TWI631100B - 用於製造含氧化銦層之調合物、製造彼等之方法及彼等之用途 - Google Patents
用於製造含氧化銦層之調合物、製造彼等之方法及彼等之用途 Download PDFInfo
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- TWI631100B TWI631100B TW103121567A TW103121567A TWI631100B TW I631100 B TWI631100 B TW I631100B TW 103121567 A TW103121567 A TW 103121567A TW 103121567 A TW103121567 A TW 103121567A TW I631100 B TWI631100 B TW I631100B
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- Prior art keywords
- indium
- blend
- patent application
- alkyl
- manufacturing
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000009472 formulation Methods 0.000 title description 2
- 229910052738 indium Inorganic materials 0.000 claims abstract description 44
- -1 indium alkoxide compound Chemical class 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 22
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 15
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 10
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000005670 electromagnetic radiation Effects 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 229940116333 ethyl lactate Drugs 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical class CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 3
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 108700031620 S-acetylthiorphan Proteins 0.000 claims description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims 1
- 239000004020 conductor Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000000576 coating method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 150000003335 secondary amines Chemical class 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 229910021617 Indium monochloride Inorganic materials 0.000 description 6
- 239000002800 charge carrier Substances 0.000 description 6
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 150000002632 lipids Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical class C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical class CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
