TWI663652B - Metal oxide semiconductor film, thin film transistor , and electronic device - Google Patents
Metal oxide semiconductor film, thin film transistor , and electronic device Download PDFInfo
- Publication number
- TWI663652B TWI663652B TW104132656A TW104132656A TWI663652B TW I663652 B TWI663652 B TW I663652B TW 104132656 A TW104132656 A TW 104132656A TW 104132656 A TW104132656 A TW 104132656A TW I663652 B TWI663652 B TW I663652B
- Authority
- TW
- Taiwan
- Prior art keywords
- oxide semiconductor
- metal oxide
- film
- semiconductor film
- tin
- Prior art date
Links
- 239000010408 film Substances 0.000 title claims abstract description 220
- 239000004065 semiconductor Substances 0.000 title claims abstract description 179
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 162
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 162
- 239000010409 thin film Substances 0.000 title claims abstract description 40
- 239000011135 tin Substances 0.000 claims abstract description 91
- 239000011701 zinc Substances 0.000 claims abstract description 69
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000001004 secondary ion mass spectrometry Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 abstract description 63
- 238000000034 method Methods 0.000 abstract description 61
- 239000000758 substrate Substances 0.000 abstract description 58
- 238000004519 manufacturing process Methods 0.000 abstract description 44
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000010438 heat treatment Methods 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 17
- 239000000243 solution Substances 0.000 description 56
- 239000010410 layer Substances 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 18
- 239000003990 capacitor Substances 0.000 description 17
- 238000005401 electroluminescence Methods 0.000 description 16
- 229910052738 indium Inorganic materials 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 14
- 238000010586 diagram Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- -1 polybutylene terephthalate Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000000059 patterning Methods 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 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 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009429 electrical wiring Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920002098 polyfluorene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 229910007604 Zn—Sn—O Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- 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
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Thin Film Transistor (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
提供一種可形成氧化物半導體膜的金屬氧化物半導體膜的製造方法及金屬氧化物半導體膜、薄膜電晶體及電子元件。本發明的金屬氧化物半導體膜的製造方法包括：金屬氧化物半導體前驅物膜形成步驟，將包含溶劑及作為金屬成分的鋅與錫的溶液塗佈於基板上，而形成金屬氧化物半導體前驅物膜；轉化步驟，藉由在加熱金屬氧化物半導體前驅物膜的狀態下進行紫外線照射，而使金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜；金屬氧化物半導體前驅物膜中的全部金屬成分的80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9。 Provided are a method for manufacturing a metal oxide semiconductor film capable of forming an oxide semiconductor film, a metal oxide semiconductor film, a thin film transistor, and an electronic component. The method for manufacturing a metal oxide semiconductor film of the present invention includes a metal oxide semiconductor precursor film forming step of applying a solution containing a solvent and zinc and tin as metal components on a substrate to form a metal oxide semiconductor precursor. A conversion step of converting the metal oxide semiconductor precursor film into a metal oxide semiconductor film by performing ultraviolet irradiation while heating the metal oxide semiconductor precursor film; all of the metal oxide semiconductor precursor film More than 80% of the metal components are zinc and tin, and the composition ratio of zinc to tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
Description
本發明是有關於一種金屬氧化物半導體膜的製造方法及金屬氧化物半導體膜、薄膜電晶體及電子元件。 The invention relates to a method for manufacturing a metal oxide semiconductor film, a metal oxide semiconductor film, a thin film transistor, and an electronic component.
作為氧化物半導體膜或氧化物導體膜的金屬氧化物膜在藉由真空成膜法的製造中實現實用化，目前受到關注。 A metal oxide film, which is an oxide semiconductor film or an oxide conductor film, has been put to practical use in production by a vacuum film formation method, and has attracted attention at present.
另外，為了在耐熱性低的樹脂基板上形成金屬氧化物半導體，而要求在低溫下形成金屬氧化物半導體膜。 In addition, in order to form a metal oxide semiconductor on a resin substrate having low heat resistance, it is required to form a metal oxide semiconductor film at a low temperature.
因此，關於以在低溫、且大氣壓下簡便地形成具有高的半導體特性的氧化物半導體膜為目的的藉由液相製程的氧化物半導體膜的製作，正在積極地進行研究開發。最近，報告了如下的方法：藉由將溶液塗佈於基板上，並使用紫外線，而在150℃以下的低溫下製造具有高的傳輸特性的薄膜電晶體(Thin Film Transistor，TFT)(參照非專利文獻1)。 Therefore, research and development are being actively conducted on the production of oxide semiconductor films by a liquid phase process for the purpose of easily forming oxide semiconductor films having high semiconductor characteristics at low temperature and atmospheric pressure. Recently, a method has been reported in which a thin film transistor (TFT) having high transmission characteristics is produced at a low temperature of 150 ° C. or lower by applying a solution on a substrate and using ultraviolet rays (refer to Patent Document 1).
另外揭示了如下的方法：在將包含硝酸鹽等的溶液塗佈於基材上後，以150℃左右加熱使溶劑揮發，藉此形成包含金屬氧化物半導體的前驅物的薄膜，然後，在氧存在下照射紫外光(Ultraviolet，UV)，從而製造金屬氧化物半導體(參照專利文獻 1)。 In addition, a method is disclosed in which a solution containing a nitrate or the like is coated on a substrate, and then the solvent is volatilized by heating at about 150 ° C to form a thin film containing a precursor of a metal oxide semiconductor. Ultraviolet (UV) irradiation in the presence of a metal oxide semiconductor (see Patent Documents) 1).
此處，在非專利文獻1中報告如下：表現出高的傳輸特性的僅為在金屬氧化物半導體膜中包含銦者，在不含銦的Zn-Sn-O系中無法確認到電晶體動作。 Here, in Non-Patent Document 1, it is reported as follows: Only those that exhibit high transmission characteristics include indium in the metal oxide semiconductor film, and the transistor operation cannot be confirmed in a Zn-Sn-O system containing no indium. .
另外，專利文獻1中僅記載了包含銦的金屬氧化物半導體。 In addition, Patent Document 1 describes only a metal oxide semiconductor containing indium.
銦是生產量有限的稀有金屬，能預料到今後的供給量的緊缺、原料價格的飛漲，因而要求不使用銦的材料作為金屬氧化物半導體的材料。 Indium is a rare metal with limited production. It can be expected that the future supply will be scarce and the price of raw materials will soar. Therefore, materials that do not use indium are required as materials for metal oxide semiconductors.
因此，研究了藉由液相製程來製作不含銦的金屬氧化物半導體。 Therefore, it has been studied to produce indium-free metal oxide semiconductors by a liquid phase process.
例如，在非專利文獻2中報告了如下的嘗試：在作為不含銦的金屬氧化物半導體的Zn-Sn-O系薄膜的製作中，應用併用紫外線照射的退火處理。 For example, Non-Patent Document 2 has reported an attempt to apply an annealing treatment in which a Zn-Sn-O-based thin film as a metal oxide semiconductor containing no indium is irradiated with ultraviolet rays.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]國際公開第2009/011224號 [Patent Document 1] International Publication No. 2009/011224
[非專利文獻] [Non-patent literature]
[非專利文獻1]自然(Nature)、489 (2012) 128. [Non-Patent Document 1] Nature, 489 (2012) 128.
[非專利文獻2]電化學與固態快報(Electrochemical and Solid-State Letters)、15 (2012) H91. [Non-Patent Document 2] Electrochemical and Solid-State Letters, 15 (2012) H91.
然而，在非專利文獻2所記載的Zn-Sn-O系薄膜的製造方法中，為了實現良好的電晶體動作，而在進行併用紫外線照射的退火處理後，必須實施真空中的退火處理。因此，存在生產成本增加的問題。 However, in the method for manufacturing a Zn-Sn-O-based thin film described in Non-Patent Document 2, in order to achieve a good transistor operation, an annealing treatment in a vacuum must be performed after performing an annealing treatment in combination with ultraviolet irradiation. Therefore, there is a problem that production costs increase.
本發明的目的在於解決此種現有技術的問題點，目的是提供一種可使用不含作為稀有金屬的銦的廉價的材料，而形成能簡便地在低溫、且大氣壓下形成、並具有高的半導體特性的氧化物半導體膜的金屬氧化物半導體膜的製造方法及金屬氧化物半導體膜、薄膜電晶體及電子元件。 An object of the present invention is to solve such a problem of the prior art, and an object of the present invention is to provide a semiconductor which can be easily formed at a low temperature and an atmospheric pressure by using an inexpensive material which does not contain indium as a rare metal, and which has a high semiconductor pressure. A method for producing a metal oxide semiconductor film having a characteristic oxide semiconductor film, a metal oxide semiconductor film, a thin film transistor, and an electronic component.
本發明者為了達成所述目的而進行努力研究，結果發現，藉由：包括金屬氧化物半導體前驅物膜形成步驟，將包含溶劑及作為金屬成分的鋅與錫的溶液塗佈於基板上，而形成金屬氧化物半導體前驅物膜；及轉化步驟，藉由在加熱金屬氧化物半導體前驅物膜的狀態下進行紫外線照射，而使金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜；金屬氧化物半導體前驅物膜中的全部金屬成分的80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9，而可使用不含銦的廉價的材料，形成能簡便地在低溫、且大氣壓下形成、並具有高的半導體特性的氧化物半導體膜，從而完成了本發明。 The present inventors conducted diligent research in order to achieve the above-mentioned object, and as a result, they found that, by including a metal oxide semiconductor precursor film formation step, a solution containing a solvent and zinc and tin as metal components was coated on a substrate, and Forming a metal oxide semiconductor precursor film; and a conversion step of converting the metal oxide semiconductor precursor film into a metal oxide semiconductor film by performing ultraviolet irradiation while heating the metal oxide semiconductor precursor film; metal oxidation More than 80% of all metal components in the bio-semiconductor precursor film are zinc and tin, and the composition ratio of zinc to tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9, and an indium-free inexpensive material can be used to form An oxide semiconductor film that can be easily formed at low temperature and atmospheric pressure and has high semiconductor characteristics has completed the present invention.
即，發現藉由以下的構成而可達成所述目的。 That is, it was found that the above-mentioned object can be achieved by the following configuration.
[1]一種金屬氧化物半導體膜的製造方法，其包括：金屬 氧化物半導體前驅物膜形成步驟，將包含溶劑及作為金屬成分的鋅與錫的溶液塗佈於基板上，而形成金屬氧化物半導體前驅物膜；及轉化步驟，藉由在加熱金屬氧化物半導體前驅物膜的狀態下進行紫外線照射，而使金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜；金屬氧化物半導體前驅物膜中的全部金屬成分的80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9。 [1] A method for manufacturing a metal oxide semiconductor film, including: a metal An oxide semiconductor precursor film forming step of applying a solution containing a solvent and zinc and tin as metal components on a substrate to form a metal oxide semiconductor precursor film; and a conversion step by heating the metal oxide semiconductor The precursor film is irradiated with ultraviolet rays to convert the metal oxide semiconductor precursor film into a metal oxide semiconductor film; more than 80% of all metal components in the metal oxide semiconductor precursor film are zinc and tin. The composition ratio of tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
[2]如[1]所記載的金屬氧化物半導體膜的製造方法，其中金屬氧化物半導體前驅物膜中的銦的成分比小於5%。 [2] The method for producing a metal oxide semiconductor film according to [1], wherein the indium component ratio in the metal oxide semiconductor precursor film is less than 5%.
[3]如[1]或[2]所記載的金屬氧化物半導體膜的製造方法，其中在轉化步驟中，將紫外線照射中的基板的溫度保持為250℃以下。 [3] The method for producing a metal oxide semiconductor film according to [1] or [2], wherein in the conversion step, the temperature of the substrate during the ultraviolet irradiation is maintained at 250 ° C. or lower.
[4]如[1]至[3]中任一項所記載的金屬氧化物半導體膜的製造方法，其中在轉化步驟中，照射至金屬氧化物半導體前驅物膜的紫外線的波長300nm以下的照度為30mW/cm2以上。 [4] The method for producing a metal oxide semiconductor film according to any one of [1] to [3], wherein in the conversion step, the irradiance of the ultraviolet rays having a wavelength of 300 nm or less is irradiated to the metal oxide semiconductor precursor film. It is 30 mW / cm 2 or more.
