TW201545988A - Oxide particles, production method of the same, oxide particles dispersion liquid, thin film layer production method of oxide particles, thin film transistor and electron element using the same - Google Patents
Oxide particles, production method of the same, oxide particles dispersion liquid, thin film layer production method of oxide particles, thin film transistor and electron element using the same Download PDFInfo
- Publication number
- TW201545988A TW201545988A TW104117083A TW104117083A TW201545988A TW 201545988 A TW201545988 A TW 201545988A TW 104117083 A TW104117083 A TW 104117083A TW 104117083 A TW104117083 A TW 104117083A TW 201545988 A TW201545988 A TW 201545988A
- Authority
- TW
- Taiwan
- Prior art keywords
- oxide particle
- oxide
- film
- oxide particles
- solvent
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 370
- 239000006185 dispersion Substances 0.000 title claims abstract description 87
- 239000010409 thin film Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 claims abstract description 76
- 229910052738 indium Inorganic materials 0.000 claims abstract description 22
- 229910052718 tin Inorganic materials 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims description 187
- 239000000758 substrate Substances 0.000 claims description 73
- 239000003446 ligand Substances 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 40
- 239000004065 semiconductor Substances 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 23
- 238000009835 boiling Methods 0.000 claims description 21
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 19
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 19
- 239000005642 Oleic acid Substances 0.000 claims description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 10
- 239000012454 non-polar solvent Substances 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical group [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 claims 1
- 239000010410 layer Substances 0.000 description 51
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- 239000003990 capacitor Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000005401 electroluminescence Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000000059 patterning Methods 0.000 description 8
- -1 polybutylene terephthalate Polymers 0.000 description 8
- 238000005530 etching Methods 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- 239000000057 synthetic resin Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009429 electrical wiring Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 3
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910020923 Sn-O Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- JEZYPUQOMROVOQ-UHFFFAOYSA-N hexadecane-2-thiol Chemical compound CCCCCCCCCCCCCCC(C)S JEZYPUQOMROVOQ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 150000003573 thiols Chemical class 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
- 238000001771 vacuum deposition Methods 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- NNWNNQTUZYVQRK-UHFFFAOYSA-N 5-bromo-1h-pyrrolo[2,3-c]pyridine-2-carboxylic acid Chemical compound BrC1=NC=C2NC(C(=O)O)=CC2=C1 NNWNNQTUZYVQRK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920002574 CR-39 Polymers 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 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
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229920000831 ionic polymer Polymers 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
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004767 nitrides Chemical class 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 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
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
本發明是有關於一種氧化物粒子及其製造方法、氧化物粒子分散液、氧化物粒子薄膜的形成方法、薄膜電晶體、以及電子元件。The present invention relates to an oxide particle, a method for producing the same, a method for forming an oxide particle dispersion, a method for forming an oxide particle film, a thin film transistor, and an electronic device.
透明、高載子移動率、且製造適應性亦優異的透明氧化物半導體（TOS：Transparent Oxide Semiconductor）正受到關注。正進行研究將使用TOS 作為薄膜電晶體（ TFT ： Thin FilmTransistor）的活性層的TOS-TFT 作為顯示裝置的驅動元件而實用化。目前實用化的TOS-TFT 中的活性層是藉由真空成膜法所製造者。然而， 於真空成膜法的情形時， 製造成本容易變高。因此， 另一方面， 旨在以液體（ 溶液或分散液） 作為原料，藉由塗佈製程實現顯示出高特性的TOS 的研究正盛行。 利用塗佈製程的半導體膜（ 例如所述TOS 的薄膜）的製造技術亦稱為「印刷電子（ Printed Electronics）」， 作為下一代半導體製造製程而正備受期待。A transparent oxide semiconductor (TOS: Transparent Oxide Semiconductor) which is transparent, has a high carrier mobility, and is excellent in manufacturing suitability is attracting attention. In the study, a TOS-TFT using TOS as an active layer of a thin film transistor (TFT: Thin Film Transistor) has been put into practical use as a driving element of a display device. The active layer in the currently practical TOS-TFT is manufactured by a vacuum film formation method. However, in the case of the vacuum film forming method, the manufacturing cost is liable to become high. Therefore, on the other hand, research aimed at realizing a TOS exhibiting high characteristics by a coating process using a liquid (solution or dispersion) as a raw material is prevailing. A manufacturing technique using a semiconductor film of a coating process (for example, a film of the TOS) is also called "printed electronics", and is expected as a next-generation semiconductor manufacturing process.
另一方面，於塗佈製程中，對製造分散於分散液中的氧化物粒子的方法正進行各種研究。On the other hand, in the coating process, various studies are being conducted on a method of producing oxide particles dispersed in a dispersion.
例如，於Q.Liu等人著的「凖單分散性In2 O3 奈米晶體的研究：合成與光學測定（Study of Quasi-Monodisperse In2 O3 Nanocrystals：Synthesis and Optical Determination）」 美國化學學會期刊（Journal of American Chemical Society）, Vol.127, No.15, pp. 5276～5277（2005年）及J.Lee等人著的「用於透明和導電的ITO奈米晶體組件的易行的液相方法（A Facile Solution-Phase Approach to Transparent and Conducting ITO Nanocrystal Assemblies）」 Journal of American Chemical Society, Vol.134, No. 32, pp. 13410～13414（2012年）中對均勻分散的球狀In2 O3 粒子（氧化銦）、及其合成有所揭示。For example, "Study of quasi monodisperse nanocrystals In 2 O 3: Synthetic optical measurement (Study of Quasi-Monodisperse In 2 O 3 Nanocrystals: Synthesis and Optical Determination) " et al in U.S. Q.Liu Chemical Society Journal of American Chemical Society, Vol. 127, No. 15, pp. 5276-5277 (2005) and J. Lee et al. "Easy for transparent and conductive ITO nanocrystal modules. A Facile Solution-Phase Approach to Transparent and Conducting ITO Nanocrystal Assemblies" Journal of American Chemical Society, Vol. 134, No. 32, pp. 13410 - 13414 (2012) for uniformly dispersed spherical In 2 O 3 particles (indium oxide), and their synthesis are disclosed.
[發明所欲解決之課題][Problems to be solved by the invention]
然而，由於藉由非專利文獻1及非專利文獻2所記載的製造方法所製作的In2 O3 粒子為球狀，因此鄰接的粒子的接觸面積小，將含有所述粒子的分散液塗佈於基材上並進行乾燥而獲得的薄膜僅可成為載子移動率低者。However, since the In 2 O 3 particles produced by the production methods described in Non-Patent Document 1 and Non-Patent Document 2 are spherical, the contact area of adjacent particles is small, and the dispersion containing the particles is coated. The film obtained by drying on a substrate can only be a carrier having a low mobility.
