WO2015142053A1 - 유기 게르마늄 아민 화합물 및 이를 이용한 박막 증착 방법 - Google Patents
유기 게르마늄 아민 화합물 및 이를 이용한 박막 증착 방법 Download PDFInfo
- Publication number
- WO2015142053A1 WO2015142053A1 PCT/KR2015/002628 KR2015002628W WO2015142053A1 WO 2015142053 A1 WO2015142053 A1 WO 2015142053A1 KR 2015002628 W KR2015002628 W KR 2015002628W WO 2015142053 A1 WO2015142053 A1 WO 2015142053A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- germanium
- carbon atoms
- substrate
- formula
- amine compound
- Prior art date
Links
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 99
- -1 germanium amine compound Chemical class 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000000151 deposition Methods 0.000 title description 24
- 239000010409 thin film Substances 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 24
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 24
- BIXHRBFZLLFBFL-UHFFFAOYSA-N germanium nitride Chemical compound N#[Ge]N([Ge]#N)[Ge]#N BIXHRBFZLLFBFL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 37
- 238000005137 deposition process Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 238000000231 atomic layer deposition Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 150000003974 aralkylamines Chemical group 0.000 claims description 6
- 125000005264 aryl amine group Chemical group 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000005265 dialkylamine group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- MOGRQVOVCATFGE-UHFFFAOYSA-N [Ge]=O.[Hf] Chemical compound [Ge]=O.[Hf] MOGRQVOVCATFGE-UHFFFAOYSA-N 0.000 claims description 3
- VLCVFPJBSMVPME-UHFFFAOYSA-N [Ge]=O.[Ti] Chemical compound [Ge]=O.[Ti] VLCVFPJBSMVPME-UHFFFAOYSA-N 0.000 claims description 3
- AZGSBPSKNYKLRH-UHFFFAOYSA-N [Ge]=O.[Zr] Chemical compound [Ge]=O.[Zr] AZGSBPSKNYKLRH-UHFFFAOYSA-N 0.000 claims description 3
- OFECSHURFOBOOE-UHFFFAOYSA-N [Hf].[Ge] Chemical compound [Hf].[Ge] OFECSHURFOBOOE-UHFFFAOYSA-N 0.000 claims description 3
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- ZPPUVHMHXRANPA-UHFFFAOYSA-N germanium titanium Chemical compound [Ti].[Ge] ZPPUVHMHXRANPA-UHFFFAOYSA-N 0.000 claims description 3
- KYXIMMOBOGDUFW-UHFFFAOYSA-N germanium zirconium Chemical compound [Ge].[Zr] KYXIMMOBOGDUFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 84
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000113 differential scanning calorimetry Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- FBGJJTQNZVNEQU-UHFFFAOYSA-N n,3-dimethylaniline Chemical compound CNC1=CC=CC(C)=C1 FBGJJTQNZVNEQU-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000007736 thin film deposition technique Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- MWVWWWNNSVBMGW-UHFFFAOYSA-N CN(C)C(C1=CC(N[Ge+2]C)=CC=C1)(N(C)C)N(C)C Chemical compound CN(C)C(C1=CC(N[Ge+2]C)=CC=C1)(N(C)C)N(C)C MWVWWWNNSVBMGW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000012686 silicon precursor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- CULSIAXQVSZNSV-UHFFFAOYSA-N germanium(4+) Chemical compound [Ge+4] CULSIAXQVSZNSV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- CLVJRAOPAJZEDS-UHFFFAOYSA-N C[Ge+2]NC1=CC=CC=C1.C(C)NCC.C(C)NCC.C(C)NCC Chemical compound C[Ge+2]NC1=CC=CC=C1.C(C)NCC.C(C)NCC.C(C)NCC CLVJRAOPAJZEDS-UHFFFAOYSA-N 0.000 description 1
- YXQACALMTLNJNL-UHFFFAOYSA-N C[Ge]NC1=CC=CC=C1.CNC.CNC.CNC Chemical compound C[Ge]NC1=CC=CC=C1.CNC.CNC.CNC YXQACALMTLNJNL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 0 Cc(c(*)c1*)c(*)c(*)c1N(*)[Ge](C)(I)I Chemical compound Cc(c(*)c1*)c(*)c(*)c1N(*)[Ge](C)(I)I 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
-
- 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
- C07F7/30—Germanium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/28—Deposition of only one other non-metal element
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C23C16/303—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02189—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
Definitions
- the present invention relates to an organic germanium amine compound and a thin film deposition method using the same. More specifically, the present invention efficiently forms a germanium-containing thin film having useful properties that can be used as a passivation layer, an interlayer insulating film, or a capacitor dielectric layer, such as germanium oxide film, metal germanium oxide film, germanium nitride film, etc. in the manufacture of semiconductor devices.
- the present invention relates to an organic germanium amine compound and a thin film deposition method using the same.
- silicon-containing thin films such as silicon films, silicon nitride films, silicon carbide nitride films, silicon oxide films, and silicon oxynitride films play a very important role in the semiconductor manufacturing process.