[5]如[1]至[4]中任一項所記載的金屬氧化物半導體膜的製造方法，其中轉化步驟是在包含1體積%以上的氧的環境中進行。 [5] The method for producing a metal oxide semiconductor film according to any one of [1] to [4], wherein the conversion step is performed in an environment containing 1% by volume or more of oxygen.
[6]如[1]至[5]中任一項所記載的金屬氧化物半導體膜的製造方法，其中金屬氧化物半導體前驅物膜中的全部金屬成分的95%以上為鋅及錫。 [6] The method for producing a metal oxide semiconductor film according to any one of [1] to [5], wherein 95% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin.
[7]如[1]至[6]中任一項所記載的金屬氧化物半導體膜的製造 方法，其中溶液是將鋅及錫的金屬鹽或金屬鹵化物溶解於溶劑中而成者。 [7] Production of the metal oxide semiconductor film according to any one of [1] to [6] A method in which the solution is obtained by dissolving a metal salt or a metal halide of zinc and tin in a solvent.
[8]如[1]至[7]中任一項所記載的金屬氧化物半導體膜的製造方法，其中溶劑為甲醇、甲氧基乙醇、或水。 [8] The method for producing a metal oxide semiconductor film according to any one of [1] to [7], wherein the solvent is methanol, methoxyethanol, or water.
[9]如[1]至[8]中任一項所記載的金屬氧化物半導體膜的製造方法，其中溶液中的金屬成分的濃度為0.01mol/L~1.0mol/L。 [9] The method for producing a metal oxide semiconductor film according to any one of [1] to [8], wherein the concentration of the metal component in the solution is 0.01 mol / L to 1.0 mol / L.
[10]一種金屬氧化物半導體膜，其是使用如[1]至[9]中任一項所記載的金屬氧化物半導體膜的製造方法而製作。 [10] A metal oxide semiconductor film produced using the method for producing a metal oxide semiconductor film according to any one of [1] to [9].
[11]如[10]所記載的金屬氧化物半導體膜，其中藉由二次離子質譜法的膜中的碳濃度為1×1019atoms/cm3以上、1×1020atoms/cm3以下。 [11] The metal oxide semiconductor film according to [10], wherein the carbon concentration in the film by secondary ion mass spectrometry is 1 × 10 19 atoms / cm 3 or more and 1 × 10 20 atoms / cm 3 or less .
[12]如[10]或[11]所記載的金屬氧化物半導體膜，其中藉由二次離子質譜法的膜中的氫濃度為2×1022atoms/cm3以上、4×1022atoms/cm3以下。 [12] The metal oxide semiconductor film according to [10] or [11], wherein the hydrogen concentration in the film by secondary ion mass spectrometry is 2 × 10 22 atoms / cm 3 or more and 4 × 10 22 atoms / cm 3 or less.
[13]一種薄膜電晶體，其具有：包含如[10]至[12]中任一項所記載的金屬氧化物半導體膜的活性層、源極電極、汲極電極、閘極絕緣膜、以及閘極電極。 [13] A thin film transistor including the active layer including the metal oxide semiconductor film according to any one of [10] to [12], a source electrode, a drain electrode, a gate insulating film, and Gate electrode.
[14]一種電子元件，其具備如[13]所記載的薄膜電晶體。 [14] An electronic component including the thin-film transistor according to [13].
如以下所說明般，根據本發明，可提供一種可使用不含作為稀有金屬的銦的廉價的材料，而形成能簡便地在低溫、且大氣壓下形成、並具有高的半導體特性的氧化物半導體膜的金屬氧 化物半導體膜的製造方法及金屬氧化物半導體膜、薄膜電晶體及電子元件。 As described below, according to the present invention, it is possible to provide an oxide semiconductor that can be easily formed at low temperature and atmospheric pressure, and has high semiconductor characteristics by using an inexpensive material that does not contain indium as a rare metal, and can be formed at a high pressure. Metal oxide Manufacturing method of compound semiconductor film, metal oxide semiconductor film, thin film transistor and electronic component.
10‧‧‧薄膜電晶體 10‧‧‧ thin film transistor
10a‧‧‧驅動用薄膜電晶體 10a‧‧‧ thin film transistor for driving
10b‧‧‧開關用薄膜電晶體 10b‧‧‧Thin-film transistor for switch
12‧‧‧基板 12‧‧‧ substrate
14‧‧‧活性層(氧化物半導體層) 14‧‧‧active layer (oxide semiconductor layer)
16‧‧‧源極電極 16‧‧‧Source electrode
18‧‧‧汲極電極 18‧‧‧ Drain electrode
20‧‧‧閘極絕緣膜 20‧‧‧Gate insulation film
22‧‧‧閘極電極 22‧‧‧Gate electrode
30、40、50‧‧‧薄膜電晶體 30, 40, 50‧‧‧ thin film transistors
100‧‧‧液晶顯示裝置 100‧‧‧LCD display device
102、202、216‧‧‧鈍化層 102, 202, 216‧‧‧ passivation layer
104‧‧‧畫素下部電極 104‧‧‧Pixel lower electrode
106‧‧‧對向上部電極 106‧‧‧upper electrode
108‧‧‧液晶層 108‧‧‧LCD layer
110‧‧‧彩色濾光片 110‧‧‧ color filter
112a、112b‧‧‧偏光板 112a, 112b ‧‧‧ polarizing plate
113、220、320‧‧‧閘極配線 113, 220, 320‧‧‧Gate wiring
114、222、322‧‧‧資料配線 114, 222, 322‧‧‧ data wiring
116、318‧‧‧接觸孔 116, 318‧‧‧ contact hole
118、226、310‧‧‧電容器 118, 226, 310‧‧‧ capacitors
200‧‧‧有機EL顯示裝置 200‧‧‧Organic EL display device
208‧‧‧下部電極 208‧‧‧Lower electrode
210、306‧‧‧上部電極 210, 306‧‧‧upper electrode
212‧‧‧有機發光層 212‧‧‧Organic emitting layer
214‧‧‧有機EL發光元件 214‧‧‧Organic EL light-emitting element
224‧‧‧驅動配線 224‧‧‧Drive wiring
300‧‧‧X射線感測器 300‧‧‧ X-ray sensor
302‧‧‧電荷收集用電極 302‧‧‧ Charge collection electrode
304‧‧‧X射線轉換層 304‧‧‧X-ray conversion layer
308‧‧‧鈍化膜 308‧‧‧Passive film
312‧‧‧電容器用下部電極 312‧‧‧Capacitor lower electrode
314‧‧‧電容器用上部電極 314‧‧‧Capacitor upper electrode
316‧‧‧絕緣膜 316‧‧‧ insulating film
圖1是表示使用藉由本發明的製造方法而製造的金屬氧化物半導體膜的本發明的薄膜電晶體的一例(頂閘極-頂接觸型)的構成的概略圖。 FIG. 1 is a schematic diagram showing a configuration of an example (top gate-top contact type) of a thin film transistor of the present invention using a metal oxide semiconductor film manufactured by the manufacturing method of the present invention.
圖2是表示使用藉由本發明的製造方法而製造的金屬氧化物半導體膜的本發明的薄膜電晶體的一例(頂閘極-底接觸型)的構成的概略圖。 FIG. 2 is a schematic diagram showing a configuration of an example (top gate-bottom contact type) of a thin film transistor of the present invention using a metal oxide semiconductor film manufactured by the manufacturing method of the present invention.
圖3是表示使用藉由本發明的製造方法而製造的金屬氧化物半導體膜的本發明的薄膜電晶體的一例(底閘極-頂接觸型)的構成的概略圖。 3 is a schematic diagram showing a configuration of an example (bottom gate-top contact type) of a thin film transistor of the present invention using a metal oxide semiconductor film manufactured by the manufacturing method of the present invention.
圖4是表示使用藉由本發明的製造方法而製造的金屬氧化物半導體膜的本發明的薄膜電晶體的一例(底閘極-底接觸型)的構成的概略圖。 FIG. 4 is a schematic view showing a configuration of an example (bottom gate-bottom contact type) of a thin film transistor of the present invention using a metal oxide semiconductor film manufactured by the manufacturing method of the present invention.
圖5是表示使用本發明的薄膜電晶體的液晶顯示裝置的一部分的概略剖面圖。 5 is a schematic cross-sectional view showing a part of a liquid crystal display device using a thin film transistor of the present invention.
圖6是圖5的液晶顯示裝置的電配線的概略構成圖。 FIG. 6 is a schematic configuration diagram of electrical wiring of the liquid crystal display device of FIG. 5.
圖7是表示使用本發明的薄膜電晶體的有機電致發光(Electroluminescence，EL)顯示裝置的一部分的概略剖面圖。 FIG. 7 is a schematic cross-sectional view showing a part of an organic electroluminescence (EL) display device using a thin film transistor of the present invention.
圖8是圖7的有機EL顯示裝置的電配線的概略構成圖。 FIG. 8 is a schematic configuration diagram of electrical wiring of the organic EL display device of FIG. 7.
圖9是表示使用本發明的薄膜電晶體的X射線感測器陣列的一部分的概略剖面圖。 FIG. 9 is a schematic cross-sectional view showing a part of an X-ray sensor array using a thin film transistor of the present invention.
圖10是圖9的X射線感測器陣列的電配線的概略構成圖。 FIG. 10 is a schematic configuration diagram of electrical wiring of the X-ray sensor array of FIG. 9.
圖11是表示測定實施例1、實施例2及比較例1、比較例2中所製作的薄膜電晶體的閘極電壓與汲極電流的關係的結果的圖表。 FIG. 11 is a graph showing the results of measuring the relationship between the gate voltage and the drain current of the thin-film transistors produced in Example 1, Example 2, and Comparative Example 1 and Comparative Example 2. FIG.
圖12是表示測定比較例1、比較例4中所製作的薄膜電晶體的閘極電壓與汲極電流的關係的結果的圖表。 FIG. 12 is a graph showing the results of measuring the relationship between the gate voltage and the drain current of the thin film transistors produced in Comparative Example 1 and Comparative Example 4. FIG.
以下，對本發明進行詳細地說明。 Hereinafter, the present invention will be described in detail.
以下所記載的構成要件的說明有時是基於本發明的代表性的實施形態而進行，但本發明並不限定於此種實施形態。 The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
再者，在本說明書中，使用「~」表示的數值範圍，是指包含「~」的前後所記載的數值作為下限值及上限值的範圍。 In addition, in this specification, the numerical range represented by "~" means the range including the numerical value described before and after "~" as a lower limit and an upper limit.
<金屬氧化物半導體膜的製造方法> <Method for Manufacturing Metal Oxide Semiconductor Film>
本發明的金屬氧化物半導體膜的製造方法(以下亦稱為「本發明的製造方法」)的特徵在於：包括金屬氧化物半導體前驅物膜形成步驟，將包含溶劑及作為金屬成分的以錫為主成分且至少包含鋅的溶液塗佈於基板上，而形成金屬氧化物半導體前驅物膜；及轉化步驟，藉由在加熱金屬氧化物半導體前驅物膜的狀態下進行紫外線照射，而使金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜；金屬氧化物半導體前驅物膜中的全部金屬成分的 80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9。 The method for producing a metal oxide semiconductor film according to the present invention (hereinafter also referred to as the "manufacturing method of the present invention") is characterized in that it includes a metal oxide semiconductor precursor film forming step, and includes tin as a metal component and a solvent. A solution containing the main component and at least zinc is coated on the substrate to form a metal oxide semiconductor precursor film; and a conversion step of oxidizing the metal by performing ultraviolet irradiation while heating the metal oxide semiconductor precursor film Semiconductor precursor film into a metal oxide semiconductor film; all of the metal components in the metal oxide semiconductor precursor film More than 80% are zinc and tin, and the composition ratio of zinc to tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
根據本發明者等人的研究發現，藉由恰當地選擇鋅與錫的組成比，而可極為提高由紫外線照射處理帶來的金屬氧化物半導體膜的特性提高效果。 According to research by the present inventors, by properly selecting the composition ratio of zinc to tin, the effect of improving the characteristics of the metal oxide semiconductor film by the ultraviolet irradiation treatment can be extremely improved.
具體而言，藉由恰當地選擇鋅與錫的組成比，而可抑制伴隨著金屬氧化物半導體膜的結晶化的粒界形成及表面粗糙度的增大，且可將載體密度控制在恰當的範圍，因此可極為提高由紫外線照射處理帶來的金屬氧化物半導體膜的特性提高效果。 Specifically, by properly selecting the composition ratio of zinc to tin, the formation of grain boundaries and increase in surface roughness accompanying the crystallization of the metal oxide semiconductor film can be suppressed, and the carrier density can be controlled to be appropriate. Range, the effect of improving the characteristics of the metal oxide semiconductor film by the ultraviolet irradiation treatment can be extremely enhanced.
