WO2013157715A1 - 저온 공정을 이용한 산화물 박막 제조방법, 산화물 박막 및 그 전자소자 - Google Patents
저온 공정을 이용한 산화물 박막 제조방법, 산화물 박막 및 그 전자소자 Download PDFInfo
- Publication number
- WO2013157715A1 WO2013157715A1 PCT/KR2012/010275 KR2012010275W WO2013157715A1 WO 2013157715 A1 WO2013157715 A1 WO 2013157715A1 KR 2012010275 W KR2012010275 W KR 2012010275W WO 2013157715 A1 WO2013157715 A1 WO 2013157715A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thin film
- oxide
- oxide thin
- zinc
- indium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 72
- 230000008569 process Effects 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims description 162
- 239000002243 precursor Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 229910052738 indium Inorganic materials 0.000 claims description 19
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 17
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- -1 zinc alkoxides Chemical class 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229940044658 gallium nitrate Drugs 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 6
- 238000007645 offset printing Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- SQICIVBFTIHIQQ-UHFFFAOYSA-K diacetyloxyindiganyl acetate;hydrate Chemical compound O.CC(=O)O[In](OC(C)=O)OC(C)=O SQICIVBFTIHIQQ-UHFFFAOYSA-K 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000007646 gravure printing Methods 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 3
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 3
- JQRBBVRBGGXTLZ-UHFFFAOYSA-N 2-methoxyethanol Chemical compound COCCO.COCCO JQRBBVRBGGXTLZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 57
- 229910052760 oxygen Inorganic materials 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229920001230 polyarylate Polymers 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NRBQACUXBZYLPJ-UHFFFAOYSA-N [In+3].O.[N+](=O)([O-])[O-].[In+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [In+3].O.[N+](=O)([O-])[O-].[In+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] NRBQACUXBZYLPJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BSIUFWMDOOFBSP-UHFFFAOYSA-N 2-azanylethanol Chemical compound NCCO.NCCO BSIUFWMDOOFBSP-UHFFFAOYSA-N 0.000 description 1
- ASQUQUOEFDHYGP-UHFFFAOYSA-N 2-methoxyethanolate Chemical compound COCC[O-] ASQUQUOEFDHYGP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- NYUMGSYSLYQDKV-UHFFFAOYSA-L dizinc;diacetate Chemical compound [Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O NYUMGSYSLYQDKV-UHFFFAOYSA-L 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- RIPZIAOLXVVULW-UHFFFAOYSA-N pentane-2,4-dione Chemical compound CC(=O)CC(C)=O.CC(=O)CC(C)=O RIPZIAOLXVVULW-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- 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
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02664—Aftertreatments
-
- 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
- H01L21/26—Bombardment with radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
Definitions
- the present invention relates to a method for producing an oxide thin film, and more particularly, to an oxide thin film manufacturing method using a low temperature process, an oxide thin film, and an electronic device thereof.
- the oxide thin film is used as an electronic device in various fields, such as a display field, a solar cell field, and a touch panel field, and an interest thereof has been increased because a simple composition change can form an optically transparent thin film having high electrical conductivity.
- Such oxide thin films include zinc oxide (ZnO), indium zinc oxide (IZO), and indium gallium zinc oxide (IGZO).
- ZnO zinc oxide
- IZO indium zinc oxide
- IGZO indium gallium zinc oxide
- the organic solvent contained in the solution is removed, and the oxide material having a specific function (conductor, semiconductor, insulator characteristics, etc.) is induced by inducing a reaction between the metallic material and oxygen.
- Heat treatment at a high temperature of 300 ° C. or higher is required in order to form and to remove impurities that combine with the oxide material and degrade the functionality of the thin film.
- the heat treatment process at a high temperature as described above has a problem of increasing the manufacturing process cost of the oxide thin film.
- the substrate is deformed (for example, a plastic substrate, a fiber substrate, etc.), and therefore, the type of substrate to which the oxide thin film is applied is limited. There was a problem that occurred.
- the oxide thin film reported to have excellent properties when manufacturing the thin film using this method has not been reported yet.
- the present inventors also produced a thin film transistor using the oxide thin film as a channel layer by the above-described conventional technique.
- the prior art method does not secure characteristics that can be utilized in actual products.
- Patent Document 0001 United States Patent Publication 2010-0261304 (Published October 14, 2010)
- Non-Patent Document 0001 K. K. Banger et. al., "Low-temperature, high-performance solution-processed metal oxide thin-film transistors formed by a 'sol-gel on chip' process", Nature Materials, Volume 10, Page 45-50, 2011.