本發明是鑒於所述情況而完成者。 即，本發明的課題在於提供一種可獲得具有高載子移動率的氧化物粒子薄膜的氧化物粒子及其製造方法、以及含有所述氧化物粒子的分散液。 另外，本發明的課題在於提供一種具有優異的載子移動率的氧化物粒子薄膜的形成方法、以及具備所述薄膜的薄膜電晶體及電子元件。 [解決課題之手段]The present invention has been completed in view of the above circumstances. That is, an object of the present invention is to provide an oxide particle which can obtain an oxide particle film having a high carrier mobility, a method for producing the same, and a dispersion liquid containing the oxide particles. Further, an object of the present invention is to provide a method for forming an oxide particle film having excellent carrier mobility, and a thin film transistor and an electronic device including the film. [Means for solving the problem]
達成所述課題的本發明如以下所述。 ＜1＞ 一種氧化物粒子，其含有選自In及Sn中的至少一種元素，且具有至少含有兩個突出部、相鄰的突出部的各突出軸方向存在互相交叉的關係的形狀。 ＜2＞ 如＜1＞所述的氧化物粒子，其含有In與選自Sn、Ga及Zn中的至少一種元素。 ＜3＞ 如＜1＞或＜2＞所述的氧化物粒子，其最大長度為3 nm以上且100 nm以下。 ＜4＞ 如＜1＞至＜3＞中任一項所述的氧化物粒子，其含有三個或四個突出部。The present invention for achieving the above problems is as follows. <1> An oxide particle containing at least one element selected from the group consisting of In and Sn, and having a shape in which each of the protruding axis directions including at least two protruding portions and adjacent protruding portions intersect each other. <2> The oxide particle according to <1>, which contains In and at least one element selected from the group consisting of Sn, Ga, and Zn. <3> The oxide particles according to <1> or <2> have a maximum length of 3 nm or more and 100 nm or less. <4> The oxide particle according to any one of <1> to <3> which has three or four protrusions.
＜5＞ 一種氧化物粒子分散液，其含有溶劑與分散於溶劑中的如＜1＞至＜4＞中任一項所述的氧化物粒子。 ＜6＞ 如＜5＞所述的氧化物微粒子分散液，其中如＜1＞至＜4＞中任一項所述的氧化物粒子的含量相對於全部氧化物粒子的質量為30質量%以上。 ＜7＞ 如＜5＞或＜6＞所述的氧化物粒子分散液，其中於氧化物粒子的表面具有含有烴基的配位子。 ＜8＞ 如＜5＞至＜7＞中任一項所述的氧化物粒子分散液，其以1 mg/ml以上且500 mg/ml以下的濃度含有氧化物粒子。 ＜9＞ 如＜5＞至＜8＞中任一項所述的氧化物粒子分散液，其中溶劑為非極性溶劑。<5> An oxide particle dispersion containing the solvent and the oxide particles according to any one of <1> to <4>, which are dispersed in a solvent. The content of the oxide particles according to any one of <1> to <4> is 30% by mass or more based on the mass of all the oxide particles. . <7> The oxide particle dispersion according to <5>, wherein the oxide particle has a ligand containing a hydrocarbon group on the surface of the oxide particle. The oxide particle dispersion liquid according to any one of <5> to <7>, which contains oxide particles at a concentration of 1 mg/ml or more and 500 mg/ml or less. The oxide particle dispersion according to any one of <5> to <8> wherein the solvent is a non-polar solvent.
＜10＞ 一種氧化物粒子的製造方法，所述氧化物粒子含有選自In及Sn中的至少一種元素，且具有至少含有兩個突出部、相鄰的突出部的各突出軸方向存在互相交叉的關係的形狀，所述氧化物粒子的製造方法包括：溶液製備步驟，製備含有溶劑、選自In及Sn中的元素的乙酸鹽及配位於元素的分散劑的溶液；及加熱步驟，於低於溶劑的沸點的溫度下對溶液進行加熱。 ＜11＞ 如＜10＞所述的氧化物粒子的製造方法，其中加熱步驟是於大氣壓下進行加熱。 ＜12＞ 如＜10＞或＜11＞所述的氧化物粒子的製造方法，其中溶劑的沸點為240℃以上，且加熱步驟中的加熱溫度為230℃以上、溶劑的沸點減去10℃而得的溫度以下。 ＜13＞ 如＜10＞至＜12＞中任一項所述的氧化物粒子的製造方法，其中分散劑具有烴基。 ＜14＞ 如＜10＞至＜13＞中任一項所述的氧化物粒子的製造方法，其中分散劑含有選自油酸及油胺中的至少一者。<10> A method for producing an oxide particle, wherein the oxide particle contains at least one element selected from the group consisting of In and Sn, and each of the protruding axis directions having at least two protruding portions and adjacent protruding portions intersect each other The shape of the relationship, the method for producing the oxide particles includes: a solution preparation step of preparing a solution containing a solvent, an acetate selected from the elements of In and Sn, and a dispersant disposed in the element; and a heating step at a low temperature The solution is heated at a temperature at the boiling point of the solvent. <11> The method for producing an oxide particle according to <10>, wherein the heating step is heating at atmospheric pressure. <12> The method for producing an oxide particle according to <10>, wherein the solvent has a boiling point of 240 ° C or higher, and the heating temperature in the heating step is 230 ° C or higher, and the boiling point of the solvent is decreased by 10 ° C. The temperature is below. The method for producing an oxide particle according to any one of <10>, wherein the dispersing agent has a hydrocarbon group. The method for producing an oxide particle according to any one of the above aspects, wherein the dispersing agent contains at least one selected from the group consisting of oleic acid and oleylamine.
＜15＞ 一種氧化物粒子薄膜的形成方法，其是於基板上形成含有氧化物粒子的薄膜，所述氧化物粒子薄膜的形成方法包括：塗佈步驟，將如＜5＞至＜9＞中任一項所述的氧化物粒子分散液塗佈於基板上；及乾燥步驟，對塗佈於基板上的氧化物粒子分散液加以乾燥而去除溶劑的至少一部分。 ＜16＞ 如＜15＞所述的氧化物粒子薄膜的形成方法，其中所述氧化物粒子分散液中的氧化物粒子於表面具有含有烴基的配位子，所述氧化物粒子薄膜的形成方法進一步包括將分散劑自形成於基板上的薄膜中去除的配位子去除步驟。 ＜17＞ 如＜16＞所述的氧化物粒子薄膜的形成方法，其中配位子去除步驟包括極性溶劑處理，藉由使形成於基板上的薄膜與至少含有極性溶劑的處理液接觸而去除分散劑。 ＜18＞ 如＜17＞所述的氧化物粒子薄膜的形成方法，其中處理液含有分子結構中至少具有選自胺基、硫醇基、羥基、硫氰基、及鹵素原子中的至少一者的化合物。<15> A method for forming an oxide particle film, wherein a film containing oxide particles is formed on a substrate, and the method for forming the oxide particle film includes a coating step, such as in <5> to <9> The oxide particle dispersion according to any one of the above is applied onto a substrate; and in the drying step, the oxide particle dispersion applied to the substrate is dried to remove at least a part of the solvent. <16> The method for forming an oxide particle film according to the above, wherein the oxide particles in the oxide particle dispersion have a hydrocarbon group-containing ligand on the surface, and the oxide particle film is formed. Further included is a ligand removal step of removing the dispersant from the film formed on the substrate. <17> The method for forming an oxide particle film according to <16>, wherein the ligand removal step comprises a polar solvent treatment, and the dispersion is removed by contacting a film formed on the substrate with a treatment liquid containing at least a polar solvent. Agent. <18> The method for forming an oxide particle film according to <17>, wherein the treatment liquid contains at least one selected from the group consisting of an amine group, a thiol group, a hydroxyl group, a thiocyano group, and a halogen atom in a molecular structure. compound of.