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
- H01L21/04—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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- 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
- C23C16/46—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 heating the substrate
-
- 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
- C23C16/48—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 by irradiation, e.g. photolysis, radiolysis, particle radiation
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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Abstract
本發明關於一種液體調合物,其可藉由將至少一種銦烷氧化物化合物溶解在至少一種溶劑中所製造,該銦烷氧化物化合物可藉由在通式ROH之醇(其中R=烷基)存在下以相對於三鹵化銦為8:1至20:1之莫耳比反應三鹵化銦InX3(其中X=F、Cl、Br、I)與式R'2NH之二級胺(其中R'=烷基)而製備;製造彼等之方法;彼等用於製造含氧化銦或(半)導體層之用途;及使用本發明之調合物製造含氧化銦層的方法。
Description
本發明關於一種用於製造含氧化銦層之調合物、製造彼等之方法及彼等之用途。
利用壓力沉積法及其他液體沉積法製造半導體電子組件層由於此情況下之半導體沉積可以連續程序進行,因而使得可獲致遠低於許多其他方法(諸如化學氣相沉積(CVD))之製造成本。此外,在相對低處理溫度之情況下,亦變得可能在撓性基板上作業,及隨意地(尤其是在非常薄之層的情況下,特別是在氧化物半導體(oxidic semiconductor)之情況下)獲致印刷層的光學透明度。在此處及下文中,在通道長度為20μm、於閘極-源極電壓為50V及源極-汲極電壓為50V之組件的電荷載子遷移率為1至50cm2/Vs之層。
由於待藉由印刷法製造之組件層的材料關鍵性地決定個別層性質,此材料之選擇對於含有此組件層之每一組件
具有重要影響。印刷半導體層之重要參數為其個別電荷載子遷移率,及在其製造中所使用之可印刷前驅物的加工性及處理溫度。該等材料應具有良好電荷載子遷移率及可從溶液且在明顯低於500℃之溫度下製造,以適用於大量應用及基板。同樣需要將半導體層製成具有光學透明性以用於許多類型之應用。
由於氧化銦(氧化銦(III),In2O3)具有在3.6與3.75eV之範圍的大能帶隙(於氣相沉積層上測得,H.S.Kim,P.D.Byrne,A.Facchetti,T.J.Marks;J.Am.Chem.Soc.2008,130,12580-12581),其為前景極佳因此為理想的導體。厚度數百奈米的薄膜在550nm下大於90%的可見光譜中可另外具有高透明度。此外,可在極有序之氧化銦單晶中量得至高達160cm2/Vs之電荷載子遷移率。然而,迄今尚未能藉由從溶液處理獲致此等值(H.Nakazawa、Y.Ito、E.Matsumoto、K.Adachi、N.Aoki、Y.Ochiai;J.Appl.Phys.2006,100,093706,及A.Gupta、H.Cao、Parekh、K.K.V.Rao、A.R.Raju、U.V.Waghmare;J.Appl.Phys.2007,101,09N513)。
氧化銦尤其經常與氧化錫(IV)(SnO2)一起使用作為半導體混合氧化物ITO。因ITO層在可見光譜中具有較高傳導性並結合透明度之故,其特別應用之一係液晶顯示器(LCD)領域,尤其是作為「透明電極」。該等通常經摻雜之金屬氧化物層係主要藉由高成本氣相沉積方法在高度真空下工業製造。因塗覆ITO之基板的重要經濟利益之故,
目前存在一些含氧化銦層的塗覆方法,尤其是以溶膠-凝膠技術為基礎者。