- One aspect of the present invention comprises the steps of coating an oxide solution on a substrate; And it provides an oxide thin film manufacturing method comprising the step of irradiating the coated oxide solution with ultraviolet rays under an inert gas atmosphere.
- the "oxide thin film” is not particularly limited and can be utilized as a semiconductor layer, a transparent conductive film, and an insulating film.
- the semiconductor layer of the electronic device is utilized.
- oxides include Indium oxide (In 2 O 3 ), Zinc oxide (ZnO), Indium zinc oxide (IZO), Indium gallium zinc oxide (IGZO), Zinc tin oxide (ZTO), Titanium Oxide (TiO 2), Indium tin oxide (ITO), Aluminum oxide (Al2O3), Silicon oxide (SiO2), and the like, and all kinds of metal oxides produced by containing various metals in addition to their metal oxides are included in the scope of the present invention.
- precursors for forming an oxide thin film by a solution process may use an indium precursor, a gallium precursor, a zinc precursor, a tin precursor, an aluminum precursor, and the like, and at least one of these precursors may be used in combination.
- Zinc precursors are zinc chloride, zinc acetate, zinc acetate hydrate, zinc nitrate, zinc nitrate hydrate, zinc alkoxides. Or a derivative thereof, and the gallium precursor may include gallium nitrate, gallium nitrate hydrate, gallium acetate, gallium acetate hydrate, and gallium alkoxide.
- the indium precursor may be indium chloride, indium acetate, indium acetate hydrate, indium nitrate, indium Indium nitrate hydrate, indium alkoxy Tin (Indium alkoxides) or derivatives thereof
- the tin precursor may be tin chloride, tin acetate, tin nitrate, tin alkoxides or derivatives thereof It may include.
- other metal precursors such as aluminum precursors may be utilized.
- Inert gas atmosphere means nitrogen atmosphere, argon atmosphere, helium atmosphere, etc., and means to exclude an environment in which oxygen is deliberately injected or a process that proceeds in air without deliberate injection of oxygen. Further, preferably, a situation in which an inert gas is introduced into the coated oxide solution in an atmospheric state in which no vacuum process is performed separately is preferable.
- the coating is preferably carried out in a spin coating, dip coating, inkjet printing, offset printing, reverse offset printing, gravure printing or roll printing process.
- the ultraviolet irradiation step comprises a first step in which metal-oxygen-metal (MOM) bonds form at least a partial network in the oxide solution and a second step of removing impurities of the formed oxide. . Therefore, the ultraviolet irradiation period can be selected from 1 minute to 240 minutes.
- the step in which the metal-oxygen-metal (MOM) bonds form at least a partial network is found after about 30 minutes of irradiation with ultraviolet light, depending on the intensity of the ultraviolet light, the ultraviolet wavelength, and the like. It can vary.
- forming at least a partial network is at least 50% of the network. However, this can be confirmed by a rapid decrease in oxygen and a sharp change in carbon content.
- 30 minutes to 120 minutes are preferably included in the first step until the time when the sudden decrease of oxygen is completed, and the impurity removal step, which is the second step after the first step has elapsed, for a predetermined period.
- the present inventors were able to confirm that the characteristics of the thin film transistor prepared by using the oxide thin film of the present invention as a channel layer in Experimental Example 2 described below were excellent when 90 minutes to 120 minutes of UV irradiation.
- the wavelength of the ultraviolet ray is preferably 150 nm to 260 nm. This is because the oxide precursor solution is somewhat different depending on the type of the solvent, but the absorption of each precursor of the precursors of the metals (In, Ga, Zn) shows the best absorption rate in the range of 150nm to 260nm, so irradiating ultraviolet rays in this range This can be more effective. More preferably, ultraviolet rays of 160 nm to 190 nm are included at least to some extent.
- the solvent included in the metal precursor solution is 2-Methoxyethanol, or deionized water.
- the ionized water (Deionized water) is used as a solvent, it is more preferable because there is an effect that the absorption rate of the ultraviolet ray is further improved.
- a process of raising the temperature of the substrate is performed before the ultraviolet irradiation or together with the ultraviolet irradiation.
- the oxide solution coated on the substrate is stabilized by heat treatment. Heat treatment is to improve the uniformity and thickness uniformity of the thin film of the oxide solution coated, it may be performed for 1 to 60 minutes at a temperature of room temperature to 200 °C.
- the thermal process may be performed at room temperature to 200 ° C. for 1 to 60 minutes.
- Another aspect of the present invention provides an oxide thin film produced by the above-described oxide thin film manufacturing method.