＜19＞ 如＜15＞至＜18＞中任一項所述的氧化物粒子薄膜的形成方法，其中氧化物粒子薄膜為導電膜。 ＜20＞ 如＜15＞至＜18＞中任一項所述的氧化物粒子薄膜的形成方法，其中氧化物粒子薄膜為半導體膜。 ＜21＞ 一種薄膜電晶體，其具備藉由如＜20＞所述的氧化物粒子薄膜的形成方法所製造的半導體膜作為活性層。 ＜22＞ 一種電子元件，其具備如＜21＞所述的薄膜電晶體。 [發明的效果]The method for forming an oxide particle film according to any one of the above aspects, wherein the oxide particle film is a conductive film. The method of forming an oxide particle film according to any one of the above aspects, wherein the oxide particle film is a semiconductor film. <21> A thin film transistor comprising a semiconductor film produced by the method for forming an oxide particle film according to <20> as an active layer. <22> An electronic component comprising the thin film transistor according to <21>. [Effects of the Invention]
根據本發明，可提供一種可獲得優異的電特性的氧化物粒子及其製造方法、以及分散液。 另外，本發明提供一種具有優異的電特性的氧化物粒子薄膜的形成方法、以及薄膜電晶體及電子元件。According to the present invention, it is possible to provide an oxide particle which can obtain excellent electrical characteristics, a method for producing the same, and a dispersion. Further, the present invention provides a method for forming an oxide particle film having excellent electrical characteristics, and a film transistor and an electronic device.
以下，一面適當參照圖式，一面對本發明的氧化物粒子及其製造方法、氧化物粒子分散液、氧化物粒子薄膜的形成方法、薄膜電晶體、以及電子元件進行具體說明。再者， 對圖中具有相同或相對應的功能的構件（ 構成要素）標註相同的符號並適當省略說明。另外， 在本說明書中， 於藉由記號「～ 」表示數值範圍的情形時， 包含下限值及上限值。Hereinafter, the oxide particles and the method for producing the same, the oxide particle dispersion, the method of forming the oxide particle film, the thin film transistor, and the electronic component will be specifically described with reference to the drawings. In addition, members (components) having the same or corresponding functions in the drawings are denoted by the same reference numerals, and their description will be omitted as appropriate. In addition, in the present specification, when the numerical value range is indicated by the symbol "-", the lower limit value and the upper limit value are included.
[氧化物粒子] 本發明的氧化物粒子含有選自In及Sn中的一種或兩種以上的元素，且具有至少含有兩個突出部、相鄰的突出部的各突出軸方向存在互相交叉的關係的形狀。[Oxide Particles] The oxide particles of the present invention contain one or two or more elements selected from the group consisting of In and Sn, and each of the protruding axis directions having at least two protruding portions and adjacent protruding portions intersect each other. The shape of the relationship.
所謂「突出部」是粒子中存在可表示具有突出軸的長度方向的形狀（例如不為圓形的橢圓形狀）的部分。參照圖16，以具有包含三個突出部的形狀的粒子的突出部為例進行具體說明。 若著眼於圖16所示的突出部621，突出部623，則於描繪包圍突出部621的區域621S、與包圍突出部623的區域623S的情形時，所謂突出部623，是指於區域623S中，相對於與區域621S重疊的部分的突出部623的突出軸上的長度B，未與區域621S重疊的部分的突出部623的突出軸上的長度A為B/2以上的部分。 突出部可藉由以穿透式電子顯微鏡（TEM）將氧化物粒子放大進行觀察而確認。 橢圓近似的方法及長度A、長度B的測定方法如以下所述。對於藉由TEM觀察所測定的粒子圖像，確定出突出部的頂點及自突出部的頂點延伸的突出軸與粒子的相反側的輪廓相接的點，將連結兩點的線作為橢圓的長軸。其次，作相對於所述兩點的垂直二等分線，將連結垂直二等分線與粒子的輪廓重疊的兩點的線作為短軸，藉由由此獲得的橢圓，對粒子的突出部進行橢圓近似。對各突出部進行橢圓近似後，求出至少兩個以上的橢圓重疊的區域。此處，根據粒子形狀而會有三個以上的橢圓重疊，於該情形時，求出三個以上的橢圓重疊的區域。對於所述區域，將與突出軸相交的兩點間的距離設為B。另一方面，將突出部的頂點和突出軸與所述區域相交而得的點中靠近突出部的點的兩點間的距離設為A。The "protrusion portion" is a portion in which particles have a shape indicating a longitudinal direction of a protruding axis (for example, an elliptical shape that is not circular). Referring to Fig. 16, a projection having particles having a shape of three projections will be specifically described as an example. When focusing on the protruding portion 621 and the protruding portion 623 shown in FIG. 16, when the region 621S surrounding the protruding portion 621 and the region 623S surrounding the protruding portion 623 are drawn, the protruding portion 623 is referred to as the region 623S. With respect to the length B on the protruding axis of the protruding portion 623 of the portion overlapping the region 621S, the length A on the protruding axis of the protruding portion 623 of the portion not overlapping the region 621S is a portion of B/2 or more. The protrusion can be confirmed by observing the oxide particles by a transmission electron microscope (TEM). The method of elliptical approximation and the method of measuring length A and length B are as follows. With respect to the particle image measured by TEM observation, the point at which the apex of the protruding portion and the protruding axis extending from the apex of the protruding portion meet the contour of the opposite side of the particle is determined, and the line connecting the two points is regarded as the length of the ellipse. axis. Next, as a vertical bisector of the two points, a line connecting two points of the vertical bisector and the contour of the particle is taken as a short axis, and the protrusion of the particle is obtained by the ellipse thus obtained. Perform an elliptical approximation. After elliptical approximation is performed on each of the protruding portions, at least two or more regions in which the ellipse overlaps are obtained. Here, three or more ellipses are overlapped depending on the particle shape, and in this case, a region in which three or more ellipses overlap is obtained. For the area, the distance between two points intersecting the protruding axis is set to B. On the other hand, the distance between the two points of the point near the protruding portion among the points at which the apex of the protruding portion and the protruding axis intersect with the region is set to A.
所謂「突出軸方向互相交叉」只要兩個突出部的突出軸方向不平行即可，包括兩個突出部的各突出軸於一平面上相交的情形（平面交叉的情形），及兩個突出部的各突出軸分別處於不同的平面上且存在立體交錯的關係的情形（立體交叉的情形）兩者。The "protruding axis directions intersect each other" as long as the protruding axis directions of the two protruding portions are not parallel, and the protruding axes including the two protruding portions intersect on one plane (the case where the plane intersects), and the two protruding portions Each of the protruding axes is on a different plane and has a three-dimensionally interlaced relationship (in the case of a three-dimensional intersection).