原則上,有兩種藉由印刷法製造氧化銦半導體的可能性:1)粒子概念,其中(奈米)粒子存在於可印刷分散液中,且在印刷操作之後利用燒結法將其轉化成所希望之半導體層,及2)前驅物概念,其中在印刷適當組成物之後,至少一種可溶性或可分散性中間物係轉化成含氧化銦層。相較於使用前驅物,粒子概念有兩個重大缺點:首先,粒子分散液具有膠體不穩定性,其使得必須使用分散添加劑(其不利於後續層之性質);其次,許多可用粒子(例如因鈍化層所致)利用燒結僅不完全地形成層,使得該等層中仍發生一些微粒結構。在其粒子邊界,存在相當高粒子-粒子電阻,此降低電荷載子之遷移率及提高一般層之電阻。
目前有各種含前驅物調合物以供製造氧化銦層。如此,不僅可使用鋰鹽亦可使用銦烷氧化物(全同配位體化合物(homoleptic compound),即,只具有銦及烷氧化物基團)作為溶液中之前驅物以供製造含氧化銦層。
例如,Marks等人描述在包含之InCl3及鹼性單乙醇胺(MEA)的含前驅物組成物之製造中的組分係作為溶於甲氧基乙醇中的溶液使用。在藉由旋塗施加該組成物之後,藉由在400℃熱處理而製造對應氧化銦層(H.S.Kim、P.D.Byrne、A.Facchetti、T.J.Marks;J.Am.Chem.Soc.2008,130,12580-12581及補充資訊)。
WO 2011/072887 A1描述用於製備銦(III)鹵化物二烷
氧化物(indium(III)halide dialkoxide)之方法及其用於製造含氧化銦層的用途。用於從銦(III)鹵化物二烷氧化物製造含氧化銦層之方法係揭示於WO 2011/073005 A2。
然而,於溶液中之銦(III)鹵化物二烷氧化物迄今仍未形成具有夠好之電性質的含氧化銦層。例如具有以下通式之化合物:In6O2X6(OR)6(R'CH(O)COOR")2(HOR)x(HNR"' 2)y、In7O2(OH)(OR)12X4(ROH)x及MxOy(OR)z[O(R'O)eH]aXbYc[R"OH]d之銦側氧基烷氧化物(Indium oxoalkoxide)形成較佳層性質,該等化合物係揭示於WO 2012/010427 A1、WO 2012/010464 A1及尚未公開之德國申請案DE 10 2012 209918。
雖然已知該等改良,但持續需要有關層形成性質及所獲得之層的性質之改良。特別的是,適用之前驅物應:- 能容易地處理,特別是在空氣中處理,- 能均勻地轉化成氧化物,- 能在極低溫下均勻地轉化成氧化物,- 形成具有優異電性質之層。
此複雜需求概要係由一種藉由溶解至少一種銦烷氧化物化合物所製造之液體調合物滿足,該銦烷氧化物化合物可藉由在通式ROH之醇(其中R=烷基)存在下令
- 三鹵化銦InX3(其中X=F、Cl、Br、I)
- 與相對於該三鹵化銦之莫耳比為8:1至20:1的式R'2NH之二級胺(其中R'=烷基)反應而製備。
可使用含有在反應中使用相對於三鹵化銦為8:1至15:1之莫耳比,更佳為8:1至12:1之莫耳比的二級胺所製備之銦烷氧化物化合物的調合物製造特別良好的層。
基於本發明目的,本情況中之銦烷氧化物化合物為具有至少一個銦原子及至少一個烷氧基(alkoxide radical)的化合物,其可藉由上述在醇存在下之三鹵化物與二級胺的反應製備。可由本發明方法獲得之該等溶解的化合物的結構測定有其困難。然而,假設所得之化合物為含鹵素銦側氧基烷氧化物化合物。此類型之固態結構能利用X射線結構分析測定。假設該等化合物之相似結構亦存在溶液中。銦側氧基烷氧化物係由側氧基橋接且可以離子形式存在之銦團簇,其中不由側氧基配位之價係至少部分由烷氧基配位。在可藉由本發明方法獲得之銦烷氧化物化合物的情況中,假設在合成之後此等經常以鹽形式存在,特別是以由陽離子配位之含鹵素的銦側氧基烷氧化物陰離子形式存在。
特佳之製程產物為具有以下通式之銦烷氧化物化合物[In6(O)(OR)12X6]2-Am z(ROH)x(其中R=烷基,X=F、Cl、Br、I,A=陽離子,z=陽離子價,m.z=2且x=0至10,其尤其可使用為9:1至10:1之比的二級胺製備。該化合物可由醇分子ROH配位,及該反應中亦可能存在其他溶劑。
典型陽離子為銨離子[NHyR4-y]+,較佳為式[NH2R2]+
之銨離子。
特佳之化合物為[In6(O)(OMe)12Cl6]2-[NH2R2]+ 2(MeOH)2,其可藉由使用InCl3、Me2NH(後者之比為9:1至10:1)及MeOH(甲醇)製備。此經由X射線結構分析測定之結構係示於圖1。
本發明之調合物較佳含有重量百分比以該調合物之總質量為基準計為0.1至10重量%,較佳為0.5至5重量%,尤佳為1至2重量%之銦烷氧化物化合物,以特別獲致良好半導體層。