- Another aspect of the present invention provides an electronic device including an oxide thin film manufactured by the oxide thin film manufacturing method described above.
- the oxide thin film may be used as an electronic device in a thin film transistor, a semiconductor field, a solar cell field, or a touch panel field in a display field, and may include a semiconductor layer, an insulating layer, and a transparent electrode of an electronic device. It can be applied to electrodes. Most preferably, it is used as a channel layer of a thin film transistor. In addition, various types of thin film transistors are possible if the present invention can be applied. For example, the structure in which the gate electrode is formed below the channel layer, or the structure in which the gate electrode is formed above the channel layer is possible.
- the uniformity of the oxide thin film may be maintained by stabilizing the coated oxide solution by heat treatment.
- deterioration of oxide characteristics can be prevented by inducing an oxide formation by irradiating ultraviolet rays under an inert gas atmosphere.
- FIG. 1 is a view for explaining a method for manufacturing an oxide thin film according to an embodiment of the present invention.
- FIG. 2 is a view conceptually illustrating a process of forming an IGZO thin film by ultraviolet irradiation according to an embodiment of the present invention.
- 3 and 4 are graphs showing absorption spectra of wavelengths of metal precursor solutions for forming various oxide thin films.
- FIG. 5 is a diagram schematically illustrating an oxide thin film transistor using an oxide thin film as a channel layer according to an exemplary embodiment of the present invention.
- FIG. 6 graphically shows the amount by which the atomic content of the oxide thin film changes with ultraviolet irradiation time.
- 7 and 8 are graphs for comparing the characteristics of each of the thin film coated with the oxide solution, the UV-irradiated thin film, and the thin film annealed at 350 °C.
- FIG. 9 is a graph comparing characteristics after ultraviolet irradiation in a nitrogen atmosphere and an oxygen atmosphere when forming an oxide thin film of the present invention.
- FIG. 10 is a graph comparing the characteristics of the thin film transistors having the IGZO, IZO, and In 2 O 3 channel layers in the experimental example of the present invention.
- FIG. 11 is a graph comparing physical properties of a thin film transistor manufactured from IGZO, IZO, and In 2 O 3 in the experimental example of the present invention when heat treated and UV irradiated.
- FIG. 13 shows average mobility characteristics according to UV irradiation time when an oxide thin film such as IGZO, IZO, In 2 O 3 , or ZTO IZTO is manufactured as a channel layer of a thin film transistor.
- oxide thin film such as IGZO, IZO, In 2 O 3 , or ZTO IZTO is manufactured as a channel layer of a thin film transistor.
- FIG. 14 is a graph illustrating typical characteristics of a thin film transistor fabricated on a PAR film
- FIG. 15 is a graph illustrating distribution of saturated field mobility by preparing 49 thin film transistors fabricated on a PAR film.
- FIG. 16 is a graph illustrating reliability of a device after applying stress by applying a positive voltage to a gate of an IGZO thin film transistor, which is an experimental example of the present invention.
- FIG. 17 is a graph showing the ring oscillator frequency of the present invention according to the supplied power voltage V DD .
- FIG. 18 is an oscillation output voltage when V DD of FIG. 17 is 5V (left) and 15V (right). It is a graph showing the situation.
- FIG. 1 is a view for explaining a method for manufacturing an oxide thin film according to an embodiment of the present invention.
- an oxide solution 2 is coated on a substrate 10, and an ultraviolet ray is irradiated to the coated oxide solution under an inert gas atmosphere.
- the oxide solution is coated onto the substrate through a solution process.
- the solution process may be spin coating, dip coating, inkjet printing, offset printing, reverse offset printing, gravure printing or roll printing, but is not limited thereto and may include all of the commonly used solution processes.
- the substrate is not limited to a specific kind, and a semiconductor substrate, a glass substrate, a polymer-based substrate such as plastic, paper, or the like can be used.
- the present invention uses an ultraviolet irradiation method to realize a low temperature process, and thus a high temperature process such as a plastic series. In the case of this impossible flexible display substrate it may be more effective.
- Zinc precursors are zinc chloride, zinc acetate, zinc acetate hydrate, zinc nitrate, zinc nitrate hydrate, zinc alkoxides. Or a derivative thereof, and the gallium precursor may include gallium nitrate, gallium nitrate hydrate, gallium acetate, gallium acetate hydrate, and gallium alkoxide.