本發明的氧化物粒子中作為除了In及Sn以外的元素，亦可含有選自Ga及Zn中的至少一種元素。 本發明的氧化物粒子較佳為至少含有In的氧化物粒子，亦可進而含有選自Sn、Ga及Zn中的至少一種元素。 於為含有In的氧化物粒子的情形時，由於In的最外殼電子軌域為5S，因此於為氧化物的情形時容易獲得更高的載子移動率。 另外，於使以In作為基底的氧化物結晶含有Sn的情形時，可實現載子濃度的增大。 另一方面，於含有Ga的情形時，變得可抑制氧缺陷，可於不大幅度降低載子移動率的情況下降低載子濃度。另外，藉由含有Zn，可期待載子移動率的增大。 藉由使用帶隙寬（～3 eV）的氧化物粒子，可製造透明且相對於光照射穩定的導電膜、半導體膜、及TFT。 就所述觀點而言，本發明的較佳的氧化物粒子較佳為：包含In與O者；包含In、Ga及O者；包含In、Zn及O者；包含In、Sn及O者；包含In、Ga、Zn及O者；包含In、Ga、Sn及O者；以及包含In、Sn、Zn及O者。The oxide particles of the present invention may contain at least one element selected from the group consisting of Ga and Zn as an element other than In and Sn. The oxide particles of the present invention preferably contain at least one oxide of In, and further contain at least one element selected from the group consisting of Sn, Ga, and Zn. In the case of the oxide particles containing In, since the outermost electron domain of In is 5S, it is easy to obtain a higher carrier mobility when it is an oxide. Further, when the oxide crystal having In as a base contains Sn, an increase in the concentration of the carrier can be achieved. On the other hand, in the case where Ga is contained, oxygen deficiency can be suppressed, and the carrier concentration can be lowered without greatly reducing the carrier mobility. Further, by containing Zn, an increase in the carrier mobility can be expected. By using oxide particles having a band gap (~3 eV), it is possible to produce a conductive film, a semiconductor film, and a TFT which are transparent and stable with respect to light irradiation. In view of the above, preferred oxide particles of the present invention are preferably those containing In and O; those containing In, Ga, and O; those containing In, Zn, and O; and those containing In, Sn, and O; Those containing In, Ga, Zn, and O; those containing In, Ga, Sn, and O; and those containing In, Sn, Zn, and O.
本發明的氧化物粒子具有至少含有兩個突出部、且相鄰的突出部的突出軸方向互相交叉的形狀（以下亦稱為「特定形狀」）。 圖11A是表示本發明的含有兩個突出部的氧化物粒子的形狀（以下亦稱為「雙股形狀」或「雙翼回力棒（boomerang）形狀」）的示意平面圖，圖11B是表示本發明的含有三個突出部的氧化物粒子的形狀的示意平面圖，及圖11C是表示本發明的含有四個突出部的氧化物粒子的形狀（以下亦稱為「四股形狀」或「四翼回力棒形狀」）的示意平面圖。 於圖11A所示的雙股形狀的氧化物粒子60中，包含兩個突出部611、及突出部612，兩個突出軸方向存在互相交叉的關係。進而，於兩個突出部611及突出部612之間含有凹部615。The oxide particles of the present invention have a shape in which at least two protruding portions are included and the protruding axis directions of the adjacent protruding portions cross each other (hereinafter also referred to as "specific shape"). Fig. 11A is a schematic plan view showing the shape of an oxide particle containing two protruding portions according to the present invention (hereinafter also referred to as "double-strand shape" or "two-wing shape" (boomerang shape), and Fig. 11B shows the present invention. FIG. 11C is a schematic plan view showing the shape of oxide particles containing three protrusions, and FIG. 11C is a view showing the shape of oxide particles containing four protrusions of the present invention (hereinafter also referred to as "four-strand shape" or "four-wing back force bar". A schematic plan view of the shape "). The double-stranded oxide particles 60 shown in FIG. 11A include two protruding portions 611 and protruding portions 612, and the two protruding axis directions have a mutual intersecting relationship. Further, a concave portion 615 is provided between the two protruding portions 611 and the protruding portion 612.
於圖11B所示的三股形狀的氧化物粒子62中，包含突出部621、突出部622及突出部623的三個突出部，三個突出軸方向存在互相交叉的關係。進而，於三個突出部之間含有凹部625、凹部626及凹部627的三個凹部。 於圖11C所示的四股形狀的氧化物粒子63中，包含四個突出部631、突出部632、突出部633及突出部634，四個突出軸方向存在互相交叉的關係。且於四個突出部之間含有凹部635、凹部636、凹部637及凹部638。四個突出部可存在於同一平面內，亦可不存在於同一平面內。較佳為不存在於同一平面。 於本發明中，氧化物粒子的形狀中，由於具有三個或四個突出部者容易獲得具有高載子移動率的氧化物粒子薄膜，故而較佳。The three-strand oxide particles 62 shown in FIG. 11B include three protruding portions of the protruding portion 621, the protruding portion 622, and the protruding portion 623, and the three protruding axis directions have a mutual intersecting relationship. Further, three concave portions of the concave portion 625, the concave portion 626, and the concave portion 627 are provided between the three protruding portions. The four-shaped oxide particles 63 shown in FIG. 11C include four protruding portions 631, a protruding portion 632, a protruding portion 633, and a protruding portion 634, and the four protruding axis directions are in a mutually intersecting relationship. A recess 635, a recess 636, a recess 637, and a recess 638 are included between the four protrusions. The four protrusions may exist in the same plane or may not exist in the same plane. Preferably, it does not exist in the same plane. In the present invention, among the shapes of the oxide particles, it is preferable to have an oxide particle film having a high carrier mobility because three or four protrusions are easily obtained.
本發明的氧化物粒子可為形狀一致者（例如僅由具有四個突出部的四股形狀所構成者），亦可為包含兩種以上的形狀的氧化物粒子而構成者（例如，包含雙股形狀者、三股形狀者、及四股形狀者的構成）。包含兩種以上的形狀的氧化物粒子而構成者由於容易獲得具有高載子移動率的氧化物粒子薄膜，故而較佳。 使用本發明的氧化物粒子所製作的氧化物粒子薄膜具有高載子移動率。推測其理由在於下述（1）～（2）中的至少一者。 （1）： 本發明的氧化物粒子薄膜於著眼於互相鄰接的兩個氧化物粒子的情形時，存在一個氧化物粒子的突出部嵌入另一個氧化物粒子的相鄰的兩個突出部所夾著的凹部中的可能性。例如，於圖11A所示的雙股形狀的情形時，存在一個氧化物粒子的突出部611及突出部612中的一者嵌入另一個氧化物粒子的凹部615中的可能性。因此，多數氧化物粒子之間的接觸面積增加。因此，形成包含互相良好地接觸的氧化物粒子的氧化物粒子薄膜，其結果，可獲得具有高電特性的氧化物粒子薄膜。 （2）： 於本發明的氧化物粒子的特定形狀例如為圖11A所示的雙股形狀的情形時，可認為是形成突出部611及突出部612的兩個球狀氧化物粒子與連結該兩個球狀氧化物粒子的球狀氧化物粒子結合而成的聚集體形狀。即，認為本發明的雙股形狀的氧化物粒子相當於三個球狀粒子聚集而成的部分。因此，與藉由球狀氧化物粒子所製作的氧化物粒子薄膜相比，粒界的影響降低，本發明的氧化物粒子薄膜顯示出高載子移動率。The oxide particles of the present invention may have a uniform shape (for example, a four-stripe shape having only four protruding portions), or may be composed of oxide particles having two or more shapes (for example, including double strands) The shape, the shape of the three-piece shape, and the shape of the four-piece shape). It is preferable that the oxide particles of two or more shapes are formed to easily obtain an oxide particle film having a high carrier mobility. The oxide particle film produced by using the oxide particles of the present invention has a high carrier mobility. The reason is presumed to be at least one of the following (1) to (2). (1): When the oxide particle film of the present invention focuses on two oxide particles adjacent to each other, there is a case where one protruding portion of the oxide particles is embedded in the adjacent two protruding portions of the other oxide particle. The possibility of the recess. For example, in the case of the double-strand shape shown in FIG. 11A, there is a possibility that one of the protrusions 611 and the protrusions 612 of one oxide particle are embedded in the recess 615 of the other oxide particle. Therefore, the contact area between most oxide particles increases. Therefore, an oxide particle film containing oxide particles which are in good contact with each other is formed, and as a result, an oxide particle film having high electric characteristics can be obtained. (2): When the specific shape of the oxide particles of the present invention is, for example, a double-strand shape as shown in FIG. 11A, it is considered that two spherical oxide particles forming the protruding portion 611 and the protruding portion 612 are connected to the same. The shape of the aggregate in which the spherical oxide particles of the two spherical oxide particles are combined. That is, it is considered that the double-stranded oxide particles of the present invention correspond to a portion in which three spherical particles are aggregated. Therefore, the influence of the grain boundary is lower than that of the oxide particle film produced by the spherical oxide particles, and the oxide particle film of the present invention exhibits a high carrier mobility.