本發明之配方進一步包含至少一種溶劑。為了獲係特別良好之調合物,該至少一種溶劑較佳係選自由以下所組成之群組:一級、二級、三級及芳族醇類(該等醇類特佳為甲醇、乙醇、丁醇、四氫糠醇及酚)、醚類(特佳者為具有式ROCH2CH(R')OR"(其中R=-H或-C1-C10烷基,R'=-H或-CH3且R"=-H或-C1-C10-烷基)之二醇醚及環醚,特別是2-甲氧基乙醇、1-甲氧基-2-丙醇、四氫呋喃以及苯基甲基醚)、酯類(特佳者為羧酸酯及乳酸烷酯,特別是乙酸丁酯、乙酸1-甲氧基-2-丙酯(PGMEA)、苯甲酸乙酯、二乙酸乙二醇酯、乳酸乙酯及乳酸丁酯)、芳族烴類(特佳者為甲苯及二甲苯)以及腈類(特佳者為乙腈)。
該至少一種溶劑較佳係選自由以下所組成之群組:甲醇、乙醇、丁醇、四氫糠醇、酚、2-甲氧基乙醇、1-甲氧基-2-丙醇、四氫呋喃、苯基甲基醚、乙酸丁酯、乙酸1-甲氧基-2-丙酯(PGMEA)、苯甲酸乙酯、二乙酸乙二醇
酯、乳酸乙酯、乳酸丁酯、甲苯、二甲苯及乙腈。
本發明之調合物更佳係包含至少兩種,又更佳係至少三種選自由上述溶劑種類所組成之群組的溶劑。
本發明之調合物較佳包含至少三種溶劑,其中一者係選自由以下所組成之群組:乳酸乙酯、苯基甲基醚、四氫糠醇、乙酸丁酯、二乙酸乙二醇酯及苯甲酸乙酯,且其他二者在SATP條件下之沸點差異為至少30℃。特佳結果可利用對應調合物獲得。
最佳結果可使用包含乙醇、1-甲氧基-2-丙醇及四氫糠醇三種溶劑之調合物獲致。
本發明之調合物較佳含有重量百分比以塗覆組成物之總質量為基準計為90至99.9重量%,較佳為95至99.5重量%,特佳為98至99重量%的溶劑。
此外,本發明之組成物可包含添加劑,特別是濕潤添加劑(特別是界面活性劑)、消泡劑、交聯添加劑、表面張力添加劑及整平劑以獲致有利性質。若存在添加劑,其重量百分比以塗覆組成物之總質量為基準計為少於5重量%,較佳為少於2重量%。然而,本發明之組成物較佳不包含任何其他添加劑,即,其只使用溶劑及銦烷氧化物化合物製造。
為獲致特別良好之性質,該調合物基本上無水,即,具有少於200ppm之H2O。此外,更佳係使用基本上無水之溶劑及化合物製造調合物。
本發明進一步提供一種製造本發明之調合物的方法,
其中至少一種上述銦烷氧化物化合物係與至少一種溶劑混合。
用以製造本發明之調合物的銦烷氧化物化合物係利用其中在通式ROH之醇(其中R=烷基)存在下令
- 三鹵化銦InX3(其中X=F、Cl、Br、I)
- 與相對於該三鹵化銦之莫耳比為8:1至20:1的式R'2NH之二級胺(其中R'=烷基)反應之方法而製備。
式InX3之三鹵化銦為熟習本領域之人士已知且可在市面購得。
式R'2NH(其中R'=烷基)之二級胺同樣為先前技術。烷基R'較佳為式CnH2n+1(其中n=1至10)之直鏈、支鏈或環狀C1至C10烷基。二級胺或二種二級胺之兩個R'基團亦可一起形成烷基CnH2n。對應之可用化合物為例如二甲胺、二乙胺、二丙胺、吡咯啶、哌啶及吡咯。較佳之R'基團為甲基、乙基、正丙基及異丙基。最佳地,R'基團為甲基,原因係此形成特別良好之產率及特別安定的化合物。
作為醇ROH,較佳係使用具有式CnH2n+1(其中n=1至10)之直鏈、支鏈或環狀C1至C10烷基者。此處,較佳之R基團亦為甲基、乙基、正丙基及異丙基。R基團最佳為甲基。
烷氧化銦較佳係以所有組分之總質量為基準計為0.1至50重量%,特佳為1至25重量%,最佳為2至10重量%的比例用於該方法。
三鹵化銦可溶解(即,解離)或以分子等級與溶劑分子/
醇分子錯合,或分散於液相中。
醇ROH較佳係以所有組分之總質量為基準計為50至99.9重量%,特佳為75至99重量%,最佳為80至96重量%的比例用於該方法。
該方法之反應混合物可進一步包括至少一種相對於反應為惰性之液態溶劑或分散液介質,即,在反應條件下不與三鹵化銦反應之溶劑/分散介質或不同溶劑/分散介質的混合物。較佳係使用非質子性溶劑,特別是選自由非質子性非極性溶劑組成之群組的溶劑,即,烷類、經取代烷類、烯類、炔類、芳族化合物(不具或具有脂族或芳族取代基)、鹵化烴類及四甲基矽氧烷;及由非質子性極性溶劑組成之群組,即醚類、芳族醚類、經取代之醚類、酯類或酸酐類、酮類、三級胺類、硝甲烷、DMF(二甲基甲醯胺)、DMSO(二甲亞碸)及碳酸丙二酯。
若此種對於反應為惰性之液體溶劑或分散液介質存在於反應混合物中,其比例以所有組分之總質量為基準計較佳為1至50重量%,特佳為1至25重量%,尤佳為1至10重量%。
二級胺較佳地係以相對於三鹵化銦為8:1至15:1之莫耳比,更佳為8:1至12:1之莫耳比用於反應中,原因係可以特別高產率製備具有特別適於層製造的銦烷氧化物化合物。