- the silicon oxide film and the silicon nitride film play an important role as a passivation layer, an interlayer insulating film, or a capacitor dielectric layer.
- Chain precursor aminosilane type silicon precursors which are widely used at present, have a high molecular weight but a low boiling point, and are used for substructures (hereinafter, simply referred to as 'substructures') such as silicon oxide films, silicon nitride films or various metal wiring films. Due to the low affinity and bonding strength, the deposition rate of the low silicon film is low, the porosity of the deposited silicon film is high, the density of the silicon film is low, and the deposition uniformity of the deposited silicon film is low.
- a silicon precursor and a nitrogen source gas are used.
- a high process temperature such as 500 to 700 ° C. is required, which may adversely affect the highly integrated device, and the step coverage may not be good.
- one object of the present invention is to improve the problems of the prior art in the manufacturing process of the semiconductor device is high boiling point and good thermal stability, excellent affinity and bonding strength to the underlying structure, excellent thin film properties, thickness uniformity
- the present invention provides a new type of organic germanium amine compound having germanium as a central atom, which can efficiently form a germanium-containing film having step coverage.
- Another object of the present invention is to provide a film forming method for forming a germanium-containing film having excellent thin film properties, thickness uniformity, and step coverage by using the above-described organic germanium amine compound as a precursor.
- an aspect of the present invention provides an organic germanium amine compound represented by Formula 1 below:
- L 1 , L 2 , L 3, and L 4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
- the compound of Formula 1 may be represented by the following formula 2:
- L 2 , L 3 and L 4 are as defined in claim 1, R 1, R 2 , R 3 , R 4 , R 5 , R 6 are each independently a hydrogen atom, carbon atoms 1 to An alkyl group of 10, an aryl group of 6 to 12 carbon atoms, an aralkyl group of 7 to 13 carbon atoms, and an alkylsilyl group of 2 to 10 carbon atoms.
- the compound of Formula 2 may be represented by the following formula 3:
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms
- R 7 , R 8, and R 9 are each independently A hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkylamine group of 1 to 10 carbon atoms, a dialkylamine group of 1 to 10 carbon atoms, an arylamine group of 6 to 12 carbon atoms, or 7 to 10 carbon atoms 13 aralkyl amine group, a C3-C10 cyclic amine group, a C3-C10 heterocyclic amine group, or a C2-C10 alkyl silylamine group.
- the compound of Formula 3 may be represented by the following formula (4):
- the compound of Formula 3 may be represented by the following formula (5):
- the compound of Formula 3 may be represented by the following formula 6:
- a method of forming a film comprising forming a germanium-containing film on a substrate by a deposition process using the organic germanium amine compound according to one aspect of the present invention as a precursor.
- the deposition process is an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, for example, metal organic chemical vapor deposition (MOCVD). ) Process.
- ALD atomic layer deposition
- CVD chemical vapor deposition
- MOCVD metal organic chemical vapor deposition
- the deposition deposition process may be carried out at 50 to 500 °C.
- thermal energy, plasma, or electrical bias may be applied to the substrate during the deposition process.
- the organic germanium amine compound is mixed with at least one carrier gas or diluent gas selected from argon (Ar), nitrogen (N 2 ), helium (He), and hydrogen (H 2 )
- carrier gas or diluent gas selected from argon (Ar), nitrogen (N 2 ), helium (He), and hydrogen (H 2 )
- the organic germanium amine compound is mixed with one or more reaction gases selected from water vapor (H 2 O), oxygen (O 2 ) and ozone (O 3 ) and transferred onto the substrate or the The reaction gas may be transferred onto the substrate separately from the organic germanium amine compound to perform a deposition process.
- the germanium-containing film formed on the substrate includes germanium oxide (Ge x O y ), hafnium germanium oxide (Hf x Ge y O z ), zirconium germanium oxide (Zr x Ge y O z ), and titanium germanium oxide (Ti x Ge y O z ) may be a germanium oxide film or a metal germanium oxide film including at least one material selected from materials.
- the organic germanium amine compound is mixed with at least one reaction gas selected from ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ) and nitrogen (N 2 ) plasma
- the substrate may be transferred onto the substrate, or the reaction gas may be transferred onto the substrate separately from the organic germanium amine compound to perform a deposition process.
- the germanium-containing film formed on the substrate is made of germanium nitride (Ge x N y ), hafnium germanium nitride (Hf x Ge y N z ), zirconium germanium nitride (Zr x Ge y N z ), and titanium germanium nitride ( Ti x Ge y N z ) may be a germanium nitride film or a metal germanium nitride film including at least one material selected from materials.
- the deposition process for example,
- the method may include forming a germanium-containing film on the substrate by decomposing the organic germanium amine compound by applying thermal energy, plasma, or electrical bias to the substrate.
- the organic germanium amine compound according to one aspect of the present invention is present in a liquid state at room temperature and has a small boiling point but high boiling point and excellent thermal stability.
- the compound has a decomposition temperature similar to that of a metal precursor compound, for example, a Zr compound, which serves as a source of the metal when forming a metal germanium composite film, for example, window) can be narrowed.