藉由使用本發明的製造方法，而可使用不含作為稀有金屬的銦的材料，在大氣壓下、250℃以下的低溫製程中，獲得具有高的電子傳遞特性的金屬氧化物半導體膜。 By using the manufacturing method of the present invention, a material containing no indium as a rare metal can be used, and a metal oxide semiconductor film having high electron transfer characteristics can be obtained in a low-temperature process at a temperature of 250 ° C. or lower under atmospheric pressure.
本發明的製造方法由於可在大氣壓下製造金屬氧化物半導體膜，因此無須使用大型的真空裝置。另外，由於可在250℃以下的低溫製程中製造，因此可使用耐熱性低的廉價的樹脂基板。可使用不含作為稀有金屬的銦的廉價的材料。因此，可大幅降低金屬氧化物半導體膜的製作成本。 Since the manufacturing method of the present invention can manufacture a metal oxide semiconductor film under atmospheric pressure, it is not necessary to use a large-scale vacuum device. In addition, since it can be manufactured in a low-temperature process at 250 ° C or lower, an inexpensive resin substrate with low heat resistance can be used. An inexpensive material that does not contain indium as a rare metal can be used. Therefore, the manufacturing cost of a metal oxide semiconductor film can be significantly reduced.
另外，由於可應用於耐熱性低的廉價的樹脂基板，因此可廉價地製作可撓性顯示器等的可撓性電子元件。 In addition, since it can be applied to an inexpensive resin substrate having low heat resistance, flexible electronic components such as a flexible display can be produced at low cost.
以下，對各步驟進行具體地說明。 Hereinafter, each step will be specifically described.
[金屬氧化物半導體前驅物膜形成步驟] [Metal Oxide Semiconductor Precursor Film Formation Step]
首先，準備包含溶劑及作為金屬成分的以錫為主成分且至少包含鋅的溶液(金屬氧化物半導體前驅物溶液)，塗佈於基板上而 形成金屬氧化物半導體前驅物膜。 First, a solution (metal oxide semiconductor precursor solution) containing a solvent and tin as a main component and containing at least zinc as a metal component is prepared and applied on a substrate to A metal oxide semiconductor precursor film is formed.
此處，在本發明中，在金屬氧化物半導體前驅物膜形成步驟中所形成的金屬氧化物半導體前驅物膜，膜中的全部金屬成分的80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9。 Here, in the present invention, in the metal oxide semiconductor precursor film formed in the metal oxide semiconductor precursor film forming step, more than 80% of all metal components in the film are zinc and tin, and the composition of zinc and tin is The ratio is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
(基板) (Substrate)
基板的形狀、結構、大小等並無特別限制，可根據目的進行適當選擇。基板的結構可為單層結構，亦可為積層結構。 The shape, structure, size, and the like of the substrate are not particularly limited, and can be appropriately selected according to the purpose. The structure of the substrate may be a single-layer structure or a laminated structure.
作為基板，並無特別限定，例如可使用：釔穩定化鋯(Yttria-Stabilized Zirconia，YSZ)、玻璃等無機基板，樹脂基板、或其複合材料等。其中就輕量、具有可撓性的方面而言，較佳為樹脂基板、其複合材料。具體可使用：聚對苯二甲酸丁二酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚苯乙烯、聚碳酸酯、聚碸、聚醚碸、聚芳酯、二乙二醇碳酸烯丙酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚苯并唑、聚苯硫醚、聚環烯烴、降冰片烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸系樹脂、環氧樹脂、矽酮樹脂、離子聚合物樹脂、氰酸酯樹脂、交聯反丁烯二酸二酯、環狀聚烯烴、芳香族醚、順丁烯二醯亞胺-烯烴、纖維素、環硫化合物等的合成樹脂基板，與氧化矽粒子的複合塑膠材料，與金屬奈米粒子、無機氧化物奈米粒子、無機氮化物奈米粒子等的複合塑膠材料，與碳纖維、碳奈米管的複合塑膠材料，與玻璃碎片、玻璃纖維、玻璃珠的複合塑膠材料，與黏土礦物或具有雲母派生結晶結構的粒子的複合 塑膠材料，在薄的玻璃與所述單獨有機材料之間具有至少一次的接合界面的積層塑膠材料，藉由交替積層無機層與有機層而具有至少一次以上的接合界面的具有阻隔性能的複合材料，不鏽鋼基板或積層有與不鏽鋼不同種金屬的金屬多層基板，鋁基板或藉由對表面實施氧化處理(例如陽極氧化處理)而提高了表面的絕緣性的附有氧化皮膜的鋁基板等。另外，樹脂基板的耐熱性、尺寸穩定性、耐溶劑性、電絕緣性、加工性、低通氣性、或低吸濕性等優異而較佳。所述樹脂基板可具備：用以防止水分或氧透過的阻氣層、或用以提高樹脂基板的平坦性或與下部電極的密接性的底塗層等。 The substrate is not particularly limited. For example, an inorganic substrate such as Yttria-Stabilized Zirconia (YSZ), glass, a resin substrate, or a composite material thereof can be used. Among them, a resin substrate and a composite material thereof are preferred in terms of light weight and flexibility. Specific use: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polyfluorene, poly Ether fluorene, polyarylate, allyl carbonate diethylene glycol, polyfluorene, polyfluorene imine, polyfluorene fluorene imine, polyether fluorene, polybenzoxazole, polyphenylene sulfide, polycyclic ring Fluorine resins such as olefins, norbornene resins, polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionic polymer resins, cyanate resins, crosslinked fumaric acid Synthetic resin substrates such as esters, cyclic polyolefins, aromatic ethers, maleimide-olefins, cellulose, episulfide compounds, composite plastic materials with silicon oxide particles, metal nano particles, and inorganic oxidation Composite plastic materials such as nano particles, inorganic nitride nano particles, composite plastic materials with carbon fibers and carbon nanotubes, composite plastic materials with glass fragments, glass fibers, and glass beads, derived from clay minerals or with mica Crystal structure of particles Plastic material, a laminated plastic material having a bonding interface between thin glass and the separate organic material at least once, and a composite material having barrier properties by alternately laminating an inorganic layer and an organic layer and having a bonding interface more than once A stainless steel substrate or a metal multilayer substrate laminated with a different kind of metal from stainless steel, an aluminum substrate, or an aluminum substrate with an oxide film on which the surface insulation is improved by performing an oxidation treatment (such as anodizing treatment) on the surface. In addition, a resin substrate is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, processability, low air permeability, and low hygroscopicity. The resin substrate may include a gas barrier layer to prevent moisture or oxygen from permeating, or an undercoat layer to improve the flatness of the resin substrate or the adhesion with the lower electrode.
另外，本發明中的基板的厚度並無特別限制，較佳為50μm以上、500μm以下。若基板的厚度為50μm以上，則基板自身的平坦性進一步提高。另外，若基板的厚度為500μm以下，則基板自身的可撓性進一步提高，作為可撓性元件用基板的使用變得更容易。 The thickness of the substrate in the present invention is not particularly limited, but it is preferably 50 μm or more and 500 μm or less. When the thickness of the substrate is 50 μm or more, the flatness of the substrate itself is further improved. In addition, when the thickness of the substrate is 500 μm or less, the flexibility of the substrate itself is further improved, and the use as a substrate for a flexible element becomes easier.
(溶液) (Solution)
所述金屬氧化物半導體前驅物溶液包含溶劑及以錫為主成分且至少包含鋅的金屬成分。此處，本發明中的主成分是指在所述溶液中錫佔全部金屬成分的50%以上，根據需要可包含少量的其他金屬成分。 The metal oxide semiconductor precursor solution includes a solvent and a metal component containing tin as a main component and at least zinc. Here, the main component in the present invention means that tin accounts for 50% or more of the total metal components in the solution, and may contain a small amount of other metal components as necessary.
另外，就所形成的金屬氧化物半導體膜的半導體特性的觀點而言，鋅及錫在全部金屬成分中的成分比較佳為90%以上，更佳 為95%以上。 In addition, from the viewpoint of the semiconductor characteristics of the formed metal oxide semiconductor film, the composition of zinc and tin in all metal components is preferably 90% or more, and more preferably More than 95%.
另外，所述溶液可包含小於5%的少量的銦，更佳為1%以下。 In addition, the solution may contain a small amount of indium less than 5%, and more preferably 1% or less.
此處，所述溶液中的金屬成分基本上與金屬氧化物半導體前驅物膜中的金屬成分相同。因此，在本發明中，所述溶液的鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9。 Here, the metal component in the solution is substantially the same as the metal component in the metal oxide semiconductor precursor film. Therefore, in the present invention, the composition ratio of zinc to tin in the solution is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
本發明中的溶液是以溶液成為所期望的濃度的方式秤量成為原料的溶質，並在溶劑中攪拌、使其溶解而得。關於進行攪拌的時間或攪拌中的溶液的溫度，若溶質充分溶解，則並無特別限制。 The solution in the present invention is obtained by measuring a solute that becomes a raw material so that the solution has a desired concentration, and stirring and dissolving in a solvent. Regarding the time for stirring or the temperature of the solution during stirring, there is no particular limitation as long as the solute is sufficiently dissolved.
所述金屬氧化物半導體前驅物溶液是將含有鋅及錫的化合物溶解而得，較佳為使用鋅及錫的金屬鹽或金屬鹵化物。藉由使用金屬鹽或金屬鹵化物，而可容易地在各種溶劑中溶解溶質，且容易獲得高的電子傳遞特性。作為金屬鹽，可列舉：硫酸鹽、磷酸鹽、碳酸鹽、乙酸鹽、草酸鹽等，作為金屬鹵化物，可列舉：氯化物、碘化物、溴化物等。 The metal oxide semiconductor precursor solution is obtained by dissolving a compound containing zinc and tin, and a metal salt or a metal halide of zinc and tin is preferably used. By using a metal salt or a metal halide, a solute can be easily dissolved in various solvents, and high electron transfer characteristics can be easily obtained. Examples of the metal salt include sulfate, phosphate, carbonate, acetate, and oxalate. Examples of the metal halide include chloride, iodide, and bromide.
再者，本發明中的溶液較佳為使用在溶液中不含金屬氧化物粒子等不溶物的溶液。藉由使用在溶液中不含金屬氧化物粒子等不溶物的溶液，形成金屬氧化物半導體膜時的表面粗糙度變小，並可形成面內均勻性優異的金屬氧化物半導體膜。 The solution in the present invention is preferably a solution containing no insoluble matter such as metal oxide particles in the solution. By using a solution containing no insoluble matter such as metal oxide particles in the solution, the surface roughness when forming a metal oxide semiconductor film is reduced, and a metal oxide semiconductor film having excellent in-plane uniformity can be formed.
本發明中的溶液所用的溶劑若為含有用作溶質的鋅及錫的化合物能溶解者，則並無特別限制，例如可列舉：水、醇溶劑(甲醇、乙醇、丙醇、乙二醇等)、醯胺溶劑(甲醯胺、N,N- 二甲基甲醯胺等)、酮溶劑(丙酮、N-甲基吡咯啶酮、環丁碸、N,N-二甲基咪唑啶酮等)、醚溶劑(四氫呋喃、甲氧基乙醇等)、腈溶劑(乙腈等)、雜環式化合物(吡啶、噻唑等)、其他所述以外的含有雜原子的溶劑等。特別是就溶解性、塗佈性的觀點而言，較佳為使用甲醇、甲氧基乙醇、或水。 The solvent used in the solution of the present invention is not particularly limited as long as it can dissolve compounds containing zinc and tin used as solutes, and examples thereof include water and alcohol solvents (methanol, ethanol, propanol, ethylene glycol, etc.) ), Amine solvents (formamide, N, N- Dimethylformamide, etc.), ketone solvents (acetone, N-methylpyrrolidone, cyclobutane, N, N-dimethylimidazolidone, etc.), ether solvents (tetrahydrofuran, methoxyethanol, etc.) , Nitrile solvents (such as acetonitrile, etc.), heterocyclic compounds (such as pyridine, thiazole, etc.), and other heteroatom-containing solvents other than those described above. In particular, from the viewpoints of solubility and coatability, it is preferable to use methanol, methoxyethanol, or water.