- the indium precursor may be indium chloride, indium acetate, indium acetate hydrate, indium nitrate, indium Indium nitrate hydrate, indium alkoxy Indium alkoxides or derivatives thereof
- the tin precursors are tin chloride, tin acetate, tin nitrate, tin alkoxides and derivatives thereof. It may include.
- other metal precursors such as aluminum precursors may be utilized.
- a solvent for liquefying the precursors of the oxide solution may be used correspondingly according to the precursors, for example, acetonitrile, 2-Methoxyethanol, Methanol , DI It may be water or isopropyl alcohol (isopropylalcohol, IPA), but is not limited thereto.
- mono-ethanolamine mono-ethanolamine
- acetic acid acetic acid
- acetylacetone acetylacetone
- the thickness of the oxide solution to be coated is not limited, and for example, the oxide solution may be coated to a thickness of 5 to 300 nm.
- One of the features of the present invention is the process of irradiating the coated oxide solution with ultraviolet light under an inert atmosphere. As described above, this is an oxide applicable to a device by performing in an atmosphere in which oxygen exists despite attempts to anneal the oxide thin film using a laser when preparing an oxide thin film using a solution process. Failed to produce thin film.
- the oxide thin film manufacturing method When ozone (O 3 ) is irradiated with ultraviolet rays under the presence of oxygen, there is a problem of lowering the characteristics of the oxide. Therefore, in the oxide thin film manufacturing method according to an embodiment of the present invention, by irradiating ultraviolet rays in an inert gas atmosphere, there is an effect of preventing the deterioration of the characteristics of the oxide.
- the inert gas atmosphere is preferably a situation in which the inert gas is introduced into the coated oxide solution in the air without performing a separate vacuum process.
- the vacuum process is an expensive process, and in the solution process oxide production of the present invention, since the vacuum process is eliminated as much as possible, the vacuum process is not introduced.
- the ultraviolet irradiation may be performed by an ultraviolet light source such as a high-pressure Mercury lamp, but is not limited thereto.
- FIG. 2 is a view conceptually illustrating a process of forming an IGZO thin film by ultraviolet irradiation according to an embodiment of the present invention.
- the inventors have found that an excellent thin film is formed through two steps when UV irradiation is performed on the oxide thin film for a predetermined time.
- the first stage is the condensation stage and the second stage is the densification stage.
- the condensation step forms a partial network of metal-oxygen-metal (M-O-M) bonds inside the oxide solution.
- Films spin-coated prior to UV irradiation eg 25-35 nm
- the spin coated oxide thin film is irradiated with ultraviolet light in an atmosphere where nitrogen is purged.
- the active metal and oxygen atoms form an M-O-M network (condensation step). It was found that cleavage and condensation caused by ultraviolet rays occurred for the first time after about 30 minutes.
- the ultraviolet radiation is maintained for a predetermined time, thereby removing the existing impurities.
- the preferable holding time of ultraviolet irradiation may be 1 minute to 240 minutes.
- the above two steps may not be sufficiently performed to form a thin film having excellent characteristics, and if the UV irradiation time exceeds 240 minutes, there is a possibility of causing oxide deformation or substrate deformation. Because.
- the oxide thin film is used as the channel layer of the thin film transistor, ultraviolet irradiation showed excellent characteristics when 90 minutes to 120 minutes. This will be described later.
- the temperature of the substrate may be maintained at room temperature to 200 °C. As such, after the impurities are removed through the ultraviolet irradiation, the oxide thin film is completed.
- the oxide solution coated on the substrate is stabilized by heat treatment.
- Heat treatment is to improve the uniformity and thickness uniformity of the thin film of the oxide solution coated, it may be performed for 1 to 60 minutes at a temperature of room temperature to 200 °C.
- the irradiated ultraviolet rays have a wavelength in the ultraviolet region and / or the extreme ultraviolet region, and may be 150 nm to 260 nm. If the wavelength is shorter than 150nm, there is a problem that the oxide is destroyed by ultraviolet rays, if the wavelength is longer than 260nm there is a problem that not enough energy for the oxide formation is supplied.
- FIG. 3 and 4 are graphs showing absorption spectra of wavelengths of metal precursor solutions for forming various oxide thin films.
- FIG. 3 shows the wavelength-specific absorption rates of the solutions of 2-Methoxyethanol and precursors of individual metals (In, Ga, Zn) for comparison with the IGZO solution.
- 2-methoxyethanol which exhibits minimal absorption at wavelengths of 225 nm to 350 nm
- the solutions of Zn (CH 3 CO 2 ) 2 2H 2 O show strong absorption at 260, 250 and 230 nm, respectively.