- the present organic germanium amine compound also exhibits strong affinity with silicon substrates and metal atoms because it contains nitrogen atoms and germanium atoms having unshared electron pairs in one molecular structure.
- the compound according to an aspect of the present invention when used in a deposition process of a germanium oxide film, a germanium nitride film, a metal germanium oxide film, or a metal germanium nitride film, the following effects can be achieved.
- the deposition rate, deposition density, and deposition uniformity, that is, step coverage of the germanium-containing film can be improved because many molecules per unit area of the substructure are adsorbed in the deposition process performed at a high temperature.
- the organic germanium amine compound according to an aspect of the present invention can be efficiently applied to a semiconductor manufacturing process for depositing a germanium-containing film using an organometallic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD).
- MOCVD organometallic chemical vapor deposition
- ALD atomic layer deposition
- a passivation layer such as a germanium oxide film, a germanium nitride film, a metal germanium oxide film, or a metal germanium nitride film, an interlayer insulating film, or a capacitor dielectric layer may be used in manufacturing a semiconductor device. It is possible to efficiently form a germanium containing film having useful properties that can be used.
- FIG. 1 summarizes the DSC heat curves and TGA heat curves obtained in a test for tris (dimethylamine) methylanilino germanium (IV) obtained in Example 1.
- FIG. 1 summarizes the DSC heat curves and TGA heat curves obtained in a test for tris (dimethylamine) methylanilino germanium (IV) obtained in Example 1.
- FIG. 2 is a synthesis of the DSC and TGA heat curves obtained in the test for tris (dimethylamino) methyl-m-toludinoino germanium (IV) obtained in Example 3.
- FIG. 2 is a synthesis of the DSC and TGA heat curves obtained in the test for tris (dimethylamino) methyl-m-toludinoino germanium (IV) obtained in Example 3.
- FIG. 3 shows the deposition results obtained in a test on tris (dimethylamine) methylanilino germanium (IV) obtained in Experimental Example 1.
- organic germanium amine compound according to one aspect of the present invention is represented by the following formula (1):
- L 1 , L 2 , L 3, and L 4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
- Group IV elements C, Si, and Ge each have a band gap of 5.5 eV, 1.11 eV, and 0.67 eV.
- the band gap refers to the energy difference between the lowest energy level in the conduction band without electrons in the highest energy state in the valence band where electrons exist in the insulator or semiconductor.
- a small band gap is a good semiconductor material because it can transfer current with a small voltage.
- the compound represented by Chemical Formula 1 is a new type of precursor having a small band gap of germanium as a central atom. In particular, the compound represented by Formula 1 exists in a liquid state at room temperature and has a small boiling point but high boiling point and excellent thermal stability.
- this compound has a decomposition temperature similar to that of a metal precursor compound, for example, a Zr compound, which serves as a source of the metal, for example, when forming a metal germanium composite film, thereby narrowing the temperature window in the deposition process.
- a metal precursor compound for example, a Zr compound
- the compounds also exhibit strong affinity with silicon substrates and metal atoms because they contain nitrogen atoms and germanium atoms with unshared electron pairs in one molecular structure. Therefore, when the compound according to an aspect of the present invention is used in the deposition process of the germanium-containing film, many molecules per unit area of the substructure are adsorbed, so that the deposition rate, deposition density, and deposition uniformity of the germanium-containing film may be improved. .
- the adhesion to the underlying structure is large, so that the deposition rate, the deposition density, and the deposition uniformity of the germanium-containing film may be further improved.
- the compound of Formula 1 may be a compound represented by the following Formula 2:
- L 2 , L 3 and L 4 are as defined in claim 1, R 1, R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, carbon number 1 It is selected from an alkyl group of 10 to 10, an aryl group of 6 to 12 carbon atoms, an aralkyl group of 7 to 13 carbon atoms, and an alkylsilyl group of 2 to 10 carbon atoms.
- the compound of Formula 2 may be a compound represented by the following formula (3):
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms
- R 7 , R 8, and R 9 are each independently A hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkylamine group of 1 to 10 carbon atoms, a dialkylamine group of 1 to 10 carbon atoms, an arylamine group of 6 to 12 carbon atoms, or 7 to 10 carbon atoms 13 aralkyl amine group, a C3-C10 cyclic amine group, a C3-C10 heterocyclic amine group, or a C2-C10 alkyl silylamine group.
- Specific examples of the compound of Formula 3 may be an organic germanium amine compound represented by Formula 4, 5, or 6:
- the preparation method of the compounds of Formulas 1 to 6 according to one aspect of the present invention is not particularly limited and may be prepared by various methods.
- the compound of formula 4 may be prepared by, for example, Scheme 1. Referring to Scheme 1 below, the resultant obtained by the one-step substitution reaction of tetrachlorogermanium and N-methylaniline, a secondary amine compound, with a dimethylamine is obtained to obtain a compound represented by the formula (4). Can be.