本發明之方法較佳係藉由最初將三鹵化銦載入醇ROH來進行。該二級胺係以氣態形式、液態形式或作為
溶劑中之溶液(尤其是包含ROH作為溶劑)來添加。
添加同樣較佳係在SATP條件(25℃及1.013巴)下進行。
由於反應可以此方式特別容易受控制且形成特別良好的銦烷氧化物化合物,二烷基胺係以每小時與每莫耳鹵化銦為0.5至5莫耳,較佳係小時與每莫耳鹵化銦為1.15至2.60莫耳之速率添加。
反應混合物更佳係在該方法中添加所有組分之後予以加熱。反應混合物較佳係在1至10小時期間加熱至40至70℃之溫度。反應混合物更佳係在1至5小時之時間加熱至45至60℃之溫度。然後將該反應混合物冷卻。
在反應已完成時,將通常沉澱之產物或產物混合物與反應組成物之其他成分分離。此較佳係藉由過濾進行。此外,分離之產物混合物較佳係經乾燥及利用適當溶劑清洗。
可用於製造本發明調合物之特別良好的銦烷氧化物化合物係當在分離及可能地乾燥及/或溶劑之後所獲的產物或產物混合物再結晶時形成。再結晶較佳係在該化合物之合成中亦使用的醇ROH中進行。再結晶較佳係藉由將分離之產物或產物混合物溶解於沸騰醇中,然後在-30至0℃之溫度下再結晶來進行。將上澄液溶劑丟棄,而結晶產物可用於進一步用途。
本發明之化合物特別有利地適用於尤其是經由濕式化學方法進行的具有經改良電性質之含氧化銦塗層的製造。
由於大體上尋求具有非常低結晶傾向之物質作為金屬氧化物的前驅物,此改善令人意外。然而,本發明之化合物經常為已具有微晶結構之團簇化合物。所希望之金屬氧化物層應具有之非晶形特徵而非結晶特徵的傾向,以具有特定良好電性質。與預期相反的,使用本發明之化合物可製造特別均勻的層。
在此情況下,用於含氧化銦塗層係指氧化銦層及基本上由氧化銦及其他金屬及/或金屬氧化物組成之層。就本發明目的而言,氧化銦層為從所提及之銦烷氧化物製造的金屬層及基本上包含銦原子或離子,該等銦原子或離子基本上以氧化物形式存在。隨意地,氧化銦層亦隨意地包括來自不完全轉化之某些比例的鹵素或烷氧化物及/或氮、氫及/或碳。類似狀態亦適用於基本上包含氧化銦及其他金屬及/或金屬氧化物之層,但其條件係進一步包括其他金屬及/或金屬氧化物。
此外,本發明調合物具有可特別容易用於製造電子組件之導電性或半導體氧化銦塗層,特別是用於製造(薄膜)電晶體、二極體或太陽能電池的令人意外之優點。
本發明另外提供一種製造含氧化銦層之方法,其中將本發明之調合物施加至(隨意地經預塗覆或預處理)的基板,隨意地利用熱及/或電磁輻射乾燥及轉化。
本發明方法中所使用之基板較佳為選自由玻璃、矽、二氧化矽、金屬氧化物或過渡金屬氧化物或聚合材料(特別是PE、PEN、PI或PET)組成之基板。
在塗覆之後且在轉化之前,該經塗覆基板亦可經乾燥。熟習本領域之人士已習知用於該目的之適當方法及條件。然而,經塗覆之基板不一定必須在轉化前乾燥。
本發明之組成物特別適用於選自以下之塗覆方法印刷法(特別是快乾/凹版印刷、噴墨印刷、(反轉)套版印刷、數位套版印刷及網版印刷)、噴淋法(噴塗)、旋轉塗覆法(「旋塗」)、浸塗法(「浸塗」)之方法,及其他液相塗覆法,諸如縫模塗布法、狹縫塗布、淋幕式塗布法及刮刀法。
將所製造之結構或層轉化成氧化銦層或含氧化銦層或氧化銦結構或含氧化銦結構可藉由熱途徑及/或利用入UV、IR或VIS輻射進行。
然而,當溫度為20℃至550℃時可獲致特別良好結果,較佳係使用100至400℃,特佳係使用150至350℃以供轉化。
此外,作為替代或者是除此之外,可使用電磁輻射(特別是UV輻射)轉化所應用之調合物。較佳係使用具有在160至300nm範圍之波長的電磁輻射來轉化。轉化較佳可利用在250至258及180至190nm之範圍中具有顯著輻射分量的UVO輻射進行,該輻射可例如利用特定汞蒸汽燈產生。亦可使用來自準分子燈或準分子雷射之轉化,特別是使用在160至190nm之範圍的波長之輻射。
當所施加之調合物係利用熱(特別是在100至400℃,特佳為150至350℃之溫度)及利用電磁輻射(特別是具有
在160至300nm之範圍的波長之電磁輻射)轉化時,形成特別良好的層。
通常使用從數秒至數小時之轉化時間。轉化時間通常為1秒至24小時,較佳為10秒至2小時,更佳為1分鐘至40分鐘,特佳為1分鐘至20分鐘。
亦可在熱處理之前藉由使在塗覆步驟之後所獲得之層與水及/或過氧化氫接觸來協助轉化,如此該層先在進行熱轉化之前的中間步驟中轉化成金屬氫氧化物。
此外,所施加之塗覆組成物的轉化可在標準大氣壓力水含量下進行。
藉由本發明方法所獲得之層的品質可藉由在轉化步驟之後結合熱處理及氣體處理(使用H2或O2)、電漿處理(Ar、N2、O2或H2電漿)、微波處理、雷射處理(使用在UV、VIS或IR範圍之波長)、UV光、紅外輻射或臭氧處理而獲得進一步改善。