本發明的氧化物粒子的最大長度、即以氧化物粒子的外周相接所包含的方式描繪的最小體積的球的直徑較佳為3 nm以上且100 nm以下。就氧化物粒子分散液的分散穩定性、容易獲得具有高載子移動率的氧化物粒子薄膜的方面而言，氧化物粒子的最大長度較佳為5 nm以上且50 nm以下的範圍，尤其更佳為5 nm以上且30 nm以下的範圍。 於本發明中，氧化物粒子的最大長度可藉由穿透式電子顯微鏡（TEM）將氧化物粒子放大觀察並進行拍攝，計測攝像（照片）中的粒子的最大長度而求出。The maximum length of the oxide particles of the present invention, that is, the diameter of the smallest volume of the spheres drawn so as to be included in the outer periphery of the oxide particles is preferably 3 nm or more and 100 nm or less. The maximum length of the oxide particles is preferably in the range of 5 nm or more and 50 nm or less, particularly in terms of dispersion stability of the oxide particle dispersion and easy formation of an oxide particle film having a high carrier mobility. It is preferably in the range of 5 nm or more and 30 nm or less. In the present invention, the maximum length of the oxide particles can be obtained by observing and photographing the oxide particles by a transmission electron microscope (TEM), and measuring the maximum length of the particles in the image (photograph).
[氧化物粒子分散液] 本發明的氧化物粒子分散液含有溶劑、及分散於溶劑中的已說明的氧化物粒子。 就溶劑中的氧化物粒子的分散性提高的方面而言，較理想為於氧化物粒子的表面具有含有烴基的配位子。就提高氧化物粒子的分散性的性質優異的方面而言，作為所述烴基，較佳為脂肪族烴基，進而較佳為碳數為6以上的飽和或不飽和的脂肪族烴基，尤其更佳為碳數為10以上的飽和或不飽和的脂肪族烴基。作為更具體的配位子，包含含有所述脂肪族烴基的羧酸、醇、胺、硫醇、氧化膦、溴化物等。 作為配位子的較佳的具體例，可列舉：癸酸、十二酸、十四酸、十六酸、硬脂酸、二十二酸、油酸、芥子酸、油胺、十二烷胺、十二烷硫醇、1,2-十六烷硫醇、三辛基氧化膦、十六烷基三甲基溴化銨等。 於本發明的氧化物粒子分散液中亦可含有兩種以上的配位子。作為較佳的組合例，例如可列舉油酸與油胺的組合。[Oxide Particle Dispersion] The oxide particle dispersion of the present invention contains a solvent and the above-described oxide particles dispersed in a solvent. In terms of improving the dispersibility of the oxide particles in the solvent, it is preferred to have a ligand containing a hydrocarbon group on the surface of the oxide particles. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably a saturated or unsaturated aliphatic hydrocarbon group having 6 or more carbon atoms, particularly preferably, in terms of improving the dispersibility of the oxide particles. It is a saturated or unsaturated aliphatic hydrocarbon group having a carbon number of 10 or more. More specific ligands include a carboxylic acid, an alcohol, an amine, a thiol, a phosphine oxide, a bromide or the like containing the aliphatic hydrocarbon group. Preferred examples of the ligand include citric acid, dodecanoic acid, tetradecanoic acid, palmitic acid, stearic acid, behenic acid, oleic acid, sinapic acid, oleylamine, and dodecane. Amine, dodecanethiol, 1,2-hexadecanethiol, trioctylphosphine oxide, cetyltrimethylammonium bromide, and the like. Two or more kinds of ligands may be contained in the oxide particle dispersion of the present invention. As a preferable combination example, the combination of oleic acid and oleylamine is mentioned, for example.
氧化物粒子分散液中的配位子的含量是根據構成氧化物粒子的元素的種類及組成、氧化物粒子的形狀、氧化物粒子的最大長度、配位子的種類等而決定最適量。具體而言，若相對於氧化物粒子分散液所含的氧化物粒子的質量為1質量%以上的範圍，則溶劑中的氧化物粒子的分散性提高。更佳為5質量%以上，尤其更佳為10質量%以上。氧化物粒子分散液中的配位子的濃度的上限適當的是相對於氧化物粒子分散液所含的氧化物粒子的質量為1000質量%以下的範圍，就容易獲得具有高載子移動率的氧化物粒子薄膜的方面而言，較佳為500質量%以下的範圍，尤其更佳為300質量%以下的範圍。The content of the ligand in the oxide particle dispersion is determined by the type and composition of the element constituting the oxide particle, the shape of the oxide particle, the maximum length of the oxide particle, the type of the ligand, and the like. Specifically, when the mass of the oxide particles contained in the oxide particle dispersion is in a range of 1% by mass or more, the dispersibility of the oxide particles in the solvent is improved. More preferably, it is 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit of the concentration of the ligand in the oxide particle dispersion is suitably in the range of 1000% by mass or less based on the mass of the oxide particles contained in the oxide particle dispersion, and it is easy to obtain a carrier having a high carrier mobility. The aspect of the oxide particle film is preferably in the range of 500% by mass or less, and more preferably in the range of 300% by mass or less.
構成本發明的氧化物粒子分散液的溶劑較理想為非極性溶劑。由於配位於氧化物粒子表面的配位子的烴基通常為疏水性，因此藉由使用非極性溶劑，可提高氧化物粒子於溶劑中的分散性。 非極性溶劑並無特別限定，例如較佳為相對介電常數為5以下的非極性溶劑。尤其是於將氧化物粒子分散液塗佈於基材上並加以乾燥而形成氧化物粒子薄膜的情形時，適合的是不易殘存於乾燥後的氧化物粒子薄膜中的低沸點溶劑。作為低沸點溶劑，可列舉甲苯、辛烷、己烷等。The solvent constituting the oxide particle dispersion of the present invention is preferably a non-polar solvent. Since the hydrocarbon group of the ligands disposed on the surface of the oxide particles is generally hydrophobic, the dispersibility of the oxide particles in the solvent can be improved by using a non-polar solvent. The nonpolar solvent is not particularly limited, and for example, a nonpolar solvent having a relative dielectric constant of 5 or less is preferable. In particular, when the oxide particle dispersion is applied onto a substrate and dried to form an oxide particle film, a low boiling point solvent which is hard to remain in the dried oxide particle film is suitable. Examples of the low boiling point solvent include toluene, octane, and hexane.