- Mercury UV lamps have two peaks at 253.7 nm and 184.9 nm, so photochemical activation of indium, gallium and zinc precursor molecules is effective by UV irradiation of the lamp.
- FIG. 4 shows the wavelength-specific absorption rates of solutions of deionized water (D. I. water) and precursors of individual metals (In, Ga, Zn) for comparison with IGZO solutions.
- D. I. water deionized water
- precursors of individual metals In, Ga, Zn
- FIG. 4 can confirm a phenomenon in which the wavelength bands of the precursors of the metals (In, Ga, and Zn) are wider. Therefore, when D. I. water is used as the solvent, UV absorption rate is expected to be higher than that of 2-Methoxyethanol.
- the oxide thin film may be used as an electronic device in a thin film transistor, a semiconductor field, a solar cell field, or a touch panel field in a display field, and may include a semiconductor layer, an insulating layer, and a transparent electrode of an electronic device. It can be applied to electrodes.
- the oxide thin film is utilized as the channel layer of the thin film transistor will be mainly described.
- FIG. 5 is a diagram schematically illustrating an oxide thin film transistor using an oxide thin film as a channel layer according to an exemplary embodiment of the present invention.
- an oxide thin film transistor forms a gate insulating layer 20 and a gate electrode 21 on a substrate 10, and forms an oxide channel layer 30 and a drain electrode 40 on the gate insulating layer 20.
- the source electrode 50 can be manufactured.
- an oxide thin film manufacturing method according to an embodiment of the present invention may be applied in the process of forming the oxide channel layer 30.
- the gate insulating layer 20, the gate electrode 21, the drain electrode 40, and the source electrode 50 are the same as or similar to a known thin film transistor, detailed description thereof will be omitted.
- an oxide solution is coated on the gate insulating layer 20 through a solution process, stabilized by heat treatment, and then irradiated with ultraviolet light in an inert gas atmosphere to induce oxide formation, and the ultraviolet irradiation is maintained for a predetermined time.
- the oxide channel layer 30 can be formed by removing impurities. Therefore, a high quality thin film transistor can be manufactured in an economical manner.
- FIG. 6 graphically shows the amount by which the atomic content of the oxide thin film changes with ultraviolet irradiation time. 6 shows that the spin-coated thin films (25-35 nm) still have organic components remaining before the ultraviolet irradiation. This is confirmed by the carbon content in the thin film.
- the spin coated oxide thin film is then irradiated with a DUV lamp (with peaks at 184.9 nm (10%) and 253.7 nm (90%)) in an atmosphere where nitrogen is purged.
- the DUV lamp is irradiated 1-5 cm away from the samples, and N 2 gas is continuously injected.
- Energy output of the lamp is 25 ⁇ 28 mWcm -2, and degree, in the case of irradiation 90 minutes 135 - 151 Jcm -2, 120 bun survey 180 were each measured with a 201 Jcm -2.
- Active metals and oxygen atoms form a MOM network by UV irradiation (condensation, step 1).
- Cleavage and condensation by ultraviolet rays is confirmed by the rapid decrease of oxygen and the carbon content (see FIG. 6). Such cleavage and condensation by ultraviolet rays occurs for about 30 minutes after the ultraviolet irradiation. In this process, 50% to 90% of the network is partially formed. For example, 24% of networks before the first survey were found to be 71% after the first survey.
- 7 and 8 are graphs for comparing the characteristics of each of the thin film coated with the oxide solution, the UV-irradiated thin film, and the thin film annealed at 350 °C.
- FIG. 7 shows the X-ray photoelectron spectrum (O (1s) peak) of each of a thin film coated with an oxide solution, a thin film irradiated with ultraviolet rays, and a thin film annealed at 350 ° C.
- the thermally annealed thin film and the ultraviolet ray irradiated thin film exhibit almost similar deconvolution peaks. This means that even in the state of atomic binding such as M-O bonding, the IGZO thin film P and the thermally annealed IGZO thin film T are similar to each other.
- FIG. 8 shows the Rutherford Backscattering Spectrometry (RBS) spectra of the IGZO thin film P and the thermally annealed IGZO thin film T by UV irradiation (the Zn component includes Ga atoms).
- the density was 52.88 X 10 15 atoms cm -2 (P) and 52.43 X 10 15 atoms cm -2 (T) by RBS measurement, and the thicknesses were high-resolution transmission electron microscopy (HRTEM) (lower limit) and ellipsometric method ( ellipsometry) (upper limit) measured 7.1 to 9.70 nm (P) and 7.1 to 10.27 nm (T). Accordingly, the characteristics of the IGZO thin film P and the thermally annealed IGZO thin film T are almost similar.