所述金屬氧化物半導體前驅物溶液中的金屬成分的濃度可根據黏度或欲獲得的膜厚而任意選擇，就薄膜的平坦性及生產性的觀點而言，較佳為0.01mol/L以上、1.0mol/L以下。 The concentration of the metal component in the metal oxide semiconductor precursor solution can be arbitrarily selected according to the viscosity or the film thickness to be obtained. From the viewpoint of the flatness and productivity of the thin film, it is preferably 0.01 mol / L or more 1.0mol / L or less.
(塗佈) (Coated)
作為將所述金屬氧化物半導體膜前驅物溶液塗佈於基板上的方法，例如可列舉：噴塗法、旋塗法、刮刀塗佈法、浸塗法、澆鑄法、輥塗法、棒塗法、模塗法、噴霧法、噴墨法、分配器法、網版印刷法、凸版印刷法、及凹版印刷法等。特別是就容易形成微細圖案的觀點而言，較佳為使用選自噴墨法、分配器法、凸版印刷法、及凹版印刷法中的至少一種塗佈法。 Examples of a method for applying the metal oxide semiconductor film precursor solution to a substrate include a spray method, a spin coating method, a doctor blade coating method, a dip coating method, a casting method, a roll coating method, and a rod coating method. , Die coating method, spray method, inkjet method, dispenser method, screen printing method, letterpress printing method, and gravure printing method. In particular, from the viewpoint of easily forming a fine pattern, it is preferable to use at least one coating method selected from the group consisting of an inkjet method, a dispenser method, a letterpress method, and a gravure method.
(乾燥) (dry)
在將所述金屬氧化物半導體前驅物溶液塗佈於基板上後，可進行自然乾燥而形成金屬氧化物半導體前驅物膜，較佳為藉由加熱處理使塗佈膜乾燥，而獲得金屬氧化物半導體前驅物膜。藉由乾燥，而可降低塗佈膜的流動性，並提高最終所得的金屬氧化物半導體膜的平坦性。另外，藉由選擇恰當的乾燥溫度(35℃以上、100℃以下)，而最終容易獲得電子傳遞特性更高的金屬氧化物半 導體膜。加熱處理的方法並無特別限定，可自加熱板加熱、電爐加熱、紅外線加熱、微波加熱等中進行選擇。 After the metal oxide semiconductor precursor solution is applied on a substrate, the metal oxide semiconductor precursor film can be naturally dried to form a metal oxide semiconductor precursor film. Preferably, the coating film is dried by heat treatment to obtain a metal oxide. Semiconductor precursor film. By drying, the fluidity of the coating film can be reduced, and the flatness of the finally obtained metal oxide semiconductor film can be improved. In addition, by selecting an appropriate drying temperature (35 ° C or higher and 100 ° C or lower), it is finally easy to obtain a metal oxide half having a higher electron transfer characteristic. Conductor film. The method of heat treatment is not particularly limited, and may be selected from heating plate heating, electric furnace heating, infrared heating, microwave heating, and the like.
就均勻地保持膜的平坦性的觀點而言，所述乾燥較佳為於在基板上塗佈溶液後，在5分鐘以內開始。 From the viewpoint of uniformly maintaining the flatness of the film, the drying is preferably started within 5 minutes after the solution is applied to the substrate.
另外，進行乾燥的時間並無特別限制，就膜的均勻性、生產性的觀點而言，較佳為15秒鐘以上、10分鐘以下。 The time for drying is not particularly limited, but it is preferably 15 seconds or more and 10 minutes or less from the viewpoint of film uniformity and productivity.
另外，乾燥時的環境並無特別限制，就製造成本等的觀點而言，較佳為在大氣壓下、大氣中進行。 In addition, the environment at the time of drying is not particularly limited, and from the viewpoint of manufacturing costs and the like, it is preferably performed under atmospheric pressure and in the atmosphere.
[轉化步驟] [Conversion step]
繼而，藉由在加熱所述金屬氧化物半導體前驅物膜的狀態下進行紫外線照射處理，而將金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜。 Then, the metal oxide semiconductor precursor film is converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment in a state where the metal oxide semiconductor precursor film is heated.
此處，如上所述般，金屬氧化物半導體前驅物膜由於膜中的全部金屬成分的80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9，因此可藉由大氣壓下、且250℃以下的低溫下的紫外線照射處理，而極為提高金屬氧化物半導體膜的特性提高效果。 Here, as described above, since 80% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin, the composition ratio of zinc to tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9, Therefore, the effect of improving the characteristics of the metal oxide semiconductor film can be greatly improved by the ultraviolet irradiation treatment at atmospheric pressure and at a low temperature of 250 ° C or lower.
(加熱處理) (Heat treatment)
向所述金屬氧化物半導體膜的轉化步驟中的基板溫度較佳為設為250℃以下，且較佳為設為超過120℃。若將轉化步驟中的基板溫度設為250℃以下，則可抑制熱能的增大而將製造成本抑制在低的水準，另外，在耐熱性低的樹脂基板中的應用變得容易。另 外，若將轉化步驟中的基板溫度設為超過120℃，則能以更短時間獲得電子傳遞特性高的金屬氧化物半導體膜。 The substrate temperature in the conversion step to the metal oxide semiconductor film is preferably set to 250 ° C or lower, and more preferably set to exceed 120 ° C. When the substrate temperature in the conversion step is 250 ° C. or lower, it is possible to suppress an increase in thermal energy and suppress a manufacturing cost to a low level, and it is easy to apply the resin substrate with low heat resistance. another In addition, if the substrate temperature in the conversion step is set to exceed 120 ° C, a metal oxide semiconductor film having a high electron transfer characteristic can be obtained in a shorter time.
另外，就製造成本的觀點及在樹脂基板中的應用的觀點而言，更佳為超過120℃、且200℃以下。 In addition, from the viewpoint of manufacturing cost and the viewpoint of application to a resin substrate, it is more preferably higher than 120 ° C and lower than 200 ° C.
轉化步驟中對基板的加熱方法並無特別限定，只要自加熱板加熱、電爐加熱、紅外線加熱、微波加熱等中進行選擇即可。 The method of heating the substrate in the conversion step is not particularly limited, as long as it is selected from heating plate heating, electric furnace heating, infrared heating, microwave heating, and the like.
(紫外線照射) (Ultraviolet radiation)
在轉化步驟中，照射至所述金屬氧化物半導體前驅物膜的紫外線的波長300nm以下的照度較佳為30mW/cm2以上，更佳為50mW/cm2。藉由將照度設為30mW/cm2以上，而可獲得電子傳遞特性高的金屬氧化物半導體膜。再者，就裝置成本的觀點而言，照度的上限較佳為500mW/cm2以下。 In the conversion step, the irradiance of the ultraviolet rays irradiating the metal oxide semiconductor precursor film with a wavelength of 300 nm or less is preferably 30 mW / cm 2 or more, and more preferably 50 mW / cm 2 . By setting the illuminance to 30 mW / cm 2 or more, a metal oxide semiconductor film having high electron transfer characteristics can be obtained. From the viewpoint of device cost, the upper limit of the illuminance is preferably 500 mW / cm 2 or less.
轉化步驟中的紫外線照射只要進行至金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜為止即可。雖然亦取決於前驅物膜的組成、加熱溫度、紫外線照度等，但就生產性的觀點而言，紫外線照射時間較佳為5分鐘以上、120分鐘以下。 The ultraviolet irradiation in the conversion step may be performed until the metal oxide semiconductor precursor film is converted into a metal oxide semiconductor film. Although it also depends on the composition of the precursor film, the heating temperature, the ultraviolet irradiance, etc., from the viewpoint of productivity, the ultraviolet irradiation time is preferably 5 minutes or more and 120 minutes or less.
另外，轉化步驟可在大氣壓下、大氣中進行，較佳為在包含1體積%以上的氧的環境中進行。若為包含氧的環境中，則容易獲得表現出高的電子傳遞特性的金屬氧化物半導體膜。另外，就生產成本的觀點而言，較佳為在大氣中的處理。 The conversion step can be performed under atmospheric pressure and in the atmosphere, and is preferably performed in an environment containing 1% by volume or more of oxygen. In an environment containing oxygen, it is easy to obtain a metal oxide semiconductor film exhibiting high electron transfer characteristics. From the viewpoint of production costs, the treatment in the atmosphere is preferred.
作為轉化步驟中的加熱處理中的紫外線照射的光源，可列舉：UV燈或UV雷射等，就大面積地均勻地藉由廉價的設備進 行紫外線照射的觀點而言，較佳為UV燈。作為UV燈，例如可列舉：準分子燈、氘燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、氦氣燈、碳弧燈、鎘燈、無電極放電燈等，特別是若使用低壓水銀燈，則容易自金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜，因此較佳。 Examples of the light source for ultraviolet irradiation during the heat treatment in the conversion step include a UV lamp, a UV laser, and the like. From the viewpoint of performing ultraviolet irradiation, a UV lamp is preferred. Examples of the UV lamp include an excimer lamp, a deuterium lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a helium lamp, a carbon arc lamp, a cadmium lamp, and an electrodeless discharge lamp. The use of a low-pressure mercury lamp is preferred because it is easy to convert from a metal oxide semiconductor precursor film to a metal oxide semiconductor film.
此處，藉由轉化步驟而形成的金屬氧化物半導體膜所含的碳濃度較佳為1×1019atoms/cm3以上、1×1020atoms/cm3以下，氫濃度較佳為2×1022atoms/cm3以上、4×1022atoms/cm3以下。若為所述濃度範圍，則容易獲得高的電子傳遞特性。 Here, the carbon concentration contained in the metal oxide semiconductor film formed by the conversion step is preferably 1 × 10 19 atoms / cm 3 or more and 1 × 10 20 atoms / cm 3 or less, and the hydrogen concentration is preferably 2 × 10 22 atoms / cm 3 or more and 4 × 10 22 atoms / cm 3 or less. If it is the said concentration range, it will become easy to obtain a high electron transfer characteristic.
再者，金屬氧化物半導體膜中的氫濃度及碳濃度是藉由二次離子質譜法(Secondary Ion Mass Spectroscopy，SIMS)而測定的值。SIMS作為能以非常高的感度檢測構成對象物的元素的分析法而為人所知，使束狀離子(一次離子)碰撞分析對象物，藉由碰撞而使構成對象物的物質進行離子化(二次離子)。藉由對所述二次離子進行質量分析，而檢測構成元素及其量。 The hydrogen concentration and carbon concentration in the metal oxide semiconductor film are values measured by a secondary ion mass spectrometry (SIMS). SIMS is known as an analysis method capable of detecting elements constituting an object with a very high sensitivity. A beam-like ion (primary ion) collides with the object to be analyzed, and the substance constituting the object is ionized by the collision ( Secondary ion). By performing mass analysis on the secondary ions, constituent elements and their amounts are detected.
另外，藉由本發明的製造方法而製作的金屬氧化物半導體膜中的金屬成分基本上與金屬氧化物半導體前驅物膜中的金屬成分相同。因此，金屬氧化物半導體膜中的全部金屬成分的80%以上為鋅及錫，鋅與錫的組成比為0.7≦Sn/(Sn+Zn)≦0.9。 The metal component in the metal oxide semiconductor film produced by the manufacturing method of the present invention is basically the same as the metal component in the metal oxide semiconductor precursor film. Therefore, more than 80% of all metal components in the metal oxide semiconductor film are zinc and tin, and the composition ratio of zinc to tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
金屬氧化物半導體膜中的鋅及錫相對於全部金屬成分的比率、以及鋅與錫的組成比，可藉由X射線光電子光譜(X-ray Photoelectron Spectrometry，XPS)測定，來測定金屬氧化物半導 體膜的表面的鋅、錫等金屬的原子數，並以鋅及錫的比率、鋅與錫的組成比而算出。或者，可將金屬氧化物半導體膜進行切片化加工，藉由膜的剖面穿透式電子顯微鏡(Transmission Electron Microscope，TEM)的能量分散型X射線分光法(EDX(Energy Dispersive X-ray)測定)，而算出鋅與錫的比率、組成比。 The ratio of zinc and tin in the metal oxide semiconductor film to all metal components and the composition ratio of zinc and tin can be measured by X-ray Photoelectron Spectrometry (XPS) to determine the metal oxide half guide The atomic number of a metal such as zinc or tin on the surface of the bulk film is calculated from the ratio of zinc to tin and the composition ratio of zinc to tin. Alternatively, the metal oxide semiconductor film can be sliced and measured by an energy dispersive X-ray (EDX) method of the transmission electron microscope (TEM) of the cross section of the film. To calculate the zinc and tin ratio and composition ratio.