本發明的氧化物粒子分散液例如可為含有單一形狀的氧化物粒子而構成者（例如，僅包含四股形狀者等），亦可為含有兩種以上的形狀的氧化物粒子而構成者（例如，三股形狀的氧化物粒子與四股形狀的氧化物粒子混合存在者等）。另外，本發明的具有特定形狀的氧化物粒子的含量較佳為相對於全部氧化物粒子的質量為含有30質量%以上，進而更佳為含有50質量%以上，尤其最佳為含有80質量%以上。 另外，於本發明中，特定形狀的氧化物粒子相對於全部氧化物粒子的質量的含量是藉由對分散液的滴加樣品進行TEM觀察，估算出非特定形狀的粒子及特定形狀粒子的體積後計算出各自的重量所測定的值。此處，於在TEM觀察的視野中存在10個以上的特定形狀粒子的條件下隨機進行TEM觀察，並估算出特定形狀粒子的重量後，估算存在於同一視野中的非特定形狀粒子的重量。The oxide particle dispersion liquid of the present invention may be composed of, for example, oxide particles having a single shape (for example, a shape containing only four strands), or may be composed of oxide particles having two or more shapes (for example, The three-strand oxide particles are mixed with the four-strand oxide particles, etc.). Further, the content of the oxide particles having a specific shape of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 80% by mass based on the mass of all the oxide particles. the above. Further, in the present invention, the content of the oxide particles of a specific shape with respect to the mass of all the oxide particles is estimated by TEM observation of the dropped sample of the dispersion liquid, and the volume of the non-specific shape particles and the specific shape particles is estimated. The values determined for the respective weights are then calculated. Here, the TEM observation is performed under the condition that there are ten or more particles of a specific shape in the TEM observation field, and the weight of the particles of the specific shape is estimated, and the weight of the non-specific shape particles existing in the same field of view is estimated.
藉由含有兩種以上的形狀的氧化物粒子所構成的氧化物粒子分散液，容易獲得具有高載子移動率的氧化物粒子薄膜，因此較佳。認為其原因在於鄰接的氧化物粒子間的接觸面積大，可容易地獲得緻密排列的氧化物粒子薄膜。It is preferable to use an oxide particle dispersion liquid composed of oxide particles having two or more shapes to easily obtain an oxide particle film having a high carrier mobility. The reason for this is considered to be that the contact area between adjacent oxide particles is large, and a densely arranged oxide particle film can be easily obtained.
於氧化物粒子分散液中，氧化物粒子的濃度較佳為1 mg/ml以上且500 mg/ml以下。藉由設為所述濃度範圍，可獲得分散狀態良好的氧化物粒子分散液，變得容易藉由一次塗佈便獲得充分的氧化物粒子薄膜的膜厚。進而，氧化物粒子彼此適度重疊，容易獲得具有高載子移動率的氧化物粒子薄膜。其中，較佳為氧化物粒子的濃度為5 mg/ml以上且200 mg/ml以下，尤其更佳為10 mg/ml以上且100 mg/ml以下。In the oxide particle dispersion, the concentration of the oxide particles is preferably 1 mg/ml or more and 500 mg/ml or less. By setting the concentration range, an oxide particle dispersion having a good dispersion state can be obtained, and a film thickness of a sufficient oxide particle film can be easily obtained by one application. Further, the oxide particles are appropriately overlapped with each other, and an oxide particle film having a high carrier mobility can be easily obtained. Among them, the concentration of the oxide particles is preferably 5 mg/ml or more and 200 mg/ml or less, and more preferably 10 mg/ml or more and 100 mg/ml or less.
[氧化物粒子的製造方法] 本發明的氧化物粒子的製造方法包括：溶液製備步驟，製備含有溶劑、選自In及Sn中的元素的乙酸鹽及配位於元素的分散劑的溶液；及加熱步驟，於低於有機溶劑的沸點的溫度下對溶液進行加熱。 所述各步驟較佳為於反應容器中進行。 進而，所述加熱步驟較佳為於大氣壓下進行。所謂大氣壓是指90 kPa～110 kPa。[Method for Producing Oxide Particles] The method for producing oxide particles of the present invention comprises: a solution preparation step of preparing a solution containing a solvent, an acetate selected from the elements of In and Sn, and a dispersant disposed in an element; and heating In the step, the solution is heated at a temperature lower than the boiling point of the organic solvent. The steps are preferably carried out in a reaction vessel. Further, the heating step is preferably carried out under atmospheric pressure. The atmospheric pressure means 90 kPa to 110 kPa.
其中，尤佳為乙酸銦（In(Ac)2 ）。於使用乙酸銦的情形時，容易引起粒子成長，容易獲得本發明的具有特定形狀的氧化物粒子。Among them, indium acetate (In(Ac) 2 ) is particularly preferred. In the case of using indium acetate, it is easy to cause particle growth, and it is easy to obtain the oxide particles having a specific shape of the present invention.
藉由溶液製備步驟所製備的溶液所含的選自In及Sn中的元素的乙酸鹽的濃度適當的是相對於所製備的溶液的總質量為1質量%以上且50質量%的範圍。尤其是就可容易地製造本發明的特定形狀的氧化物粒子的方面而言，較佳為5質量%以上且30質量%的範圍，尤其更佳為5質量%以上且20質量%的範圍。The concentration of the acetate of the element selected from the group consisting of In and Sn contained in the solution prepared by the solution preparation step is suitably in the range of 1% by mass or more and 50% by mass based on the total mass of the solution to be prepared. In particular, in terms of easily producing oxide particles of a specific shape of the present invention, it is preferably in the range of 5% by mass or more and 30% by mass, and more preferably in the range of 5% by mass or more and 20% by mass.
溶劑中具有160℃以上且360℃以下的沸點者容易於大氣壓下製造本發明的氧化物粒子，因此較佳。就與加熱步驟中的加熱溫度的關係而言，更佳為於240℃以上且360℃以下的範圍具有沸點者，尤其更佳為於275℃以上且360℃以下的範圍具有沸點者。 於使用具有所述沸點的有機溶劑製造本發明的氧化物粒子的情形時，容易將加熱步驟中的反應溫度設為容易引起氧化物粒子的粒子成長的範圍。其結果，容易由所製造的氧化物粒子獲得具有高載子移動率的氧化物粒子薄膜。 具有160℃以上且360℃以下的沸點的有機溶劑的較佳的具體例中包含例如十八烯、辛醚、三辛基膦、三辛基氧化膦、油酸、油胺等。It is preferred that the solvent having a boiling point of 160 ° C or higher and 360 ° C or lower in the solvent is easy to produce the oxide particles of the present invention under atmospheric pressure. The relationship with the heating temperature in the heating step is more preferably a boiling point in the range of 240 ° C or more and 360 ° C or less, and more preferably a boiling point in the range of 275 ° C or more and 360 ° C or less. When the oxide particles of the present invention are produced using an organic solvent having the above boiling point, the reaction temperature in the heating step is easily made to be a range in which the particles of the oxide particles are easily grown. As a result, an oxide particle film having a high carrier mobility can be easily obtained from the produced oxide particles. Preferred specific examples of the organic solvent having a boiling point of 160 ° C or more and 360 ° C or less include, for example, octadecene, octyl ether, trioctylphosphine, trioctylphosphine oxide, oleic acid, oleylamine and the like.