- HRTEM transmission electron microscopy
- ellipsometric method ellipsometry
- the inventors interpret this densification after 60 minutes to decompose organic residues (solvent molecules and residual alkoxy groups) by ultraviolet irradiation photolysis and reorganization of the M-O-M network.
- the inventors have found that when irradiated with ultraviolet light in this setup, the oxide thin film is increased to about 150 ° C. by the lamp, contrary to the original intention. This temperature was maintained even when the UV lamp was continuously irradiated with 180-201 Jcm -2 for more than 120 minutes.
- the device was fabricated by annealing at 150 ° C. without UV irradiation or by ultraviolet irradiation and cooling at 40-70 ° C. at a cooling stage. In this case, however, the required electrical characteristics were not secured at all.
- a silicon oxide film was formed to a thickness of 200 nm on a heavily p-doped silicon wafer.
- a solution containing metal precursors for the IGZO thin film was coated on the silicon oxide film by spin coating.
- 2-methoxyethanol was used as the solvent in the IGZO solution, 0.085M of indium nitrate hydrate, 0.0125M of gallium nitrate hydrate, and zinc acetate Zinc acetate dehydrate 0.0275M was used.
- the coated IGZO solution was irradiated with ultraviolet light using a UV lamp to induce oxide formation, but in the comparative example, ultraviolet irradiation was performed under the presence of oxygen, and in the embodiment, ultraviolet irradiation was performed under nitrogen atmosphere (nitrogen). Is supplied continuously). The ultraviolet light was irradiated using the UV lamp of Experimental Example 1.
- oxide thin film transistors were fabricated by using the formed IGZO oxide thin film as a channel layer, and forming an IZO electrode layer on the IGZO oxide thin film and patterning the source and drain electrodes.
- FIG. 9 is a graph comparing characteristics after ultraviolet irradiation in a nitrogen atmosphere and an oxygen atmosphere when forming an oxide thin film of the present invention.
- current transfer characteristics were measured and the results are shown in FIG. 9.
- the current transfer characteristic was achieved by changing the voltage in the forward direction of -30V at the reverse direction of + 30V to the gate terminal and measuring the drain current change.
- the inventors judge that the light activation by the UV lamp (the light activation by 184.9 nm is drastically reduced) is due to the drastic decrease in the absorption of oxygen molecules. This phenomenon is considered to have a bad influence when the thin film transistor is formed in an oxygen atmosphere.
- the light activation by the UV lamp may have an important meaning in the ultraviolet wavelength region of 160 nm to 190 nm. That is, when there is ultraviolet light having a wavelength of 160 nm to 190 nm, an excellent oxide thin film having a predetermined level or more may be secured.
- the DUV lamps used in this experiment had peaks at 184.9 nm (10%) and 253.7 nm (90%).
- the photon flux of the DUV lamp is 2.88 to 3.22 X 10 20 / m 2 sec (253.7 nm), 2.32 to 2.6 X 10 19 / m 2 sec (184.9 nm).
- the cause of the deterioration of the oxide thin film property due to the rapid decrease in the light activation at 184.9 nm serves to suppress the process of making ozone even though UV having relatively low power at 184.9 nm.
- the wavelength band that can play this role has been calculated from 160nm to 190nm.
- IGZO films have been described so far, but other oxide thin films (Zinc Tin Oxide (ZTO), Indium Zinx Oxide (IZO), Zinc Tin Oxide (ZTO), and Indium Zinc Tin Oxide (IZTO)) may also be applied.
- ZTO Zinc Tin Oxide
- IZO Zinc Tin Oxide
- IZTO Indium Zinc Tin Oxide
- the inventors have concluded that by fabricating a variety of oxide thin film transistors, the method of the present invention is applicable to an oxide thin film based on a solution process, which is not particularly limited. However, it was confirmed that the use of ZnCl 2 solution should be avoided if possible. This exclusion is due to the fact that the ZnCl 2 solution has little ultraviolet absorption.
- IGZO, IZO, IZTO, and In 2 O 3 solutions were prepared by indium nitrate hydrate (In (NO 3 ) 3 x H 2 O), gallium nitrate hydrate (Ga) (NO 3 ) 3 ⁇ xH 2 O) and Zinc Acetate (Zn (CH 3 CO 2 ) 2 ⁇ 2H 2 O), Zinc chloride (ZnCl 2 ), tin acetate ( Sn (CH 3 CO 2 ), tin cloride (SnCl 2 ) are dissolved in 2-Methoxyethanol, and the precursor solution was steered at 75 ° C. for more than 12 hours.
