was found that when the silane compound proposed in the present invention was used as an additive, the stability of the active silicon-based structure was improved compared to the short-chain silane compound of Comparative Example 1.
Claims (24)
[화학식 1]
상기 화학식 1에서,
R1 내지 R6는 독립적으로 수소, 하이드로카빌(hydrocarbyl) 또는 비-하이드로카빌(non-hydrocarbyl)이며, R1 내지 R6 중 적어도 하나가 옥소(oxo)이고,
Lp는 하이드로카빌렌이고, p는 0 또는 1이며,
A는 n가의 라디칼이고,
n은 1 내지 4의 정수이다.An etching composition comprising phosphoric acid and a silane compound represented by the following formula (1).
[Formula 1]
In Formula 1,
R 1 to R 6 are independently hydrogen, hydrocarbyl or non-hydrocarbyl, and at least one of R 1 to R 6 is oxo;
L p is hydrocarbylene, p is 0 or 1,
A is an n-valent radical,
n is an integer from 1 to 4.
여기서, R11 및 R12는 독립적으로 수소, C1-C20알킬, C1-C20아미노알킬 또는 CONH2이고, R13 내지 R17은 독립적으로 수소 또는 C1-C20알킬이며, L1은 C1-C20알킬렌이다.The method of claim 4, wherein the radical where the binding site is N is *-NR 11 R 12 , *-NR 13 -*, *-NR 14 CONR 15 -*, *-NR 16 CSNR 17 -* or Phosphorus etching composition.
Here, R 11 and R 12 are independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 aminoalkyl, or CONH 2 , R 13 to R 17 are independently hydrogen or C 1 -C 20 alkyl, L 1 is C 1 -C 20 alkylene.
여기서, R18 및 R19는 독립적으로, 수소, C1-C20알킬, C6-C20아릴, 또는 C1-C20알킬C1-C20알콕시이다.The method of claim 4, wherein the radical where the binding site is P is , , or Phosphorus etching composition.
Here, R 18 and R 19 are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or C 1 -C 20 alkylC 1 -C 20 alkoxy.
n은 1이며;
Lp는 C1-C5알킬렌이고, p는 0 또는 1이며,
A는 수소, 할로겐, 치환 또는 비치환된 C1-C20알킬, 치환 또는 비치환된 C1-C20알케닐, *-NH2, *-NH-(CH2)l-NH2, *-NH-CO-NH2, 또는 *-(CH2)m-C6H5이고;
l 및 m은 독립적으로 0 내지 10의 정수인 식각 조성물.According to paragraph 1,
n is 1;
L p is C 1 -C 5 alkylene, p is 0 or 1,
A is hydrogen, halogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkenyl, *-NH 2 , *-NH-(CH 2 ) l -NH 2 , * -NH-CO-NH 2 , or *-(CH 2 ) m -C 6 H 5 ;
l and m are independently integers from 0 to 10.
n은 2이며;
Lp는 C1-C5알킬렌이고, p는 0 또는 1이며,
A는 C1-C20알킬렌, *-NR13-*, *-NR14-CO-NR15-*, *-O-*, *-S-*, *-S-S-*, , 또는 이고,
R13 내지 R15, R18 및 R19는 독립적으로 수소, C1-C20알킬, C6-C20아릴, 또는 C1-C20알킬C1-C20알콕시인 식각 조성물.According to paragraph 1,
n is 2;
L p is C 1 -C 5 alkylene, p is 0 or 1,
A is C 1 -C 20 alkylene, *-NR 13 -*, *-NR 14 -CO-NR 15 -*, *-O-*, *-S-*, *-SS-*, , or ego,
R 13 to R 15 , R 18 and R 19 are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or C 1 -C 20 alkylC 1 -C 20 alkoxy.
n은 3이고,
Lp는 C1-C5알킬렌이고, p는 0 또는 1이며,
A는 또는 인 식각 조성물.According to paragraph 1,
n is 3,
L p is C 1 -C 5 alkylene, p is 0 or 1,
A is or Phosphorus etching composition.
n은 4이고;
Lp는 C1-C5알킬렌이고, p는 0 또는 1이며;
A는 이고;
여기서 L1은 C1-C10알킬렌인, 식각 조성물.According to paragraph 1,
n is 4;
L p is C 1 -C 5 alkylene, p is 0 or 1;
A is ego;
wherein L 1 is C 1 -C 10 alkylene.