- the compound of Formula 6 may be obtained by using N-methyl-m-toluidine instead of N-methylaniline in the one-step substitution reaction of Scheme 1.
- the compound of formula 5 may be prepared by, for example, Scheme 2.
- Scheme 2 the resultant obtained by the one-step substitution reaction of tetrachlorogermanium and N-methylaniline, a secondary amine compound, with a diethylamine is a compound represented by the formula (5) You can get it.
- the one-step substitution reaction in the chemical reactions according to Schemes 1 and 2 may be carried out in a nonpolar solvent such as pentane, hexane or benzene, or a polar solvent such as diethyl ether, tetrahydrofuran (THF) or methylal.
- the one-step substitution reaction is typically carried out at a reaction temperature of 0 to 30 ° C., preferably at a reaction temperature of 0 to 20 ° C. for about 1 to about 100 hours, preferably about 3 to about 72 hours.
- the two-step substitution reaction can be carried out in a nonpolar solvent such as pentane, hexane or benzene or a polar solvent such as diethyl ether, tetrahydrofuran or methylal.
- the two stage substitution reaction typically proceeds for about 6 to about 50 hours, preferably about 6 to about 20 hours, at a reaction temperature of 0 to 30 ° C, preferably 0 to 10 ° C.
- the amount of the reaction solvent used in the first and second stage substitution reactions in the chemical reactions according to Schemes 1 to 3 is about 10 to 50% by weight, preferably about 20 to 40% by weight. It is preferable that the range to be.
- Triethylamine (TEA) or trimethylamine (TMA) may be preferably used as the tertiary amine to capture hydrochloric acid issued in the first and second stage substitution reactions.
- a film forming method according to another aspect of the present invention is a film forming method comprising forming a germanium-containing film on a substrate by a deposition process using an organic germanium amine compound according to one aspect of the present invention.
- the deposition process may be an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, for example, an organic metal deposition chemical vapor deposition (MOCVD) process.
- ALD atomic layer deposition
- CVD chemical vapor deposition
- MOCVD organic metal deposition chemical vapor deposition
- the deposition deposition process may be carried out at 50 to 500 °C.
- the organic germanium amine compound is mixed with at least one carrier gas or diluent gas selected from argon (Ar), nitrogen (N 2), helium (He), and hydrogen (H 2) to be transported onto the substrate and deposited.
- carrier gas or diluent gas selected from argon (Ar), nitrogen (N 2), helium (He), and hydrogen (H 2) to be transported onto the substrate and deposited.
- the process can be carried out.
- the germanium-containing film formed on the substrate may be a germanium film.
- a Ge seed layer may be deposited on a substrate by using the organic germanium amine compound according to the present invention as a precursor, and the method using the Ge seed layer uses a conventional polysilicon seed layer.
- the problem of the method can be improved a lot. That is, the Ge seed layer using the organic germanium amine compound according to the present invention has a problem of surface roughness of the polysilicon during the thin polysilicon deposition process and voids in the polysilicon film during the polysilicon gap fill process. It is expected to be able to improve a lot of problems.
- the organic germanium amine compound may be mixed with at least one reaction gas selected from water vapor (H 2 O), oxygen (O 2), and ozone (O 3) to be transferred onto the substrate, or the reaction gas may be transferred to the organic germanium amine compound.
- the deposition process may be performed by transferring onto the substrate.
- the germanium-containing film formed on the substrate may include germanium oxide (Ge x O y ), hafnium germanium oxide (Hf x Ge y O z ), zirconium germanium oxide (Zr x Ge y O z ), and titanium germanium oxide ( Ti x Ge y O z ) may be a germanium oxide film or a metal germanium oxide film including at least one material selected from the group.
- the organic germanium amine compound is mixed with at least one reactive gas selected from ammonia (NH 3), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ) and nitrogen (N 2 ) plasma to be transported onto the substrate.
- the reaction gas may be transferred onto the substrate separately from the organic germanium amine compound to perform a deposition process.
- the germanium-containing film formed on the substrate is made of germanium nitride (Ge x N y ), hafnium germanium nitride (Hf x Ge y N z ), zirconium germanium nitride (Zr x Ge y N z ), and titanium germanium nitride ( Ti x Ge y N z ) may be a germanium nitride film or a metal germanium nitride film including at least one material selected from materials.
- the germanium oxide film, the metal germanium oxide film, the germanium nitride film, or the metal germanium nitride film is useful as a dielectric film when forming a capacitor during a DRAM device and a phase-change random access memory (PRAM) device manufacturing process. Can be used.
- the organic germanium amine compound When the organic germanium amine compound is transferred onto a substrate in the specific deposition process, for example, the organic germanium amine compound may be bubbling, vapor phase, mass flow controller, or direct liquid injection. Direct liquid injection (DLI) or liquid transfer method in which the compound is dissolved in organic solvents and transported can be transferred onto a substrate and used for thin film deposition. In this case, thermal energy, plasma, or electrical bias may be applied to the substrate during the deposition process to increase deposition efficiency.