- Table 1 describes the molar concentrations of metal precursors of IGZO, IZO, IZTO, In2O3 solutions.
- ZTO solution is composed of zinc chloride (ZnCl 2) and tin cloride (SnCl 2 ) powders, respectively. . After dissolving the precursors in the solvent, it was steered at room temperature for 15 minutes.
- FIG. 10 is a graph comparing the characteristics of the thin film transistors having the IGZO, IZO, and In 2 O 3 channel layers in the experimental example of the present invention.
- the Al 2 O 3 gate insulating film 35 nm
- the thin film transistors having the IGZO, IZO, and In 2 O 3 channel layers are heat-treated and 20, respectively, 20 are manufactured. It was.
- the IGZO, IZO, and In 2 O 3 channel layers were applied by spin coating, baked at 200 ° C. for 10 minutes, and annealed at 350 ° C. for 60 minutes on a hot plate.
- An oxide thin film such as ZTO IZTO was baked at 200 ° C. for 10 minutes and annealed at 500 ° C. for 10 minutes on a hot plate.
- FIG. 11 is a graph comparing the mobility, threshold voltage (Vt), and swing (SS) of the thin film transistor fabricated with IGZO, IZO, and In 2 O 3 but subjected to heat treatment and UV irradiation. admit.
- FIGS. 10 and 11 show that the UV-irradiated thin film transistor has similar characteristics or rather excellent characteristics compared with the case of heat treatment.
- a and b were 20 IGZO TFTs fabricated on a silicon wafer, and their mobility was statistically treated at 30, 60, 90 and 120 minutes of ultraviolet irradiation time, respectively.
- c and d were 20 In 2 O 3 TFTs fabricated on a silicon wafer, and their mobility was statistically treated at 30, 60, 90 and 120 minutes, respectively.
- FIG. 13 shows average mobility characteristics according to UV irradiation time when an oxide thin film such as IGZO, IZO, In 2 O 3 , or ZTO IZTO is manufactured as a channel layer of a thin film transistor.
- oxide thin film such as IGZO, IZO, In 2 O 3 , or ZTO IZTO is manufactured as a channel layer of a thin film transistor.
- FIG. 15 is a graph illustrating distribution of saturated field mobility by preparing 49 thin film transistors prepared on a PAR film. Referring to FIG. 15, the field effect mobility is distributed around 3.77 cm 2 V ⁇ 1 s ⁇ 1 , and includes an on / off ratio, a sub-threshold swing (SS), and a threshold voltage (Vth). Has excellent characteristics of 10 8 , 95.8 ⁇ 20.8 mV per decade, and 2.70 ⁇ 0.47 V, respectively.
- SS sub-threshold swing
- Vth threshold voltage
- FIG. 16 is a graph illustrating reliability of a device after applying stress by applying a positive voltage to a gate of an IGZO thin film transistor, which is an experimental example of the present invention.
- the device subjected to ultraviolet irradiation and the PMMA film as a protective film had a threshold voltage of 1.12 V changed after 10,000 seconds, and the device thermally annealed at 350 ° C. changed 0.86 V, showing almost similar threshold voltage changes. .
- FIG. 17 is a graph showing the ring oscillator frequency of the present invention according to the supplied power voltage V DD .
- FIG. 18 is an oscillation output voltage when V DD of FIG. 17 is 5V (left) and 15V (right). It is a graph showing the situation.
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Abstract
Description
Claims (17)
- 산화물 용액을 기판 상에 코팅하는 단계; 및불활성 가스 분위기 하에서 상기 코팅된 산화물 용액에 자외선 조사하는 단계를 포함하는 산화물 박막 제조방법.
- 제1 항에 있어서,상기 불활성 가스 분위기는 별도로 진공 프로세스를 진행하지 않은 대기 상태에서 상기 코팅된 산화물 용액에 상기 불활성 가스가 유입되는 것인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 자외선 조사 단계는 산화물 용액 내부에 금속-산소-금속(Metal-Oxygen-Metal, M-O-M) 본드들이 적어도 부분적인 네트워크를 형성하는 단계와 형성된 산화물의 불순물을 제거하는 단계를 포함하여 구성되는 산화물 박막 제조방법.
- 제3 항에 있어서,상기 적어도 부분적인 네트워크를 형성하는 것은 50% 이상의 네트워크를 형성하는 것인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 불활성 가스 분위기는 질소 분위기, 아르곤 분위기, 또는 헬륨 분위기인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 금속 전구체 용액에 포함되는 용매는 2-메톡시에탄올(2-Methoxyethanol), 또는 이온제거수(Deionized water)인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 자외선의 파장은 150nm 내지 260nm인 산화물 박막 제조방법.