<薄膜電晶體> <Thin Film Transistor>
藉由本發明的製造方法而製作的金屬氧化物半導體膜由於表現出高的電子傳遞特性，因此可適宜地用於薄膜電晶體(Thin Film Transistor，TFT)的活性層。 Since the metal oxide semiconductor film produced by the manufacturing method of the present invention exhibits high electron transfer characteristics, it can be suitably used for an active layer of a thin film transistor (TFT).
以下，對使用利用本發明的製造方法而製作的金屬氧化物半導體膜作為薄膜電晶體的活性層時的實施形態進行說明。再者，本發明的金屬氧化物半導體膜的製造方法及藉由所述製造方法而製造的金屬氧化物半導體膜並不限定於TFT的活性層。 Hereinafter, an embodiment when a metal oxide semiconductor film produced by the manufacturing method of the present invention is used as an active layer of a thin film transistor will be described. The method for manufacturing a metal oxide semiconductor film and the metal oxide semiconductor film manufactured by the manufacturing method of the present invention are not limited to an active layer of a TFT.
本發明的TFT的元件結構並無特別限定，可為基於閘極電極的位置的所謂的逆交錯結構(亦稱為底閘極型)及交錯結構(亦稱為頂閘極型)的任一種形態。另外，還可為基於活性層與源極電極及汲極電極(適當稱為「源極-汲極電極」)的接觸部分的所謂的頂接觸型、底接觸型的任一種形態。 The element structure of the TFT of the present invention is not particularly limited, and may be any of a so-called inverse staggered structure (also referred to as a bottom gate type) and an interleaved structure (also referred to as a top gate type) based on the positions of the gate electrodes. form. In addition, it may be in any of a so-called top-contact type and a bottom-contact type based on a contact portion between the active layer and the source electrode and the drain electrode (referred to as a "source-drain electrode" as appropriate).
所謂頂閘極型，是在將形成有TFT的基板設為最下層時，在閘極絕緣膜的上側配置有閘極電極，在閘極絕緣膜的下側形成有活性層的形態，所謂底閘極型，是在閘極絕緣膜的下側配置有閘極電極，在閘極絕緣膜的上側形成有活性層的形態。另外， 所謂底接觸型，是源極-汲極電極較活性層先形成而活性層的下表面與源極-汲極電極接觸的形態，所謂頂接觸型，是活性層較源極-汲極電極先形成而活性層的上表面與源極-汲極電極接觸的形態。 The top-gate type is a configuration in which a gate electrode is disposed on the gate insulating film and an active layer is formed on the lower side of the gate insulating film when the substrate on which the TFT is formed is the lowermost layer. The gate type is a configuration in which a gate electrode is arranged on the lower side of the gate insulating film, and an active layer is formed on the upper side of the gate insulating film. In addition, The so-called bottom contact type is a form in which the source-drain electrode is formed before the active layer and the lower surface of the active layer is in contact with the source-drain electrode. Formed while the upper surface of the active layer is in contact with the source-drain electrode.
圖1是表示頂閘極結構且頂接觸型的本發明的TFT的一例的示意圖。在圖1所示的薄膜電晶體(TFT)10中，在基板12的一個主面上積層作為活性層14的所述氧化物半導體膜。並且，在所述活性層14上源極電極16及汲極電極18彼此隔開而設置，繼而在該些之上依序積層閘極絕緣膜20、以及閘極電極22。 FIG. 1 is a schematic diagram showing an example of a TFT of the present invention having a top-gate structure and a top-contact type. In the thin film transistor (TFT) 10 shown in FIG. 1, the oxide semiconductor film as the active layer 14 is laminated on one main surface of the substrate 12. In addition, the source electrode 16 and the drain electrode 18 are provided on the active layer 14 apart from each other, and a gate insulating film 20 and a gate electrode 22 are sequentially stacked on the active layer 14.
圖2是表示頂閘極結構且底接觸型的本發明的TFT的一例的示意圖。在圖2所示的TFT30中，在基板12的一個主面上源極電極16及汲極電極18彼此隔開而設置。並且，依序積層作為活性層14的所述氧化物半導體膜、閘極絕緣膜20、以及閘極電極22。 FIG. 2 is a schematic diagram showing an example of a TFT of the present invention having a top gate structure and a bottom contact type. In the TFT 30 shown in FIG. 2, the source electrode 16 and the drain electrode 18 are provided on one main surface of the substrate 12 while being separated from each other. The oxide semiconductor film, the gate insulating film 20, and the gate electrode 22 as the active layer 14 are sequentially laminated.
圖3是表示底閘極結構且頂接觸型的本發明的TFT的一例的示意圖。在圖3所示的TFT40中，在基板12的一個主面上依序積層閘極電極22、閘極絕緣膜20、以及作為活性層14的所述氧化物半導體膜。並且，在所述活性層14的表面上源極電極16及汲極電極18彼此隔開而設置。 FIG. 3 is a schematic diagram showing an example of a TFT of the present invention having a bottom gate structure and a top contact type. In the TFT 40 shown in FIG. 3, a gate electrode 22, a gate insulating film 20, and the oxide semiconductor film as the active layer 14 are sequentially laminated on one main surface of the substrate 12. Further, the source electrode 16 and the drain electrode 18 are provided on the surface of the active layer 14 and spaced apart from each other.
圖4是表示底閘極結構且底接觸型的本發明的TFT的一例的示意圖。在圖4所示的TFT50中，在基板12的一個主面上依序積層閘極電極22、以及閘極絕緣膜20。並且，在所述閘極絕緣膜20的表面上源極電極16及汲極電極18彼此隔開而設置，繼而 在該些之上，積層有作為活性層14的所述氧化物半導體膜。 FIG. 4 is a schematic diagram showing an example of a TFT of the present invention having a bottom gate structure and a bottom contact type. In the TFT 50 shown in FIG. 4, a gate electrode 22 and a gate insulating film 20 are sequentially laminated on one main surface of the substrate 12. Further, the source electrode 16 and the drain electrode 18 are provided on the surface of the gate insulating film 20 apart from each other, and then On these layers, the oxide semiconductor film as the active layer 14 is laminated.
作為以下的實施形態，主要對圖1所示的頂閘極型的薄膜電晶體10進行說明，但本發明的薄膜電晶體並不限定於頂閘極型，亦可為底閘極型的薄膜電晶體。 As the following embodiment, the top-gate thin film transistor 10 shown in FIG. 1 is mainly described, but the thin-film transistor of the present invention is not limited to the top-gate thin film, and may be a bottom-gate thin film. Transistor.
(活性層) (Active layer)
在製造本實施形態的薄膜電晶體10時，首先，經過所述金屬氧化物半導體前驅物膜形成步驟及轉化步驟在基板12上形成金屬氧化物半導體膜，並將所述金屬氧化物半導體膜圖案化為活性層的形狀。圖案化較佳為藉由所述噴墨法、分配器法、凸版印刷法、及凹版印刷法的任一種方法，預先形成具有活性層的圖案的金屬氧化物半導體前驅物膜，而轉化為金屬氧化物半導體膜。 When manufacturing the thin film transistor 10 of this embodiment, first, a metal oxide semiconductor film is formed on the substrate 12 through the metal oxide semiconductor precursor film forming step and conversion step, and the metal oxide semiconductor film is patterned. Into the shape of an active layer. The patterning is preferably performed by any one of the inkjet method, dispenser method, letterpress method, and gravure method to form a metal oxide semiconductor precursor film having a pattern of an active layer in advance, and convert it into a metal. An oxide semiconductor film.
就平坦性及膜形成所需要的時間的觀點而言，活性層14的厚度較佳為5nm以上、50nm以下。 From the viewpoint of flatness and the time required for film formation, the thickness of the active layer 14 is preferably 5 nm or more and 50 nm or less.
另外，較佳為在活性層14上形成保護膜(未圖示)，所述保護膜在源極電極16、汲極電極18的蝕刻時用以保護活性層14。保護膜的成膜方法並無特別限定，可與金屬氧化物半導體膜連續地成膜，亦可在金屬氧化物半導體膜的圖案化後形成。另外，作為保護膜，可為金屬氧化物層，亦可為如樹脂般的有機材料。另外，保護層可在源極-汲極電極形成後除去。 In addition, a protective film (not shown) is preferably formed on the active layer 14, and the protective film is used to protect the active layer 14 when the source electrode 16 and the drain electrode 18 are etched. The method for forming the protective film is not particularly limited, and it may be formed continuously with the metal oxide semiconductor film, or may be formed after patterning the metal oxide semiconductor film. The protective film may be a metal oxide layer or an organic material such as a resin. In addition, the protective layer can be removed after the source-drain electrode is formed.
(源極-汲極電極) (Source-drain electrode)
在所述活性層14上形成源極電極16、汲極電極18。源極-汲極電極分別使用具有高的導電性者以便發揮出作為電極的功 能，可使用Al、Mo、Cr、Ta、Ti、Au、Ag等金屬，Al-Nd、Ag合金、氧化錫、氧化鋅、氧化銦、氧化銦錫(Indium Tin Oxide，ITO)、氧化鋅銦(Indium Zinc Oxide，IZO)、In-Ga-Zn-O等金屬氧化物導電體薄膜等而形成。 A source electrode 16 and a drain electrode 18 are formed on the active layer 14. Source-drain electrodes use those with high conductivity to perform their functions as electrodes. Yes, metals such as Al, Mo, Cr, Ta, Ti, Au, Ag can be used, Al-Nd, Ag alloy, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), In-Ga-Zn-O, and other metal oxide conductor films.
源極電極16、汲極電極18的形成只要根據考慮到與所使用的材料的適性而自例如印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍敷法等物理方式，化學氣相沈積(Chemical Vapor Deposition，CVD)、電漿CVD法等化學方式等中適當選擇的方法進行成膜即可。 The source electrode 16 and the drain electrode 18 may be formed by a wet method such as a printing method, a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, or the like according to the suitability with the materials used. The film may be formed by a physical method, a chemical method such as chemical vapor deposition (CVD), or a chemical method such as plasma CVD.
若考慮到成膜性、藉由蝕刻或舉離法的圖案化性、導電性等，則各電極的膜厚較佳為設為10nm以上、1000nm以下，更佳為設為50nm以上、100nm以下。 In consideration of film-forming property, patterning property by etching or lift-off method, conductivity, etc., the film thickness of each electrode is preferably 10 nm or more and 1000 nm or less, and more preferably 50 nm or more and 100 nm or less. .
源極電極16、汲極電極18可藉由蝕刻或舉離法圖案化為特定形狀而形成，亦可藉由噴墨法等直接形成圖案。此時，較佳為將源極電極16、汲極電極18的全部層及與所述電極連接的配線同時圖案化。 The source electrode 16 and the drain electrode 18 may be formed by patterning into a specific shape by etching or lift-off method, or may be directly formed by an inkjet method or the like. At this time, it is preferable that all layers of the source electrode 16 and the drain electrode 18 and wirings connected to the electrodes are simultaneously patterned.
(閘極絕緣膜) (Gate insulation film)
在形成源極電極16、汲極電極18及配線後，形成閘極絕緣膜20。閘極絕緣膜20較佳為具有高的絕緣性者，例如可設為SiO2、SiNx、SiON、Al2O3、Y2O3、Ta2O5、HfO2等絕緣膜、或包含至少兩種以上的所述化合物的絕緣膜，可為單層結構，亦可為積層結構。 After the source electrode 16, the drain electrode 18, and the wiring are formed, a gate insulating film 20 is formed. The gate insulating film 20 is preferably one having high insulating properties. For example, the gate insulating film 20 may be an insulating film such as SiO 2 , SiNx, SiON, Al 2 O 3 , Y 2 O 3 , Ta 2 O 5 , HfO 2 or the like. The insulating film of two or more kinds of the compounds may have a single-layer structure or a laminated structure.
閘極絕緣膜20可根據考慮到與所使用的材料的適性而自印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍敷法等物理方式，CVD、電漿CVD法等化學方式等中適當選擇的方法進行成膜。 The gate insulating film 20 may be a wet method such as a printing method or a coating method, a physical method such as a vacuum evaporation method, a sputtering method, or an ion plating method, or a CVD method, or a plasma method, depending on the suitability of the material used. The film is formed by a method appropriately selected from chemical methods such as the CVD method.