- the deposition process may include, for example, heating the substrate to a temperature of 50 ° C. to 500 ° C. under a vacuum, active or inert atmosphere; Introducing the organic germanium amine compound heated to a temperature of 20 ° C. to 100 ° C.
- the organic germanium amine precursor compound may provide a time of less than 1 minute as a time to form a layer on the substrate.
- Excess organic germanium amine precursor compound that is not adsorbed on the substrate is preferably removed using one or more inert gases such as argon (Ar), nitrogen (N 2 ) and helium (He). Less than one minute may be provided as the time to remove excess precursor.
- one or more inert gases such as argon (Ar), nitrogen (N 2 ) and helium (He), may be introduced into the chamber in less than one minute to remove excess reactant gases and by-products. have.
- the organic germanium amine compound according to the present invention is a liquid at room temperature, has high thermal stability, high boiling point and high volatility, and thus is used as a precursor in a CVD process or an ALD process in manufacturing a semiconductor device, such as germanium oxide film, germanium nitride film, and metal germanium.
- a germanium-containing film having useful properties that can be used as a passivation layer, an interlayer insulating film, or a capacitor dielectric layer, such as an oxide film or a metal germanium nitride film, can be efficiently formed.
- N-BuLi and DMA in the second flask were maintained at an internal temperature of 500 ml branched first flask containing GeCl 4 , TEA, and N-methyl-m-toluidine.
- the dissolved hexane solution was slowly added into the first flask.
- lithium salts were generated.
- dissolved was added completely, the internal temperature of the 1st flask was heated up to 30 degreeC, and it stirred for about 15 hours further. After the reaction was completed, the mixture was filtered under reduced pressure to completely remove the salt. Fractional distillation under reduced pressure can yield a pale yellow product (9 g, 90%).
- DSC Differential Scanning Calorimetry
- TGA Thermogravimetric Test for Tris (dimethylamine) methylanilino germanium (IV) and Tris (dimethylamino) methyl-m-toluidino germanium (IV) obtained in Examples 1 and 3 Analytical (TGA) tests were conducted together.
- DSC test was carried out in the differential scanning calorimetry mode of the thermal analyzer (manufacturer: TA Instruments, model name: TA-Q 600) to measure the thermal stability and pyrolysis temperature, TGA test to determine the residual amount (residue)
- the thermal analyzer was run in thermogravimetric analysis mode for measurement.
- the thermal analysis test conditions were as follows.
- Transport gas argon (ar) gas
- Heating profile Heat from 30 ° C. to 500 ° C. at a rate of 10 ° C./min.
- the pyrolysis temperature was determined at the point where the amount of heat flow decreased and then suddenly rose in the DSC thermogram of FIGS. 1 and 2 described below.
- FIG. 1 summarizes the DSC heat curves and TGA heat curves obtained in a test for tris (dimethylamine) methylanilino germanium (IV) obtained in Example 1.
- FIG. 1 the heat curve indicated by the thick solid line is the result obtained by the DSC test, and the heat curve indicated by the dotted line is the result obtained by the TGA test.
- the thermal decomposition temperature of tris (dimethylamine) methylanilino germanium (IV) was about 219.95 ° C., and the residual amount was about 1.07% based on the initial weight.
- FIG. 2 is a synthesis of DSC and TGA heat curves obtained in a test for tris (dimethylamino) methyl-m-toludinoino germanium (IV) obtained in Example 3.
- FIG. 2 the heat curve indicated by the thick solid line is the result obtained by the DSC test, and the heat curve indicated by the dotted line is the result obtained by the TGA test.
- the thermal decomposition temperature of tris (dimethylamino) methyl-m-toluidino germanium (IV) was about 233.04 ° C. and the amount of residual components was about 0.97% based on the initial weight, which was very excellent in thermal stability.
- Film formation evaluation by an Atomic layer deposition (ALD) process was performed using the tris (dimethylamine) methylanilino germanium (IV) precursor prepared in Example 1.
- Argon an inert gas, was used for purge and precursor transfer purposes. Injecting the precursor, argon, plasma and argon into one cycle, and deposition was performed on a SiO 2 deposited thin film formed on a P-type Si (100) wafer.
- the ALD process may be performed at 250 ° C. to 350 ° C. using tris (dimethylamine) methylanilino germanium (IV), and the deposition results are shown in FIG. 3.
- the germanium oxide film could be grown to a thickness of about 50 GPa.
- the tris (dimethylamine) methylanilino germanium (IV) precursor is a suitable candidate for depositing germanium oxide by atomic layer deposition.
- germanium-containing thin film having useful properties that can be used as a passivation layer, an interlayer insulating film, or a capacitor dielectric layer, such as germanium oxide film, metal germanium oxide film, germanium nitride film, etc. in the manufacture of semiconductor devices.
- a capacitor dielectric layer such as germanium oxide film, metal germanium oxide film, germanium nitride film, etc. in the manufacture of semiconductor devices.