- 제7 항에 있어서,상기 자외선의 파장은 160nm 내지 190nm인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 자외선 조사의 이전, 또는 상기 자외선 조사와 함께, 상기 기판의 온도를 변화시키는 공정이 수행되는 산화물 박막 제조방법.
- 제1 항에 있어서,상기 자외선 조사의 유지 시간은 1분 내지 240분인 산화물 박막 제조방법.
- 제10 항에 있어서,상기 자외선 조사의 유지 시간은 30분 내지 120분인 산화물 박막 제조방법.
- 제10 항에 있어서,상기 자외선 조사의 유지 시간은 90분 내지 120분인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 산화물 박막은 채널층인 산화물 박막 제조방법.
- 제1 항에 있어서,상기 코팅은 스핀 코팅, 딥 코팅, 잉크젯 프린팅, 옵셋 프린팅, 리버스 옵셋 프린팅, 그라비어 프린팅 또는 롤 프린팅 공정으로 진행되는 산화물 박막 제조방법.
- 제1 항에 있어서,상기 산화물 용액은 징크 클로라이드(Zinc chloride), 징크 아세테이트(Zinc acetate), 징크 아세테이트 하이드레이트(Zinc acetate hydrate), 징크 나이트레이트(Zinc nitrate), 징크 나이트레이트 하이드레이트(Zinc nitrate hydrate), 징크 알콕사이드(Zinc alkoxides) 또는 이들의 유도체를 포함하는 아연 전구체;갈륨 나이트레이트(Gallium nitrate), 갈륨 나이트레이트 하이드레이트(Gallium nitrate hydrate), 갈륨 아세테이트(Gallium acetate), 갈륨 아세테이크 하이드레이트(Gallium acetate hydrate), 갈륨 알콕사이드(Gallium alkoxides) 또는 이들의 유도체를 포함하는 갈륨 전구체;인듐 클로라이드(Indium chloride), 인듐 아세테이트(Indium acetate), 인듐 아세테이트 하이드레이트(Indium acetate hydrate), 인듐 나이트레이트(Indium nitrate), 인듐 알콕사이드(Indium alkoxides) 또는 이들의 유도체를 포함하는 인듐 전구체;틴 클로라이드(Tin chloride), 틴 아세테이트(Tin acetate), 틴 나이트레이트(Tin nitrate), 틴 알콕사이드(Tin alkoxides) 또는 이들의 유도체를 포함하는 주석 전구체 및 이들의 혼합물 중에서 선택되는 산화물 박막 제조방법.
- 제1 항 내지 제 15항 중 어느 한 항에 따른 산화물 박막 제조방법에 의해 제조되는 산화물 박막.
- 제1 항 내지 제 15항 중 어느 한 항에 따른 산화물 박막 제조방법에 의해 제조되는 산화물 박막을 포함하는 전자소자.
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US14/394,869 US9881791B2 (en) | 2012-04-16 | 2012-11-30 | Method for producing an oxide film using a low temperature process, an oxide film and an electronic device thereof |
JP2015506879A JP6014243B2 (ja) | 2012-04-16 | 2012-11-30 | 酸化物薄膜の製造方法 |
EP12874836.5A EP2840590A4 (en) | 2012-04-16 | 2012-11-30 | PROCESS FOR PRODUCING LOW TEMPERATURE PROCESSING OXIDE FILM, OXIDE FILM, AND ELECTRONIC DEVICE |
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KR1020120137532A KR101456237B1 (ko) | 2012-04-16 | 2012-11-30 | 저온 공정을 이용한 산화물 박막 제조방법, 산화물 박막 및 그 전자소자 |
KR10-2012-0137532 | 2012-11-30 |
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EP (1) | EP2840590A4 (ko) |
JP (1) | JP6014243B2 (ko) |
KR (1) | KR101456237B1 (ko) |
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Also Published As
Publication number | Publication date |
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JP6014243B2 (ja) | 2016-10-25 |
KR101456237B1 (ko) | 2014-11-03 |
KR20130116785A (ko) | 2013-10-24 |
US20150123115A1 (en) | 2015-05-07 |
EP2840590A4 (en) | 2015-09-02 |
EP2840590A1 (en) | 2015-02-25 |
US9881791B2 (en) | 2018-01-30 |
JP2015520716A (ja) | 2015-07-23 |
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