再者，閘極絕緣膜20必須具有用以降低洩漏電流及提高電壓耐性的厚度，另一方面，若閘極絕緣膜20的厚度過大，則會導致驅動電壓上升。雖然亦取決於閘極絕緣膜20的材質，但閘極絕緣膜20的厚度較佳為10nm以上、10μm以下，更佳為50nm以上、1000nm以下，特佳為100nm以上、400nm以下。 Furthermore, the gate insulating film 20 must have a thickness for reducing leakage current and improving voltage resistance. On the other hand, if the thickness of the gate insulating film 20 is too large, the driving voltage will increase. Although it also depends on the material of the gate insulating film 20, the thickness of the gate insulating film 20 is preferably 10 nm or more and 10 μm or less, more preferably 50 nm or more and 1000 nm or less, and particularly preferably 100 nm or more and 400 nm or less.
(閘極電極) (Gate electrode)
在形成閘極絕緣膜20後，形成閘極電極22。閘極電極22使用具有高的導電性者，例如可使用Al、Mo、Cr、Ta、Ti、Au、Ag等金屬，Al-Nd、Ag合金、氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化鋅銦(IZO)、IGZO等金屬氧化物導電膜等而形成。作為閘極電極22，可將所述導電膜製成單層結構或兩層以上的積層結構而使用。 After the gate insulating film 20 is formed, a gate electrode 22 is formed. The gate electrode 22 is made of a material having high conductivity. For example, metals such as Al, Mo, Cr, Ta, Ti, Au, Ag, Al-Nd, Ag alloy, tin oxide, zinc oxide, indium oxide, and indium tin oxide can be used. (ITO), indium zinc oxide (IZO), IGZO and other metal oxide conductive films. As the gate electrode 22, the conductive film may be used in a single-layer structure or a multilayer structure of two or more layers.
閘極電極22根據考慮到與所使用的材料的適性而自例如印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍敷法等物理方式，CVD、電漿CVD法等化學方式等中適當選擇的方法進行成膜。 The gate electrode 22 may be a wet method such as a printing method or a coating method, a physical method such as a vacuum evaporation method, a sputtering method, or an ion plating method, or a CVD method, or a plasma CVD method. The film is formed by a method appropriately selected from chemical methods such as a chemical method.
若考慮到成膜性、藉由蝕刻或舉離法的圖案化性、導電性等，則閘極電極22的膜厚較佳為設為10nm以上、1000nm以下，更 佳為設為50nm以上、200nm以下。 In consideration of film-forming property, patterning property by etching or lift-off method, electrical conductivity, and the like, the film thickness of the gate electrode 22 is preferably set to 10 nm or more and 1000 nm or less, more preferably Preferably, it is 50 nm or more and 200 nm or less.
在成膜後，可藉由蝕刻或舉離法圖案化為特定形狀，而形成閘極電極22，亦可藉由噴墨法等直接形成圖案。此時，較佳為將閘極電極22及與閘極電極22連接的配線同時圖案化。 After the film formation, the gate electrode 22 can be formed by patterning into a specific shape by etching or lift-off method, or the pattern can be directly formed by an inkjet method or the like. At this time, it is preferable to pattern the gate electrode 22 and the wiring connected to the gate electrode 22 at the same time.
以上所說明的本發明的薄膜電晶體的用途並無特別限定，就表現出高的傳輸特性的方面而言，例如適合於用於電光學裝置(例如液晶顯示裝置、有機EL(Electro Luminescence)顯示裝置、無機EL顯示裝置等顯示裝置等)中的驅動元件、在耐熱性低的樹脂基板上形成的可撓性顯示器的情形。 The application of the thin film transistor of the present invention described above is not particularly limited, and it is suitable for use in an electro-optical device (for example, a liquid crystal display device, an organic EL (Electro Luminescence) display) in terms of exhibiting high transmission characteristics Device, display device such as an inorganic EL display device, etc.), and a flexible display formed on a resin substrate having low heat resistance.
而且，本發明的薄膜電晶體適合用作X射線感測器等各種感測器、微機電系統(Micro Electro Mechanical System，MEMS)等各種電子元件中的驅動元件(驅動電路)。 Furthermore, the thin film transistor of the present invention is suitable for use as a driving element (driving circuit) in various sensors such as an X-ray sensor, and various electronic components such as a micro electro mechanical system (MEMS).
<液晶顯示裝置> <Liquid crystal display device>
對於使用本發明的薄膜電晶體的液晶顯示裝置的一例，圖5表示其一部分的概略剖面圖，圖6表示電配線的概略構成圖。 An example of a liquid crystal display device using the thin film transistor of the present invention is a schematic cross-sectional view of a part thereof, and FIG. 6 is a schematic configuration diagram of an electric wiring.
如圖5所示般，本實施形態的液晶顯示裝置100是如下的構成：具備圖1所示的頂閘極結構且頂接觸型的TFT10、在由TFT10的鈍化層102保護的閘極電極22上由畫素下部電極104及其對向上部電極106夾持的液晶層108、與各畫素對應而用以發出不同顏色的R(紅)G(綠)B(藍)的彩色濾光片110，並且在TFT10的基板12側及RGB彩色濾光片110上分別具備偏光板112a、偏光板112b。 As shown in FIG. 5, the liquid crystal display device 100 of this embodiment has a structure including a top-gate TFT 10 shown in FIG. 1 and a top-contact type TFT 10, and a gate electrode 22 protected by a passivation layer 102 of the TFT 10. The liquid crystal layer 108 on the upper part is held by the pixel lower electrode 104 and its upper electrode 106, and the color filters corresponding to each pixel are used to emit different colors of R (red) G (green) B (blue). 110, and a polarizing plate 112a and a polarizing plate 112b are provided on the substrate 12 side of the TFT 10 and the RGB color filter 110, respectively.
另外，如圖6所示般，本實施形態的液晶顯示裝置100具備：彼此平行的多條閘極配線113、與所述閘極配線113交叉的彼此平行的資料配線114。此處，閘極配線113與資料配線114電性絕緣。在閘極配線113與資料配線114的交叉部附近具備TFT10。 As shown in FIG. 6, the liquid crystal display device 100 of the present embodiment includes a plurality of gate wirings 113 parallel to each other, and data wirings 114 that intersect with the gate wirings 113 and are parallel to each other. Here, the gate wiring 113 and the data wiring 114 are electrically insulated. A TFT 10 is provided near the intersection of the gate wiring 113 and the data wiring 114.
TFT10的閘極電極22與閘極配線113連接，TFT10的源極電極16與資料配線114連接。另外，TFT10的汲極電極18經由設置於閘極絕緣膜20的接觸孔116(在接觸孔116中嵌入導電體)而與畫素下部電極104連接。所述畫素下部電極104與接地的對向上部電極106一起構成電容器118。 The gate electrode 22 of the TFT 10 is connected to the gate wiring 113, and the source electrode 16 of the TFT 10 is connected to the data wiring 114. The drain electrode 18 of the TFT 10 is connected to the pixel lower electrode 104 via a contact hole 116 (a conductor is embedded in the contact hole 116) provided in the gate insulating film 20. The pixel lower electrode 104 forms a capacitor 118 together with a grounded upper electrode 106.
<有機EL顯示裝置> <Organic EL Display Device>
對於使用本發明的薄膜電晶體的主動矩陣方式的有機EL顯示裝置的一例，圖7表示一部分的概略剖面圖，圖8表示電配線的概略構成圖。 For an example of an active matrix organic EL display device using the thin film transistor of the present invention, FIG. 7 is a schematic cross-sectional view of a portion, and FIG. 8 is a schematic configuration diagram of an electrical wiring.
本實施形態的主動矩陣方式的有機EL顯示裝置200設為如下的構成：在具備鈍化層202的基板12上，具備圖1所示的頂閘極結構的TFT10作為驅動用薄膜電晶體(TFT)10a及開關用薄膜電晶體(TFT)10b，在驅動用TFT10a、開關用TFT10b上具備包含由下部電極208及上部電極210夾持的有機發光層212的有機EL發光元件214，上表面亦由鈍化層216保護。 The active-matrix organic EL display device 200 of this embodiment has a structure in which a substrate 12 having a passivation layer 202 is provided with a TFT 10 having a top-gate structure as shown in FIG. 1 as a driving thin film transistor (TFT). 10a and a switching thin film transistor (TFT) 10b are provided with an organic EL light emitting element 214 including an organic light emitting layer 212 sandwiched between a lower electrode 208 and an upper electrode 210 on the driving TFT 10a and the switching TFT 10b. Layer 216 is protected.
另外，如圖8所示般，本實施形態的有機EL顯示裝置200具備：彼此平行的多條閘極配線220、與所述閘極配線220交叉的彼此平行的資料配線222及驅動配線224。此處，閘極配線 220與資料配線222、驅動配線224電性絕緣。開關用TFT10b的閘極電極22與閘極配線220連接，開關用TFT10b的源極電極16與資料配線222連接。另外，開關用TFT10b的汲極電極18與驅動用TFT10a的閘極電極22連接，並且藉由使用電容器226而將驅動用TFT10a保持為接通狀態。驅動用TFT10a的源極電極16與驅動配線224連接，汲極電極18與有機EL發光元件214連接。 As shown in FIG. 8, the organic EL display device 200 according to the present embodiment includes a plurality of gate wirings 220 parallel to each other, a data wiring 222 and a driving wiring 224 parallel to each other and intersecting the gate wirings 220. Here, the gate wiring 220 is electrically insulated from the data wiring 222 and the driving wiring 224. The gate electrode 22 of the switching TFT 10 b is connected to the gate wiring 220, and the source electrode 16 of the switching TFT 10 b is connected to the data wiring 222. In addition, the drain electrode 18 of the switching TFT 10b is connected to the gate electrode 22 of the driving TFT 10a, and the driving TFT 10a is kept in an on state by using a capacitor 226. The source electrode 16 of the driving TFT 10 a is connected to the driving wiring 224, and the drain electrode 18 is connected to the organic EL light-emitting element 214.
再者，在圖7所示的有機EL顯示裝置中，可將上部電極210設為透明電極而設為頂部發光型，亦可藉由將下部電極208及TFT的各電極設為透明電極而設為底部發光型。 Furthermore, in the organic EL display device shown in FIG. 7, the upper electrode 210 may be a transparent electrode and a top-emission type, or the lower electrode 208 and each electrode of the TFT may be provided as transparent electrodes. It is a bottom emission type.
<X射線感測器> <X-ray sensor>
對於使用本發明的薄膜電晶體的X射線感測器的一例，圖9表示其一部分的概略剖面圖，圖10表示其電配線的概略構成圖。 An example of an X-ray sensor using the thin film transistor of the present invention is a schematic cross-sectional view of a part thereof, and FIG. 10 is a schematic configuration diagram of an electric wiring.
本實施形態的X射線感測器300具備形成於基板12上的TFT10及電容器310、形成於電容器310上的電荷收集用電極302、X射線轉換層304、以及上部電極306而構成。在TFT10上設置有鈍化膜308。 The X-ray sensor 300 according to the present embodiment includes a TFT 10 and a capacitor 310 formed on the substrate 12, a charge collection electrode 302 formed on the capacitor 310, an X-ray conversion layer 304, and an upper electrode 306. A passivation film 308 is provided on the TFT 10.
電容器310成為由電容器用下部電極312與電容器用上部電極314夾持絕緣膜316的結構。電容器用上部電極314經由設置於絕緣膜316的接觸孔318，而與TFT10的源極電極16及汲極電極18的任一電極(圖9中為汲極電極18)連接。 The capacitor 310 has a structure in which an insulating film 316 is sandwiched between a capacitor lower electrode 312 and a capacitor upper electrode 314. The capacitor upper electrode 314 is connected to any one of the source electrode 16 and the drain electrode 18 (the drain electrode 18 in FIG. 9) through a contact hole 318 provided in the insulating film 316.
電荷收集用電極302設置於電容器310的電容器用上部電極314上，與電容器用上部電極314接觸。 The charge collection electrode 302 is provided on the capacitor upper electrode 314 of the capacitor 310 and is in contact with the capacitor upper electrode 314.
X射線轉換層304為包含非晶硒的層，以覆蓋TFT10及電容器310的方式設置。 The X-ray conversion layer 304 is a layer containing amorphous selenium, and is provided so as to cover the TFT 10 and the capacitor 310.