- An organic germanium amine compound and a thin film deposition method using the same can be obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
Claims (17)
- 청구항 2에 있어서, 상기 화학식 2의 화합물은 하기 화학식 3으로 표시되는 것을 특징으로 하는 유기 게르마늄 아민 화합물:<화학식 3>상기 화학식 3에서, R1, R2, R3, R4, R5, R6는 각각 독립적으로 수소 원자, 탄소수 1 내지 10의 알킬기 중에서 선택되고, R7, R8 및 R9 는 각각 독립적으로 수소 원자, 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 12의 아릴기, 탄소수 1 내지 10의 알킬아민기, 탄소수 1 내지 10의 다이알킬아민기, 탄소수 6 내지 12의 아릴아민기, 탄소수 7 내지 13의 아랄킬아민기, 탄소수 3 내지 10의 사이클릭 아민기, 탄소수 3 내지 10의 헤테로사이클릭 아민기 또는 탄소수 2내지 10의 알킬실릴아민기 중에서 선택된다.
- 막 형성 방법으로서,청구항 1 내지 6 중 어느 한 항에 따른 유기 게르마늄 아민 화합물을 전구체로서 이용하는 증착 공정에 의하여 기판상에 게르마늄 함유막을 형성하는 단계를 포함하는 막 형성 방법.
- 청구항 7에 있어서, 상기 증착 공정은 원자층 증착(atomic layer deposition: ALD) 공정 또는 화학 증착(chemical vapor deposition: CVD) 공정인 것을 특징으로 하는 막 형성 방법.
- 청구항 7에 있어서, 상기 증착 공정이 50 내지 500℃에서 실시되는 것을 특징으로 하는 막 형성 방법.
- 청구항 7에 있어서, 상기 증착 공정 동안 상기 기판에 열에너지, 플라즈마, 또는 전기적 바이어스를 인가하는 것을 특징으로 하는 막 형성 방법.
- 청구항 7에 있어서, 상기 유기 게르마늄 아민 화합물을 아르곤(Ar), 질소(N2), 헬륨(He), 및 수소(H2) 중에서 선택된 1종 이상의 캐리어 가스 또는 희석 가스와 혼합하여 상기 기판상으로 이송하여 증착 공정을 실시하는 것을 특징으로 하는 막 형성 방법.
- 청구항 11에 있어서, 상기 기판상에 형성된 게르마늄 함유막은 게르마늄막인 것을 특징으로 하는 막 형성 방법.
- 청구항 7에 있어서, 상기 유기 게르마늄 아민 화합물을 수증기(H2O), 산소(O2) 및 오존(O3) 중에서 선택된 1종 이상의 반응 가스와 혼합하여 상기 기판상으로 이송하거나 또는 상기 반응 가스를 상기 유기 게르마늄 아민 화합물과 별도로 상기 기판상으로 이송하여 증착 공정을 실시하는 것을 특징으로 하는 막 형성 방법.
- 청구항 13에 있어서, 상기 기판상에 형성된 게르마늄 함유막은 게르마늄 산화물(GexOy), 하프늄 게르마늄 산화물(HfxGeyOz), 지르코늄 게르마늄 산화물(ZrxGeyOz), 및 티타늄 게르마늄 산화물(TixGeyOz)에서 선택된 적어도 1종의 물질을 포함하는 게르마늄 산화물막 또는 금속 게르마늄 산화물막인 것을 특징으로 하는 막 형성 방법.
- 청구항 14에 있어서, 상기 유기 게르마늄 아민 화합물을 암모니아(NH3), 히드라진(N2H4), 이산화질소(NO2) 및 질소(N2) 플라즈마 중에서 선택된 1종 이상의 반응 가스와 혼합하여 상기 기판 상으로 이송하거나 또는 상기 반응 가스를 상기 유기 게르마늄 아민 화합물과 별도로 상기 기판상으로 이송하여 증착 공정을 실시하는 것을 특징으로 하는 막 형성 방법.
- 청구항 15에 있어서, 상기 기판상에 형성된 게르마늄 함유막은 게르마늄 질화물(GexNy), 하프늄 게르마늄 질화물(HfxGeyNz), 지르코늄 게르마늄 질화물(ZrxGeyNz), 및 티타늄 게르마늄 질화물(TixGeyNz)에서 선택된 적어도 1종의 물질을 포함하는 게르마늄 질화물막 또는 금속 게르마늄 질화물막인 것을 특징으로 하는 막 형성 방법.