溶液製備步驟所使用的分散劑可根據構成所製備的氧化物粒子的元素的種類及組成等而決定最適量。分散劑可自配位於構成氧化物粒子的金屬者（以下亦稱為「配位子」）中選擇。分散劑的一部分藉由進行配位成為粒子表面的配位子，因此較佳的分散劑的形態與配位子的較佳的形態相同。就提高於有機溶劑中的分散性的性質優異的方面而言，分散劑較佳為具有脂肪族烴基者。尤其是就提高氧化物粒子的分散的性質優異的方面而言，較佳為具有碳數為6以上的飽和或不飽和的脂肪族烴基的分散劑，尤其更佳為具有碳數為10以上的飽和或不飽和的脂肪族烴基的分散劑。作為碳數為6以上的飽和或不飽和的脂肪族烴基，例如可列舉辛基、十二烷基、肉豆蔻基、油烯基等。作為更具體的配位子，包含含有所述脂肪族烴基的羧酸、醇、胺、硫醇、氧化膦、溴化物等。The dispersing agent used in the solution preparation step can be determined according to the kind, composition, and the like of the elements constituting the prepared oxide particles. The dispersant can be selected from those which are located in the metal constituting the oxide particles (hereinafter also referred to as "coordination"). Since a part of the dispersing agent is coordinated to form a ligand on the surface of the particle, the preferred form of the dispersing agent is the same as that of the preferred form of the ligand. The dispersant is preferably one having an aliphatic hydrocarbon group in terms of being excellent in the property of improving dispersibility in an organic solvent. In particular, in terms of improving the dispersion property of the oxide particles, a dispersant having a saturated or unsaturated aliphatic hydrocarbon group having 6 or more carbon atoms is preferable, and more preferably having a carbon number of 10 or more. A dispersing agent of a saturated or unsaturated aliphatic hydrocarbon group. Examples of the saturated or unsaturated aliphatic hydrocarbon group having 6 or more carbon atoms include an octyl group, a dodecyl group, a myristyl group, and an oleyl group. More specific ligands include a carboxylic acid, an alcohol, an amine, a thiol, a phosphine oxide, a bromide or the like containing the aliphatic hydrocarbon group.
作為分散劑的較佳的具體例，可列舉癸酸、十二酸、十四酸、十六酸、硬脂酸、二十二酸、油酸、芥子酸、油胺、十二烷胺、十二烷硫醇、1,2-十六烷硫醇、三辛基氧化膦、十六烷基三甲基溴化銨等。 藉由所述分散劑的一部分作為配位子而鍵結於氧化物粒子的表面，粒子彼此不會超過所需程度地凝聚，容易保持分散性。進而，於加熱步驟中，於保持所述分散性的狀態下進行粒子成長。 分散劑可組合兩種以上而使用。較佳的組合例包含例如油酸與油胺的組合。Preferred examples of the dispersing agent include capric acid, dodecanoic acid, tetradecanoic acid, palmitic acid, stearic acid, behenic acid, oleic acid, sinapic acid, oleylamine, and dodecylamine. Dodecanethiol, 1,2-hexadecanethiol, trioctylphosphine oxide, cetyltrimethylammonium bromide, and the like. By bonding a part of the dispersant as a ligand to the surface of the oxide particles, the particles do not aggregate to a desired degree, and the dispersibility is easily maintained. Further, in the heating step, the particles are grown while maintaining the dispersibility. The dispersing agent can be used in combination of two or more. Preferred combinations include, for example, a combination of oleic acid and oleylamine.
藉由溶液製備步驟所製備的溶液所含的分散劑的含量可根據構成所製備的氧化物粒子的元素的種類及組成、氧化物粒子的形狀、氧化物粒子的最大長度、配位子的種類等而決定最適量。具體而言，就維持所形成的粒子的分散性，並且容易地獲得粒子的方面而言，較佳為相對於藉由溶液製備步驟所製備的溶液所含的選自In及Sn中的元素的乙酸鹽的質量為10質量%以上且2000質量%的範圍，尤其更佳為50質量%以上且1000質量%的範圍。The content of the dispersant contained in the solution prepared by the solution preparation step may be based on the type and composition of the elements constituting the prepared oxide particles, the shape of the oxide particles, the maximum length of the oxide particles, and the type of the ligand. And then decide the optimal amount. Specifically, in terms of maintaining the dispersibility of the formed particles and easily obtaining the particles, it is preferably an element selected from the group consisting of In and Sn contained in the solution prepared by the solution preparation step. The mass of the acetate is in the range of 10% by mass or more and 2000% by mass, and more preferably in the range of 50% by mass or more and 1000% by mass.
將藉由溶液製備步驟所製備的溶液供於在低於溶液所含的溶劑的沸點的溫度下進行加熱的加熱步驟。藉由加熱步驟，可形成本發明的具有特定形狀的氧化物粒子。 就無需準備特殊的反應容器或反應裝置的方面而言，加熱步驟較佳為於大氣壓下進行。 加熱溫度只要為所加熱的溶液所含的溶劑的沸點以下的溫度即可，較佳為以所述沸點減去10℃而得的溫度作為上限，進而較佳為以較所述沸點低45℃的溫度作為上限，且較佳為加熱至230℃以上。 就可高效率地獲得特定形狀的氧化物粒子的方面而言，加熱溫度適當的是160℃以上且310℃以下的範圍，尤其更佳為230℃以上且270℃以下的範圍。 於加熱溫度過低的情形時，無法充分進行核形成，因此必需某種程度的加熱溫度（例如230℃等）。另一方面，若溶劑的溫度變高而接近溶劑的沸點附近，則根據奧士華（Ostwald）成長的原理，有粒界變大、或導致粒子尺寸的不均勻化之虞。另外，於在高溫下進行加熱的情形時，推測由於加熱中全部配位子變得容易自粒子表面脫離，因此粒子尺寸容易變大，且粒子會進行等向性成長。另一方面，於略低於沸點的溫度下的加熱條件下，成為配位子鍵結於粒子的一部分的狀態，因此推測其他粒子會鍵結於粒子表面未鍵結有配位子的部位，或未鍵結有配位子的部位進行選擇性異向結晶成長，因此形成具有特定形狀的氧化物粒子。 加熱時間適當的是1分鐘以上，就同時實現使之充分進行結晶成長及縮短製造製程所花費的時間的觀點而言，較佳為20分鐘以上且5小時以下的範圍，尤其更佳為30分鐘以上且3小時以下的範圍。The solution prepared by the solution preparation step is supplied to a heating step of heating at a temperature lower than the boiling point of the solvent contained in the solution. The oxide particles having a specific shape of the present invention can be formed by a heating step. The heating step is preferably carried out under atmospheric pressure insofar as it is not necessary to prepare a special reaction vessel or reaction apparatus. The heating temperature may be a temperature equal to or lower than the boiling point of the solvent contained in the heated solution, preferably a temperature obtained by subtracting 10 ° C from the boiling point as an upper limit, and further preferably 45 ° C lower than the boiling point. The temperature is taken as an upper limit, and is preferably heated to 230 ° C or higher. In terms of efficiently obtaining oxide particles having a specific shape, the heating temperature is suitably in the range of 160 ° C or more and 310 ° C or less, and more preferably in the range of 230 ° C or more and 270 ° C or less. When the heating temperature is too low, the formation of nuclei cannot be sufficiently performed, and thus a certain heating temperature (for example, 230 ° C or the like) is required. On the other hand, when the temperature of the solvent becomes high and approaches the vicinity of the boiling point of the solvent, the grain boundary becomes large or the particle size is uneven due to the principle of growth of Ostwald. Further, when heating is performed at a high temperature, it is presumed that all the ligands in the heating are easily detached from the surface of the particles, so that the particle size tends to increase and the particles grow isotropically. On the other hand, in a heating condition at a temperature slightly lower than the boiling point, the ligand is bonded to a part of the particles, and therefore it is presumed that the other particles are bonded to the site where the ligand is not bonded to the surface of the particle. The site where the ligand is not bonded is subjected to selective anisotropic crystal growth, thereby forming oxide particles having a specific shape. The heating time is suitably 1 minute or longer, and it is preferably 20 minutes or longer and 5 hours or shorter, and more preferably 30 minutes, from the viewpoint of sufficiently increasing the crystal growth and shortening the time required for the production process. Above and below 3 hours.