圖1顯示本發明之最佳化合物[In6(O)(OMe)12Cl6]2-[NH2R2]+ 2(MeOH)2的結構,其係藉由X射線結構分析測定。
以下實例說明本發明標的物且其本身不具限制效果。
在30l之無殘留水分的反應器中,在保護性氣體氣氛下藉由攪拌將1.30kg之氯化銦(III)(InCl3,5.9莫耳)懸浮在17.38kg之乾燥甲醇中。在室溫下利用質量流控制器計量加入二甲胺(2.57kg,57莫耳)(0.86kg/h,約4小時),其過程中可觀察到稍微放熱反應。然後,使反應混合物在50℃加熱2小時,冷卻至室溫及過濾之。過濾器殘留物係以4×500ml之經乾燥之甲醇清洗,且在減壓下(0.1毫巴)乾燥8小時。將該材料溶解於沸騰甲醇中且於-20℃結晶出來。
將所獲得之材料以50mg/ml之濃度溶解於1-甲氧基-2-丙醇中。所獲得之濃縮物係如下調配:1份濃縮物對2份1-甲氧基-2-丙醇對1份乙醇。於此調合物中另外添加3重量%之四氫糠醇(THFA)。所使用之所有溶劑均為無水的(<200ppm H2O),且混合係在惰性條件(同樣為無水)下進行。所獲得之調合物最終經過200nm PTFE過濾器過濾。
以100μl上述調合物濕潤邊緣長度為約15mm且約200nm厚之氧化矽塗層及ITO/金所構成的指狀結構之經摻雜矽基板。然後以2000rpm進行旋塗(30秒)。在此塗覆操作之後立刻以來自汞蒸汽燈之在150至300nm之波
長範圍的UV輻射照射經塗覆基板10分鐘。該基板隨後係在熱板上以350℃之溫度的加熱1小時。在轉化之後,可於套手工作箱中在2VDS下測定μFET場效移動性之值(線性範圍)為=14cm2/Vs。
在500ml之無殘留水分的圓底燒瓶中,在保護氣體氣氛下藉由攪拌將5.0g之氯化銦(III)(InCl3,22.5毫莫耳)溶解於250ml乾燥甲醇中,留下<10重量%(以秤入之量為基準計)之InCl3殘留物。二甲胺鹼(5.0g,對應於111毫莫耳)之計量添加係利用質量流控制器來確保,且在5小時期間於室溫下以根據InCl3為基準的化學計量之量添加該鹼,觀察到在開始時有些微放熱反應。隨後,該溶液完全蒸發,以250ml之乾燥甲醇收集殘留固體,在保護氣體(N2)下過濾該混合物,以乾燥甲醇清洗多次(10次操作)及在減壓(<10毫巴)下於室溫乾燥12小時。產物產率為>80莫耳%之氯二甲氧化銦(III)(indium(III)chlordimethoxide)。
將所獲得之材料以50mg/ml之濃度溶解於1-甲氧基-2-丙醇中。所獲得之濃縮物係如下調配:1份濃縮物對2份1-甲氧基-2-丙醇對1份乙醇。於此調合物中另外添加3
重量%之四氫糠醇(THFA)。所使用之所有溶劑均為無水的(<200ppm H2O),且混合係在惰性條件(同樣為無水)下進行。所獲得之調合物最終經過200nm PTFE過濾器過濾。
以100μl上述調合物濕潤邊緣長度為約15mm且約200nm厚之氧化矽塗層及ITO/金所構成的指狀結構之經摻雜矽基板。然後以2000rpm進行旋塗(30秒)。在此塗覆操作之後立刻以來自汞蒸汽燈之在150至300nm之波長範圍的UV輻射照射經塗覆基板10分鐘。該基板隨後係在熱板上以350℃之溫度的加熱1小時。在轉化之後,可於套手工作箱中在2VDS下測定μFET場效移動性之值(線性範圍)為=8cm2/Vs。
Claims (14)
- 一種液體調合物,其可藉由將至少一種銦烷氧化物化合物溶解於至少一種溶劑所製造,該銦烷氧化物化合物可藉由在通式ROH之醇(其中R=烷基)存在令- 三鹵化銦(InX3其中X=F、Cl、Br、I)- 與相對於該三鹵化銦之莫耳比為8:1至20:1的式R'2NH之二級胺(其中R'=烷基)反應而製備,其中該化合物具有通式[In6(O)(OR)12X6]2-Am z(ROH)x其中R=烷基,X=F、Cl、Br、I,A=陽離子,z=陽離子價,m.z=2且x=0至10。
- 如申請專利範圍第1項之調合物,其中該化合物具有通式[In6(O)(OMe)12Cl6]2-[NH2R2]+ 2(MeOH)2。
- 如申請專利範圍第1至2項中任一項之調合物,其包含根據該調合物之總質量計為0.1至10重量%之比例的銦烷氧化物化合物。
- 如申請專利範圍第1至2項中任一項之調合物,其中該至少一種溶劑係選自由以下所組成之群組:一級、二級、三級及芳族醇類、醚類、酯類、芳族烴類及腈類。
- 如申請專利範圍第1至2項中任一項之調合物,其中該至少一種溶劑係選自由以下所組成之群組:甲醇、乙醇、丁醇、四氫糠醇、酚、2-甲氧基乙醇、1-甲氧基-2-丙醇、四氫呋喃、苯基甲基醚、乙酸丁酯、乙酸1-甲氧基-2-丙酯(PGMEA)、苯甲酸乙酯、二乙酸乙二醇酯、乳酸乙酯、乳酸丁酯、甲苯、二甲苯及乙腈。