- 청구항 7에 있어서, 상기 증착 공정은,진공, 활성 또는 비활성 분위기 하에서 상기 기판을 50℃ 내지 500℃의 온도로 가열하는 단계;20℃ 내지 100℃의 온도로 가열된 상기 유기 게르마늄 아민 화합물을 상기 기판상에 도입하는 단계;상기 유기 게르마늄 아민 화합물을 상기 기판상에 흡착시켜 상기 유기 게르마늄 아민 화합물층을 상기 기판상에 형성하는 단계; 및상기 기판에 열에너지, 플라즈마, 또는 전기적 바이어스를 인가하여 상기 유기 게르마늄 아민 화합물을 분해함으로써 상기 기판상에 게르마늄 함유막을 형성하는 단계를 포함하는 것을 특징으로 하는 막 형성 방법.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580014038.7A CN106103456A (zh) | 2014-03-18 | 2015-03-18 | 有机锗胺化合物及用其沉积薄膜的方法 |
US15/126,876 US20170117142A1 (en) | 2014-03-18 | 2015-03-18 | Organic Germanium Amine Compound and Method for Depositing Thin Film Using the Same |
JP2016557652A JP2017511308A (ja) | 2014-03-18 | 2015-03-18 | 有機ゲルマニウムアミン化合物、及びそれを利用した薄膜蒸着方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2014-0031828 | 2014-03-18 | ||
KR20140031828 | 2014-03-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015142053A1 true WO2015142053A1 (ko) | 2015-09-24 |
Family
ID=54144942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2015/002628 WO2015142053A1 (ko) | 2014-03-18 | 2015-03-18 | 유기 게르마늄 아민 화합물 및 이를 이용한 박막 증착 방법 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20170117142A1 (ko) |
JP (1) | JP2017511308A (ko) |
KR (1) | KR101659610B1 (ko) |
CN (1) | CN106103456A (ko) |
WO (1) | WO2015142053A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019504509A (ja) * | 2015-11-19 | 2019-02-14 | ユージーンテック マテリアルズ カンパニー リミテッド | 有機4族化合物を含む前駆体造成物及びそれを利用した薄膜形成方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017086630A1 (ko) * | 2015-11-19 | 2017-05-26 | 주식회사 유진테크 머티리얼즈 | 유기 4족 화합물을 포함하는 전구체 조성물 및 이를 이용한 박막 형성 방법 |
WO2018111277A1 (en) * | 2016-12-15 | 2018-06-21 | Intel Corporation | P-dopant precursors for iii-v semiconductor devices |
CN107118230A (zh) * | 2017-06-26 | 2017-09-01 | 江苏南大光电材料股份有限公司 | 四(二甲氨基)锗的合成方法 |
US10522623B1 (en) * | 2018-08-15 | 2019-12-31 | Taiwan Semiconductor Manufacturing Co., Ltd. | Germanium nitride layers on semiconductor structures, and methods for forming the same |
US10964536B2 (en) * | 2019-02-06 | 2021-03-30 | Micron Technology, Inc. | Formation of an atomic layer of germanium in an opening of a substrate material having a high aspect ratio |
KR102366555B1 (ko) * | 2021-01-05 | 2022-02-23 | 주식회사 이지티엠 | 핵성장 지연을 이용한 영역 선택적 박막 형성 방법 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004025083A1 (de) * | 2004-05-21 | 2005-12-29 | Infineon Technologies Ag | Verfahren zum Herstellen eines Festkörperelektrolytmaterialbereichs für ein Speicherelement einer Festkörperelektrolytspeicherzelle |
KR20060074236A (ko) * | 2004-12-27 | 2006-07-03 | 삼성전자주식회사 | 게르마늄 전구체, 이를 이용하여 형성된 gst 박막,상기 박막의 제조 방법 및 상변화 메모리 소자 |
KR100695168B1 (ko) * | 2006-01-10 | 2007-03-14 | 삼성전자주식회사 | 상변화 물질 박막의 형성방법, 이를 이용한 상변화 메모리소자의 제조방법 |
JP2011086862A (ja) * | 2009-10-19 | 2011-04-28 | Central Glass Co Ltd | 非晶質半導体膜用オリゴメチルゲルマン化合物とこれを用いる成膜ガス |
KR20120118060A (ko) * | 2006-11-02 | 2012-10-25 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 금속 박막의 cvd/ald용으로 유용한 안티몬 및 게르마늄 착체 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4689969B2 (ja) * | 2003-04-05 | 2011-06-01 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | Iva族およびvia族化合物の調製 |
JP4954448B2 (ja) * | 2003-04-05 | 2012-06-13 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | 有機金属化合物 |
US7619093B2 (en) * | 2004-10-15 | 2009-11-17 | Praxair Technology, Inc. | Organometallic compounds and mixtures thereof |
KR100640620B1 (ko) * | 2004-12-27 | 2006-11-02 | 삼성전자주식회사 | 트윈비트 셀 구조의 nor형 플래쉬 메모리 소자 및 그제조 방법 |
-
2015
- 2015-03-17 KR KR1020150036798A patent/KR101659610B1/ko active IP Right Grant
- 2015-03-18 JP JP2016557652A patent/JP2017511308A/ja active Pending
- 2015-03-18 WO PCT/KR2015/002628 patent/WO2015142053A1/ko active Application Filing