上部電極306設置於X射線轉換層304上，與X射線轉換層304接觸。 The upper electrode 306 is disposed on the X-ray conversion layer 304 and is in contact with the X-ray conversion layer 304.
如圖10所示般，本實施形態的X射線感測器300具備：彼此平行的多條閘極配線320、與閘極配線320交叉的彼此平行的多條資料配線322。此處，閘極配線320與資料配線322電性絕緣。在閘極配線320與資料配線322的交叉部附近具備TFT10。 As shown in FIG. 10, the X-ray sensor 300 according to this embodiment includes a plurality of gate wirings 320 parallel to each other, and a plurality of data wirings 322 parallel to each other crossing the gate wirings 320. Here, the gate wiring 320 and the data wiring 322 are electrically insulated. A TFT 10 is provided near the intersection of the gate wiring 320 and the data wiring 322.
TFT10的閘極電極22與閘極配線320連接，TFT10的源極電極16與資料配線322連接。另外，TFT10的汲極電極18與電荷收集用電極302連接，而且所述電荷收集用電極302與電容器310連接。 The gate electrode 22 of the TFT 10 is connected to the gate wiring 320, and the source electrode 16 of the TFT 10 is connected to the data wiring 322. The drain electrode 18 of the TFT 10 is connected to a charge collection electrode 302, and the charge collection electrode 302 is connected to a capacitor 310.
在本實施形態的X射線感測器300中，在圖9中，X射線自上部電極306側入射而在X射線轉換層304生成電子-電洞對。預先藉由上部電極306對X射線轉換層304施加高電場，藉此所生成的電荷儲存在電容器310中，藉由依序掃描TFT10而讀出。 In the X-ray sensor 300 of this embodiment, in FIG. 9, X-rays are incident from the upper electrode 306 side to generate an electron-hole pair in the X-ray conversion layer 304. A high electric field is applied to the X-ray conversion layer 304 through the upper electrode 306 in advance, whereby the generated charges are stored in the capacitor 310 and read out by sequentially scanning the TFT 10.
再者，在所述實施形態的液晶顯示裝置100、有機EL顯示裝置200、及X射線感測器300中，雖然設為具備頂閘極結構的TFT者，但TFT並不限定於此，亦可為圖2~圖4所示的結構的TFT。 Furthermore, although the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 according to the embodiment are provided with TFTs having a top gate structure, the TFTs are not limited to this, and It may be a TFT having a structure shown in FIGS. 2 to 4.
[實施例] [Example]
以下基於實施例對本發明進行更詳細地說明。以下的實施例所示的材料、使用量、比例、處理內容、處理順序等，只要不脫離本發明的主旨，則可進行適當變更。因此，本發明的範圍不應由以下所示的實施例進行限定性地解釋。 Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.
[實施例1] [Example 1]
<金屬氧化物半導體膜的製作> <Production of Metal Oxide Semiconductor Film>
將以下所示的溶液塗佈於基板上，而形成金屬氧化物半導體前驅物膜，在加熱所述金屬氧化物半導體前驅物膜的狀態下進行紫外線照射，藉此使金屬氧化物半導體前驅物膜轉化為金屬氧化物半導體膜，而製作金屬氧化物半導體膜。 The metal oxide semiconductor precursor film is formed by applying the solution shown below on a substrate, and the metal oxide semiconductor precursor film is heated while the metal oxide semiconductor precursor film is heated to irradiate the metal oxide semiconductor precursor film. It is converted into a metal oxide semiconductor film to produce a metal oxide semiconductor film.
[金屬氧化物半導體前驅物膜形成步驟] [Metal Oxide Semiconductor Precursor Film Formation Step]
(溶液) (Solution)
使氯化錫(SnCl4．xH2O、3 N、高純度化學研究所股份有限公司製造)及乙酸鋅(Zn(CH3COO)2．2H2O、高純度化學研究所股份有限公司製造)分別溶解於2-甲氧基乙醇(試劑特級、和光純藥工業股份有限公司製造)中，而製備濃度為0.3mol/L的氯化錫溶液及乙酸鋅溶液，然後，將氯化錫溶液與乙酸鋅溶液以9：1的比例混合，藉此製備金屬氧化物半導體前驅物溶液。 Tin chloride (SnCl 4 .xH 2 O, 3 N, for producing high-purity Chemistry Co.) and zinc acetate (Zn (CH 3 COO) 2 .2H 2 O, manufactured by Kojundo Chemical Co., Ltd. ) Were dissolved in 2-methoxyethanol (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare tin chloride solution and zinc acetate solution with a concentration of 0.3mol / L, and then the tin chloride solution It was mixed with a zinc acetate solution at a ratio of 9: 1, thereby preparing a metal oxide semiconductor precursor solution.
即，所述溶液的鋅及錫的比例為100%，鋅與錫的組成比Sn/(Sn+Zn)為0.9。 That is, the ratio of zinc and tin in the solution was 100%, and the composition ratio Sn / (Sn + Zn) of zinc to tin was 0.9.
(基板) (Substrate)
使用附有熱氧化膜的p型矽基板作為基板。設為使用所述基 板的熱氧化膜作為TFT的閘極絕緣膜的構成。 As the substrate, a p-type silicon substrate with a thermal oxide film was used. Set to use the base The thermal oxide film of the plate is configured as a gate insulating film of the TFT.
(塗佈、乾燥) (Coating, drying)
在附有熱氧化膜的p型矽1英吋×1英吋基板上，以5000rpm的旋轉速度將所製備的溶液旋塗30秒鐘後，在加熱至60℃的加熱板上進行5分鐘乾燥。 The prepared solution was spin-coated on a p-type silicon 1-inch x 1-inch substrate with a thermal oxide film at a rotation speed of 5000 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C for 5 minutes. .
[轉化步驟] [Conversion step]
在下述條件下進行所得的金屬氧化物半導體前驅物膜向金屬氧化物半導體膜的轉化。 Conversion of the obtained metal oxide semiconductor precursor film to a metal oxide semiconductor film was performed under the following conditions.
作為裝置，使用具備低壓水銀燈的真空紫外線(vacuum ultraviolet，VUV)乾式處理器(dry processor)(奧珂製作所(ORC MANUFACTURING)股份有限公司製造、VUE-3400-F)。 As the device, a vacuum ultraviolet (VUV) dry processor (VCO-3400-F manufactured by ORC MANUFACTURING Co., Ltd.) equipped with a low-pressure mercury lamp was used.
在將試樣設置於裝置內的未加熱的加熱板上後，待機5分鐘。期間，在裝置處理室內流動20L/min的乾燥空氣。 After the sample was set on an unheated hot plate in the apparatus, it stood for 5 minutes. During this period, 20 L / min of dry air was flowed in the processing chamber of the device.
在5分鐘的待機後，打開裝置內的閘門，歷時30分鐘升溫至250℃，到達250℃後，歷時60分鐘一邊保持溫度一邊進行紫外線照射處理，藉此獲得金屬氧化物半導體膜。在加熱處理下的紫外線照射處理的期間，始終流動20L/min的乾燥空氣。 After 5 minutes of standby time, the shutter in the device was opened, and the temperature was raised to 250 ° C. for 30 minutes. After reaching 250 ° C., UV irradiation was performed while maintaining the temperature for 60 minutes to obtain a metal oxide semiconductor film. During the ultraviolet irradiation treatment under the heat treatment, a dry air of 20 L / min was always flowing.
使用紫外線累計光量計(濱松光子學(Hamamatsu Photonics)股份有限公司製造、控制器C9536、感測器頭H9536-254、在超過200nm且300nm左右的範圍內具有分光感度)，測定試樣位置的將波長254nm設為峰值波長的紫外線照度，結果為51mW/cm2。 Using an ultraviolet cumulative light meter (manufactured by Hamamatsu Photonics Co., Ltd., controller C9536, sensor head H9536-254, and having a spectral sensitivity in the range of more than 200 nm and about 300 nm), the position of the sample will be measured. The ultraviolet illuminance having a wavelength of 254 nm was set to a peak wavelength, and was 51 mW / cm 2 .
[TFT的製作] [Manufacture of TFT]
藉由蒸鍍，在所述獲得的金屬氧化物半導體膜上將源極-汲極電極成膜，而製作簡易型TFT。源極-汲極電極成膜藉由使用金屬遮罩的圖案成膜而製作，將Ti成膜50nm。源極-汲極電極尺寸分別設為1mm×1mm，電極間距離設為0.2mm。 A source-drain electrode was formed on the obtained metal oxide semiconductor film by vapor deposition to produce a simple TFT. The source-drain electrode was formed by patterning using a metal mask, and Ti was formed into a film of 50 nm. The source-drain electrode size is set to 1mm × 1mm, and the distance between the electrodes is set to 0.2mm.
[實施例2] [Example 2]
將氯化錫溶液與乙酸鋅溶液的混合比例設為7：3而製備溶液，將金屬氧化物半導體前驅物膜的鋅與錫的組成比Sn/(Sn+Zn)設為0.7，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 A solution was prepared by setting the mixing ratio of the tin chloride solution and the zinc acetate solution to 7: 3, and setting the composition ratio of zinc to tin of the metal oxide semiconductor precursor film Sn / (Sn + Zn) to 0.7. In the same manner as in Example 1, a metal oxide semiconductor film was formed to produce a simple TFT.
[實施例3] [Example 3]
將轉化步驟中的紫外線照射處理時的基板溫度設為230℃，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 Except that the substrate temperature during the ultraviolet irradiation treatment in the conversion step was set to 230 ° C., a metal oxide semiconductor film was formed in the same manner as in Example 1 to produce a simple TFT.
[實施例4] [Example 4]
將轉化步驟中的紫外線照射處理時的紫外線光照度設為80mW/cm2，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 Except that the ultraviolet irradiance during the ultraviolet irradiation treatment in the conversion step was set to 80 mW / cm 2 , a metal oxide semiconductor film was formed in the same manner as in Example 1 to produce a simple TFT.
[實施例5] [Example 5]
使用下述所示的金屬氧化物半導體前驅物溶液，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 A simple type TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the metal oxide semiconductor precursor solution shown below was used.
使硝酸鎵(Ga(NO3)3．xH2O、5 N、高純度化學研究所股 份有限公司製造)及硝酸銦(In(NO3)3．xH2O、4 N、高純度化學研究所股份有限公司製造)分別溶解於2-甲氧基乙醇(試劑特級、和光純藥工業股份有限公司製造)中，而製備濃度為0.3mol/L的硝酸鎵溶液及硝酸銦溶液，然後，將硝酸鎵溶液與硝酸銦溶液以1：4的比例混合，藉此製備鎵銦混合溶液。然後，藉由將實施例1中所用的鋅與錫的組成比Sn/(Sn+Zn)為0.9的溶液、和鎵銦混合溶液以4：1的比例混合，而製備金屬氧化物半導體前驅物溶液。 Study on gallium nitrate (Ga (NO 3 ) 3. xH 2 O, 5 N, manufactured by High Purity Chemical Research Institute Co., Ltd.) and indium nitrate (In (NO 3 ) 3. xH 2 O, 4 N, high purity chemical research Co., Ltd.) were dissolved in 2-methoxyethanol (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 0.3mol / L gallium nitrate solution and an indium nitrate solution, and then, A gallium nitrate solution and an indium nitrate solution were mixed at a ratio of 1: 4, thereby preparing a gallium indium mixed solution. Then, a metal oxide semiconductor precursor was prepared by mixing a solution having a composition ratio Sn / (Sn + Zn) of 0.9 used in Example 1 and a gallium indium mixed solution at a ratio of 4: 1. Solution.
即，所述溶液的鋅及錫的比例為80%，鋅與錫的組成比Sn/(Sn+Zn)為0.9。 That is, the ratio of zinc and tin in the solution was 80%, and the composition ratio Sn / (Sn + Zn) of zinc to tin was 0.9.
[實施例6] [Example 6]
將實施例1中所用的鋅與錫的組成比Sn/(Sn+Zn)為0.9的溶液、和鎵銦混合溶液的混合比例設為9：1，除此以外，以與實施例5相同的方式，製備金屬氧化物半導體前驅物溶液，形成金屬氧化物半導體膜，而製作簡易型TFT。 The solution with a composition ratio of Sn / (Sn + Zn) of 0.9 and a gallium-indium mixed solution used in Example 1 was set to 9: 1, except that the same ratio as in Example 5 was used. Method, a metal oxide semiconductor precursor solution is prepared, a metal oxide semiconductor film is formed, and a simple TFT is manufactured.