- 如申請專利範圍第5項之調合物,其包含至少三種溶劑,其中一者係選自由以下所組成之群組:乳酸乙酯、苯基甲基醚、四氫糠醇、乙酸丁酯、二乙酸乙二醇酯及苯甲酸乙酯,且其他二者在SATP條件下之沸點差異為至少30℃。
- 如申請專利範圍第1至2項中任一項之調合物,其包含乙醇、1-甲氧基-2-丙醇及四氫糠醇三種溶劑。
- 如申請專利範圍第1至2項中任一項之調合物,其基本上不含水。
- 一種用於製造如申請專利範圍第1至8項中任一項之調合物的方法,其中可藉由將至少一種銦烷氧化物化合物與至少一種溶劑混合,該銦烷氧化物化合物可藉由在通式ROH之醇(其中R=烷基)存在下令- 三鹵化銦(InX3其中X=F、Cl、Br、I)- 與相對於該三鹵化銦之莫耳比為8:1至20:1的式R'2NH之二級胺(其中R'=烷基)反應而製備。
- 一種如申請專利範圍第1至8項中任一項之調合物的用途,其係用於製造含氧化銦層。
- 一種如申請專利範圍第1至8項中任一項之調合物的用途,其係用於製造電子組件之半導體層或導電層。
- 一種如申請專利範圍第1至8項中任一項之調合物的用途,其係用於製造(薄膜)電晶體、二極體或太陽能電池。
- 一種用於製造含氧化銦層之方法,其中將如申請專利範圍第1至8項中任一項之調合物施用於基板且藉由熱及/或電磁輻射予以轉化。
- 如申請專利範圍第13項之方法,其中該施用之調合物係藉由熱及電磁輻射予以轉化。
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DE102013212017A1 (de) | 2013-06-25 | 2015-01-08 | Evonik Industries Ag | Verfahren zur Herstellung von Indiumalkoxid-Verbindungen, die nach dem Verfahren herstellbaren Indiumalkoxid-Verbindungen und ihre Verwendung |
CN109063980A (zh) * | 2018-07-16 | 2018-12-21 | 北京科东电力控制***有限责任公司 | 适用于电网分析的内存计算方法和*** |
CN112480906A (zh) * | 2020-11-24 | 2021-03-12 | 苏州星烁纳米科技有限公司 | 一种铟氧簇合物及其制备方法、由其制备的量子点及该量子点的制备方法 |
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CN102652137A (zh) * | 2009-12-18 | 2012-08-29 | 赢创德固赛有限公司 | 制备铟氯二醇盐的方法 |
CN103003286A (zh) * | 2010-07-21 | 2013-03-27 | 赢创德固赛有限公司 | 用于制备含氧化铟层的铟氧桥醇盐 |
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RU2181389C2 (ru) * | 1999-06-29 | 2002-04-20 | Омский научно-исследовательский институт приборостроения | Способ получения прозрачной электропроводящей пленки на основе оксидов индия и олова |
KR100627631B1 (ko) * | 2005-02-18 | 2006-09-25 | 한국화학연구원 | 휘발성 인듐 아미노 알콕사이드 화합물 및 그 제조 방법 |
DE102009009337A1 (de) | 2009-02-17 | 2010-08-19 | Evonik Degussa Gmbh | Verfahren zur Herstellung halbleitender Indiumoxid-Schichten, nach dem Verfahren hergestellte Indiumoxid-Schichten und deren Verwendung |