(1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17)The etching composition according to claim 1, wherein the silane compound is selected from the following structures.
(One), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17)
[화학식 2]
상기 화학식 2에서, R51 내지 R54는 서로 독립적으로 수소, C1-C20의 하이드로카빌, C1-C20의 헤테로하이드로카빌이고, R51 내지 R54는 각각 존재하거나 또는 2개 이상이 헤테로 원소를 통해 서로 연결된 고리형태이다.The etching composition of claim 15, further comprising a silane compound represented by the following formula (2).
[Formula 2]
In Formula 2, R 51 to R 54 are independently hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 heterohydrocarbyl, and R 51 to R 54 are each present or two or more It is in the form of rings connected to each other through hetero elements.
[화학식 1]
상기 화학식 1에서,
R1 및 R2는 옥소이고, R3 내지 R6는 독립적으로 수소, 하이드로카빌 또는 비-하이드로카빌이고,
Lp는 C1-C5알킬렌이고, p는 0 또는 1이며,
A는 수소, 할로겐, 치환 또는 비치환된 C1-C20알킬, 치환 또는 비치환된 C1-C20알케닐, *-NH2, *-NH-(CH2)l-NH2, *-NH-CO-NH2, 또는 *-(CH2)m-C6H5이고,
l 또는 m은 독립적으로 0 내지 10의 정수며,
n은 1 내지 4의 정수이다.A silane compound represented by the following formula (1).
[Formula 1]
In Formula 1,
R 1 and R 2 are oxo, R 3 to R 6 are independently hydrogen, hydrocarbyl or non-hydrocarbyl,
Lp is C 1 -C 5 alkylene, p is 0 or 1,
A is hydrogen, halogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkenyl, *-NH 2 , *-NH-(CH 2 ) l -NH 2 , * -NH-CO-NH 2 , or *-(CH 2 ) m -C 6 H 5 ,
l or m is independently an integer from 0 to 10,
n is an integer from 1 to 4.
The silane compound according to claim 21, wherein Chemical Formula 1 is expressed by the following structure.
[화학식 1]
상기 화학식 1에서,
R1 내지 R6 중 적어도 하나는 옥소이고, 나머지는 독립적으로 수소, 하이드로카빌 또는 비-하이드로카빌이고,
Lp는 C1-C5알킬렌이고, p는 0 또는 1이며,
A는 C1-C20알킬렌, *-NR13-*, *-NR14-CO-NR15-*, *-O-*, *-S-*, *-S-S-*, , , , , , 또는 이고,
R13 내지 R15, R18 또는 R19는 독립적으로 수소, C1-C20알킬, C6-C20아릴, 또는 C1-C20알킬C1-C20알콕시이고, L1은 C1-C10알킬렌이며,
n은 2 내지 4의 정수이다.A silane compound represented by the following formula (1).
[Formula 1]
In Formula 1,
At least one of R 1 to R 6 is oxo, and the others are independently hydrogen, hydrocarbyl, or non-hydrocarbyl,
L p is C 1 -C 5 alkylene, p is 0 or 1,
A is C 1 -C 20 alkylene, *-NR 13 -*, *-NR 14 -CO-NR 15 -*, *-O-*, *-S-*, *-SS-*, , , , , , or ego,
R 13 to R 15 , R 18 or R 19 are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, or C 1 -C 20 alkylC 1 -C 20 alkoxy, and L 1 is C 1 -C 10 alkylene,
n is an integer from 2 to 4.
(6), (7), (8), (9), (10), (11), (12), (13),
(14), (15), (16), (17)The silane compound according to claim 23, wherein Formula 1 is expressed by any one of the following structures.
(6), (7), (8), (9), (10), (11), (12), (13),
(14), (15), (16), (17)
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| JP2008169157A (en) | 2007-01-12 | 2008-07-24 | Dow Corning Toray Co Ltd | Method for producing bis(silatranylalkyl)polysulfide or the like, and mixture of bis(silatranylalkyl)polysulfide or the like |
| JP2016044305A (en) | 2014-08-19 | 2016-04-04 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニーＴｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏｍｐａｎｙ | Bifunctionalized polymer |
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| JP2016044305A (en) | 2014-08-19 | 2016-04-04 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニーＴｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏｍｐａｎｙ | Bifunctionalized polymer |
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