即，所述溶液的鋅及錫的比例為90%，鋅與錫的組成比Sn/(Sn+Zn)為0.9。 That is, the ratio of zinc and tin in the solution was 90%, and the composition ratio Sn / (Sn + Zn) of zinc to tin was 0.9.
[比較例1] [Comparative Example 1]
使用氯化錫溶液作為溶液，將金屬氧化物半導體前驅物膜的鋅與錫的組成比Sn/(Sn+Zn)設為1，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 A metal chloride was formed in the same manner as in Example 1 except that the tin / tin composition ratio Sn / (Sn + Zn) of the metal oxide semiconductor precursor film was set to 1 using a tin chloride solution as the solution. And a simple semiconductor TFT.
[比較例2] [Comparative Example 2]
將氯化錫溶液與乙酸鋅溶液的混合比例設為6：4而製備溶 液，將金屬氧化物半導體前驅物膜的鋅與錫的組成比Sn/(Sn+Zn)設為0.6，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 The mixing ratio of the tin chloride solution and the zinc acetate solution was set to 6: 4 to prepare a solvent. Except that the zinc / tin composition ratio Sn / (Sn + Zn) of the metal oxide semiconductor precursor film was 0.6, and a metal oxide semiconductor film was formed in the same manner as in Example 1 except that Simple TFT.
[比較例3] [Comparative Example 3]
在轉化步驟中不進行紫外線的照射，除此以外，以與實施例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 Except that no ultraviolet irradiation was performed in the conversion step, a metal oxide semiconductor film was formed in the same manner as in Example 1 to fabricate a simple TFT.
[比較例4] [Comparative Example 4]
在轉化步驟中不進行紫外線的照射，除此以外，以與比較例1相同的方式，形成金屬氧化物半導體膜，而製作簡易型TFT。 A metal oxide semiconductor film was formed in the same manner as in Comparative Example 1 except that the ultraviolet irradiation was not performed in the conversion step, and a simple TFT was produced.
<SIMS分析> <SIMS analysis>
藉由SIMS分析(二次離子質譜法)，對實施例1及比較例3中所製作的金屬氧化物半導體膜求出膜中的氫濃度及碳濃度。 The SIMS analysis (secondary ion mass spectrometry) was used to determine the hydrogen concentration and carbon concentration in the metal oxide semiconductor films produced in Example 1 and Comparative Example 3.
測定裝置使用優貝克菲(ULVAC-PHI)股份有限公司製造的PHI ADEPT-1010。 As a measuring device, PHI ADEPT-1010 manufactured by ULVAC-PHI Co., Ltd. was used.
作為測定條件，一次離子種設為Cs+、一次加速電壓設為1.0kV、檢測區域設為140μm×140μm。 As the measurement conditions, the primary ion species was set to Cs + , the primary acceleration voltage was set to 1.0 kV, and the detection area was set to 140 μm × 140 μm.
將藉由SIMS分析而估計的氫及碳的濃度表示於表1。再者，由於在深度方向濃度產生差異，因此以濃度範圍表示。 Table 1 shows the hydrogen and carbon concentrations estimated by SIMS analysis. Moreover, since the density | concentration difference arises in a depth direction, it is expressed as a density range.
根據表1的實施例1與比較例3的對比可知，藉由本發明的方法而製作的金屬氧化物半導體膜藉由紫外線照射而膜中的氫濃度及碳濃度降低。 According to the comparison between Example 1 and Comparative Example 3 in Table 1, it can be seen that the metal oxide semiconductor film produced by the method of the present invention decreases the hydrogen concentration and carbon concentration in the film by ultraviolet irradiation.
[評價] [Evaluation]
<電晶體特性> <Transistor Characteristics>
使用半導體參數分析儀4156C(安捷倫科技(Agilent Technologies)股份有限公司製造)，對所製作的各簡易型TFT測定電晶體特性Vg-Id，並求出線性遷移率。 Using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies Co., Ltd.), transistor characteristics V g -I d were measured for each of the simple TFTs manufactured, and the linear mobility was determined.
電晶體特性Vg-Id的測定藉由以下方式而進行：將汲極電壓(Vd)固定為+20V，使閘極電壓(Vg)在-15V~+30V的範圍內變化，測定各閘極電壓下的汲極電流(Id)。 The transistor characteristics V g -I d were measured by fixing the drain voltage (V d ) to + 20V and changing the gate voltage (V g ) within the range of -15V to + 30V. Drain current (I d ) at each gate voltage.
再者，關於比較例1，無法確認到導通關斷動作，表現出導體的行為。 Furthermore, in Comparative Example 1, it was not possible to confirm the on-off operation, and the behavior of the conductor was exhibited.
另外，關於比較例3，未表現出電傳導性，表現出絕緣體的行為。 In Comparative Example 3, no electrical conductivity was exhibited, and the behavior of an insulator was exhibited.
將評價結果表示於表2。另外，將實施例1、實施例2及比較例1、比較例2的電晶體特性Vg-Id的圖表表示於圖11。另外，將 比較例1、比較例4的電晶體特性Vg-Id的圖表表示於圖12。 The evaluation results are shown in Table 2. In addition, a graph of the transistor characteristics V g -I d of Example 1, Example 2, and Comparative Example 1 and Comparative Example 2 is shown in FIG. 11. A graph of the transistor characteristics V g -I d of Comparative Example 1 and Comparative Example 4 is shown in FIG. 12.
如表2所示般可知，具備藉由本發明的製造方法而製作的金屬氧化物半導體膜的實施例的簡易型TFT，與比較例的簡易型TFT相比，線性遷移率大，具有高的半導體特性。 As shown in Table 2, it can be seen that the simple type TFT of the example having the metal oxide semiconductor film produced by the manufacturing method of the present invention has a higher linear mobility and a higher semiconductor than the simple type TFT of the comparative example. characteristic.
此處，根據實施例1、實施例2及比較例1、比較例2的對比可知，藉由將金屬氧化物半導體前驅物膜的鋅與錫的組成比設為0.7≦Sn/(Sn+Zn)≦0.9的範圍，而可增大線性遷移率。 Here, according to the comparison between Example 1, Example 2, and Comparative Example 1 and Comparative Example 2, it can be seen that the composition ratio of zinc to tin of the metal oxide semiconductor precursor film is set to 0.7 ≦ Sn / (Sn + Zn ) ≦ 0.9, and the linear mobility can be increased.
另外，根據實施例1與實施例5、實施例6的對比可知，全部金屬成分中的錫及鋅的比例越高，則越可增大線性遷移率。 In addition, according to the comparison between Example 1 and Examples 5 and 6, it can be seen that the higher the ratio of tin and zinc in all metal components, the more the linear mobility can be increased.
另外，根據實施例1與實施例4的對比可知，即便增大轉化步驟中的紫外線的照度，線性遷移率亦不變。由此可知，只要照射金屬氧化物半導體前驅物膜的轉化所必需充分的照度的紫外線 即可。 In addition, it can be seen from the comparison between Example 1 and Example 4 that even if the illuminance of ultraviolet rays in the conversion step is increased, the linear mobility does not change. From this, it can be seen that as long as the ultraviolet ray with sufficient illuminance necessary for conversion of the metal oxide semiconductor precursor film is irradiated, Just fine.
另外，根據實施例1~實施例4可知，即便是250℃以下的低溫的加熱，亦可增大線性遷移率。 In addition, it is understood from Examples 1 to 4 that the linear mobility can be increased even at a low temperature of 250 ° C or lower.
另外，如圖12所示般可知，比較例1及比較例4均表現出導體的行為，但與進行了紫外線照射的比較例1相比，未進行紫外線照射的比較例4的電子傳遞特性變高。由此可知，為了獲得紫外線照射處理的效果，必須恰當選擇鋅與錫的組成比的範圍。 In addition, as shown in FIG. 12, it can be seen that both Comparative Example 1 and Comparative Example 4 exhibited the behavior of a conductor, but the electron transfer characteristics of Comparative Example 4 which was not subjected to ultraviolet irradiation changed compared to Comparative Example 1 which was subjected to ultraviolet irradiation. high. This shows that in order to obtain the effect of the ultraviolet irradiation treatment, the range of the composition ratio of zinc to tin must be appropriately selected.
根據以上所述可知曉本發明的效果。 As described above, the effects of the present invention are known.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014218391 | 2014-10-27 | ||
| JP2014-218391 | 2014-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201616578A TW201616578A (en) | 2016-05-01 |
| TWI663652B true TWI663652B (en) | 2019-06-21 |
Family
ID=55857145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104132656A TWI663652B (en) | 2014-10-27 | 2015-10-05 | Metal oxide semiconductor film, thin film transistor , and electronic device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6257799B2 (en) |
| KR (1) | KR101967564B1 (en) |
| TW (1) | TWI663652B (en) |
| WO (1) | WO2016067799A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6741439B2 (en) * | 2016-02-24 | 2020-08-19 | 日本放送協会 | Method of manufacturing thin film transistor |
| CN112805813A (en) * | 2018-11-22 | 2021-05-14 | 三井化学株式会社 | Semiconductor element intermediate and method for manufacturing semiconductor element intermediate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010258057A (en) * | 2009-04-22 | 2010-11-11 | Konica Minolta Holdings Inc | Metal oxide semiconductor, method of manufacturing the same, and thin film transistor using the same |
| TW201236163A (en) * | 2011-01-28 | 2012-09-01 | Univ Northwestern | Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films |
| CN102986034A (en) * | 2010-07-02 | 2013-03-20 | 惠普发展公司，有限责任合伙企业 | Thin film transistors |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2009011224A1 (en) | 2007-07-18 | 2010-09-16 | コニカミノルタホールディングス株式会社 | Method for producing metal oxide semiconductor and thin film transistor obtained thereby |
| US8946066B2 (en) * | 2011-05-11 | 2015-02-03 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device |
-
2015
- 2015-09-28 KR KR1020177010201A patent/KR101967564B1/en active IP Right Grant
- 2015-09-28 WO PCT/JP2015/077296 patent/WO2016067799A1/en active Application Filing
- 2015-09-28 JP JP2016556442A patent/JP6257799B2/en active Active
- 2015-10-05 TW TW104132656A patent/TWI663652B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010258057A (en) * | 2009-04-22 | 2010-11-11 | Konica Minolta Holdings Inc | Metal oxide semiconductor, method of manufacturing the same, and thin film transistor using the same |
| CN102986034A (en) * | 2010-07-02 | 2013-03-20 | 惠普发展公司，有限责任合伙企业 | Thin film transistors |
| TW201236163A (en) * | 2011-01-28 | 2012-09-01 | Univ Northwestern | Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016067799A1 (en) | 2016-05-06 |
| JP6257799B2 (en) | 2018-01-10 |
| JPWO2016067799A1 (en) | 2017-08-17 |
| KR101967564B1 (en) | 2019-04-09 |
| TW201616578A (en) | 2016-05-01 |
| KR20170051519A (en) | 2017-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6180908B2 (en) | Metal oxide semiconductor film, thin film transistor, display device, image sensor and X-ray sensor | |
| US9515193B2 (en) | Metal oxide film, method for manufacturing same, thin film transistor, display apparatus, image sensor, and X-ray sensor | |
| TWI671820B (en) | Method of producing metal oxide film, metal oxide film, thin-film transistor, and electronic device | |
| US9779938B2 (en) | Metal oxide thin film, method of producing same, and coating solution for forming metal oxide thin film used in said method | |
| TWI663652B (en) | Metal oxide semiconductor film, thin film transistor , and electronic device | |
| TW201526071A (en) | Method of producing metal oxide film, metal oxide film, thin-film transistor, display device, image sensor, and x-ray sensor | |
| TWI648795B (en) | Method of producing metal oxide film | |
| JP6061831B2 (en) | Method for producing metal oxide film and method for producing thin film transistor | |
| TWI689622B (en) | Method of producing metal oxide film, metal oxide film, thin-film transistor, method of producing thin-film transistor, electronic device and ultra-violet light irradiation apparatus | |
| TWI659451B (en) | Method of producing metal oxide film, metal oxide film, thin-film transistor, method of producing thin-film transistor, and electronic device | |
| JP6086854B2 (en) | Metal oxide film manufacturing method, metal oxide film, thin film transistor, display device, image sensor, and X-ray sensor |