DE102009009338A1 (de) | 2009-02-17 | 2010-08-26 | Evonik Degussa Gmbh | Indiumalkoxid-haltige Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE102009028801B3 (de) | 2009-08-21 | 2011-04-14 | Evonik Degussa Gmbh | Verfahren zur Herstellung Indiumoxid-haltiger Schichten, nach dem Verfahren herstellbare Indiumoxid-haltige Schicht und deren Verwendung |
DE102009054997B3 (de) | 2009-12-18 | 2011-06-01 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Indiumoxid-haltigen Schichten, nach dem Verfahren hergestellte Indiumoxid-haltige Schichten und ihre Verwendung |
DE102010031895A1 (de) | 2010-07-21 | 2012-01-26 | Evonik Degussa Gmbh | Indiumoxoalkoxide für die Herstellung Indiumoxid-haltiger Schichten |
DE102010043668B4 (de) | 2010-11-10 | 2012-06-21 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Indiumoxid-haltigen Schichten, nach dem Verfahren hergestellte Indiumoxid-haltige Schichten und ihre Verwendung |
DE102012209918A1 (de) | 2012-06-13 | 2013-12-19 | Evonik Industries Ag | Verfahren zur Herstellung Indiumoxid-haltiger Schichten |
DE102013212017A1 (de) | 2013-06-25 | 2015-01-08 | Evonik Industries Ag | Verfahren zur Herstellung von Indiumalkoxid-Verbindungen, die nach dem Verfahren herstellbaren Indiumalkoxid-Verbindungen und ihre Verwendung |
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CN102652137A (zh) * | 2009-12-18 | 2012-08-29 | 赢创德固赛有限公司 | 制备铟氯二醇盐的方法 |
CN103003286A (zh) * | 2010-07-21 | 2013-03-27 | 赢创德固赛有限公司 | 用于制备含氧化铟层的铟氧桥醇盐 |
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EP3013837A1 (de) | 2016-05-04 |
CN105555790B (zh) | 2018-12-28 |
US9812330B2 (en) | 2017-11-07 |
RU2016101886A (ru) | 2017-07-28 |
JP6366702B2 (ja) | 2018-08-01 |
RU2659030C2 (ru) | 2018-06-27 |
JP2016534993A (ja) | 2016-11-10 |
DE102013212019A1 (de) | 2015-01-08 |
TW201516022A (zh) | 2015-05-01 |
EP3013837B1 (de) | 2017-05-31 |
US20160141177A1 (en) | 2016-05-19 |
WO2014206599A1 (de) | 2014-12-31 |
KR102123262B1 (ko) | 2020-06-17 |
CN105555790A (zh) | 2016-05-04 |
KR20160022887A (ko) | 2016-03-02 |
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