- 2015-03-18 CN CN201580014038.7A patent/CN106103456A/zh active Pending
- 2015-03-18 US US15/126,876 patent/US20170117142A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004025083A1 (de) * | 2004-05-21 | 2005-12-29 | Infineon Technologies Ag | Verfahren zum Herstellen eines Festkörperelektrolytmaterialbereichs für ein Speicherelement einer Festkörperelektrolytspeicherzelle |
KR20060074236A (ko) * | 2004-12-27 | 2006-07-03 | 삼성전자주식회사 | 게르마늄 전구체, 이를 이용하여 형성된 gst 박막,상기 박막의 제조 방법 및 상변화 메모리 소자 |
KR100695168B1 (ko) * | 2006-01-10 | 2007-03-14 | 삼성전자주식회사 | 상변화 물질 박막의 형성방법, 이를 이용한 상변화 메모리소자의 제조방법 |
KR20120118060A (ko) * | 2006-11-02 | 2012-10-25 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 금속 박막의 cvd/ald용으로 유용한 안티몬 및 게르마늄 착체 |
JP2011086862A (ja) * | 2009-10-19 | 2011-04-28 | Central Glass Co Ltd | 非晶質半導体膜用オリゴメチルゲルマン化合物とこれを用いる成膜ガス |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019504509A (ja) * | 2015-11-19 | 2019-02-14 | ユージーンテック マテリアルズ カンパニー リミテッド | 有機4族化合物を含む前駆体造成物及びそれを利用した薄膜形成方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2017511308A (ja) | 2017-04-20 |
US20170117142A1 (en) | 2017-04-27 |
CN106103456A (zh) | 2016-11-09 |
KR20150108779A (ko) | 2015-09-30 |
KR101659610B1 (ko) | 2016-09-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015142053A1 (ko) | 유기 게르마늄 아민 화합물 및 이를 이용한 박막 증착 방법 | |
WO2015105350A1 (en) | Novel cyclodisilazane derivative, method for preparing the same and silicon-containing thin film using the same | |
WO2015105337A1 (en) | Novel trisilyl amine derivative, method for preparing the same and silicon-containing thin film using the same | |
WO2019103500A1 (ko) | 실리콘 함유 박막 증착용 조성물 및 이를 이용한 실리콘 함유 박막의 제조방법 | |
WO2012176989A1 (en) | A diamine compound or its salt, preparing method of the same, and uses of the same | |
WO2015190749A1 (en) | Novel amino-silyl amine compound and the manufacturing method of dielectric film containing si-n bond by using atomic layer deposition | |
WO2015130108A1 (ko) | 지르코늄 함유막 형성용 전구체 조성물 및 이를 이용한 지르코늄 함유막 형성 방법 | |
WO2017135715A1 (ko) | 4 족 금속 원소-함유 화합물, 이의 제조 방법, 이를 포함하는 막 증착용 전구체 조성물, 및 이를 이용하는 막의 증착 방법 | |
WO2014084557A1 (ko) | 실리콘 전구체 화합물 및 이를 이용한 실리콘-함유 박막의 증착 방법 | |
WO2016133365A1 (ko) | 알루미늄 화합물 및 이를 이용한 알루미늄-함유 막의 형성 방법 | |
WO2020130216A1 (ko) | 희토류 전구체, 이의 제조방법 및 이를 이용하여 박막을 형성하는 방법 | |
JP6651663B1 (ja) | アミノシラン化合物、前記アミノシラン化合物を含むシリコン含有膜形成用の組成物 | |
WO2021085810A2 (ko) | 4족 전이금속 화합물, 이의 제조방법 및 이를 포함하는 박막증착용 조성물 | |
WO2021261890A1 (ko) | 박막 형성용 프리커서, 이의 제조방법 및 이를 포함하는 박막 제조 방법 | |
WO2017082541A1 (ko) | 금속 전구체, 이의 제조방법, 및 이를 이용하여 박막을 형성하는 방법 | |
WO2018182305A9 (en) | Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition | |
WO2022025332A1 (ko) | 코발트 화합물, 이를 포함하는 전구체 조성물, 및 이를 이용한 박막의 제조방법 | |
WO2015141956A1 (ko) | 전구체 화합물 및 이를 이용한 박막 증착 방법, 아모퍼스 실리콘막의 증착방법 | |
WO2023113308A1 (ko) | 몰리브데넘 화합물, 이의 제조방법 및 이를 포함하는 박막 증착용 조성물 | |
WO2022169290A1 (ko) | 하프늄 전구체 화합물, 이를 포함하는 하프늄 함유 막 형성용 조성물 및 하프늄-함유 막 형성 방법 | |
WO2024049037A1 (ko) | 신규한 아미디네이트 리간드, 상기 리간드를 포함하는 박막 형성용 전구체 | |
WO2018182318A1 (en) | Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same | |
WO2024117807A1 (ko) | 스칸듐 또는 이트륨 함유 박막 형성용 전구체, 이를 이용한 스칸듐 또는 이트륨 함유 박막 형성 방법 및 상기 스칸듐 또는 이트륨 함유 박막을 포함하는 반도체 소자. | |
WO2014073892A1 (ko) | 실리콘-함유 박막의 제조 방법 | |
WO2022169232A1 (ko) | 4족 전이금속 화합물, 이의 제조방법 및 이를 이용하여 박막을 형성하는 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15765497 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016557652 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15126876 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15765497 Country of ref document: EP Kind code of ref document: A1 |