本發明的氧化物粒子的製造方法亦可視需要而具有其他步驟。 藉由本發明的氧化物粒子的製造方法，可製造含有選自In及Sn中的至少一種元素，且具有特定形狀的氧化物粒子。將含有本發明的具有特定形狀的氧化物粒子的分散液塗佈於基板上並加以乾燥所形成的氧化物粒子薄膜與藉由現有的製造方法所製造的主要為球狀的氧化物粒子的情形相比，具有如下優異的電特性：具有高載子移動率、或低電阻值。 因此，本發明的氧化物粒子薄膜作為導電膜、或半導體膜而具有優異的性能，可用作構成電子元件的導電膜或半導體膜。The method for producing oxide particles of the present invention may have other steps as needed. According to the method for producing oxide particles of the present invention, oxide particles having a specific shape and containing at least one element selected from the group consisting of In and Sn can be produced. A case where an oxide particle film formed by applying a dispersion liquid containing oxide particles having a specific shape of the present invention onto a substrate and drying the film and a main spherical oxide particle produced by a conventional production method In comparison, it has excellent electrical characteristics: high carrier mobility, or low resistance. Therefore, the oxide particle film of the present invention has excellent performance as a conductive film or a semiconductor film, and can be used as a conductive film or a semiconductor film constituting an electronic component.
[氧化物粒子薄膜的形成方法] 本發明的氧化物粒子薄膜的形成方法包括：塗佈步驟，將本發明的已說明的氧化物粒子分散液塗佈於基板上；乾燥步驟，將塗佈於基板上的氧化物粒子分散液加以乾燥而去除分散液所含的溶劑的至少一部分。[Method of Forming Oxide Particle Thin Film] The method for forming an oxide particle thin film of the present invention includes a coating step of applying the above-described oxide particle dispersion of the present invention onto a substrate, and a drying step of applying it to The oxide particle dispersion on the substrate is dried to remove at least a part of the solvent contained in the dispersion.
＜塗佈步驟＞ -基板- 所述基板的形狀、結構、大小等並無特別限制，可根據目的而適當選擇。 基板的結構可為單層結構，亦可為積層結構。 作為基板，例如可使用含有YSZ（釔穩定化鋯）或玻璃等無機材料、樹脂或樹脂複合材料等的基板。 其中，就輕量的方面、具有可撓性的方面而言，較佳為含有樹脂或樹脂複合材料的基板。 具體而言，可使用：含有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、烯丙基二甘醇碳酸酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚吲哚（polybenzazole）、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、環硫化合物等合成樹脂的基板；含有已說明的合成樹脂等與氧化矽粒子的複合塑膠材料的基板；含有已說明的合成樹脂等與金屬奈米粒子、無機氧化物奈米粒子或無機氮化物奈米粒子等的複合塑膠材料的基板；含有已說明的合成樹脂等與碳纖維或碳奈米管的複合塑膠材料的基板；含有已說明的合成樹脂等與玻璃片、玻璃纖維或玻璃珠的複合塑膠材料的基板；含有已說明的合成樹脂等與具有黏土礦物或雲母衍生結晶結構的粒子的複合塑膠材料的基板；於薄玻璃與已說明的任一合成樹脂之間具有至少一個接合界面的積層塑膠基板；含有藉由交替積層無機層與有機層（已說明的合成樹脂）而具有一個以上的接合界面的具有障壁性能的複合材料的基板；將不鏽鋼基板或不鏽鋼與異種金屬積層而成的金屬多層基板；藉由對鋁基板或表面實施氧化處理（例如陽極氧化處理）來提高表面的絕緣性的附氧化皮膜的鋁基板；等。<Coating Step> - Substrate - The shape, structure, size, and the like of the substrate are not particularly limited, and may be appropriately selected depending on the purpose. The structure of the substrate may be a single layer structure or a laminate structure. As the substrate, for example, a substrate containing an inorganic material such as YSZ (yttrium stabilized zirconium) or glass, a resin, or a resin composite material can be used. Among them, a substrate containing a resin or a resin composite material is preferred in terms of light weight and flexibility. Specifically, it can be used: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, Polyfluorene, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzazole, poly Fluororesin such as phenyl sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, cross-linking a substrate of a synthetic resin such as a butenedioic acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound; and a synthetic resin or the like which is described above and a cerium oxide particle a substrate of a composite plastic material; a substrate containing a composite plastic material such as a synthetic resin or the like, such as a metal nanoparticle, an inorganic oxide nanoparticle, or an inorganic nitride nanoparticle; and a synthetic resin or the like and carbon fiber or Carbon nanotube tube composite plastic material base a substrate comprising a composite plastic material such as a synthetic resin or the like, a glass sheet, a glass fiber or a glass bead; a substrate comprising a composite plastic material having a synthetic mineral resin or the like and a particle having a clay mineral or a mica-derived crystal structure; a laminated plastic substrate having at least one bonding interface between the thin glass and any of the synthetic resins described; having barrier properties with more than one bonding interface by alternately laminating inorganic layers and organic layers (synthetic resin as described) a substrate of a composite material; a metal multilayer substrate in which a stainless steel substrate or a stainless steel and a dissimilar metal are laminated; an oxide-attached aluminum which is improved in surface insulation by an oxidation treatment (for example, anodizing treatment) on an aluminum substrate or a surface Substrate; etc.
再者，基板較佳為耐熱性、尺寸穩定性、耐溶劑性、電絕緣性、加工性、低通氣性、及低吸濕性等優異。 另外，基板亦可具備用以防止水分或氧透過的阻氣層、或用以提高基板的平坦性或與下部電極的密合性的底塗層等。 另外，於基板上可具備下部電極、或絕緣膜，於該情形時，較佳為於基板上的下部電極或絕緣膜上形成本發明的氧化物粒子薄膜（例如半導體膜）。Further, the substrate is preferably excellent in heat resistance, dimensional stability, solvent resistance, electrical insulating properties, workability, low air permeability, and low moisture absorption. Further, the substrate may be provided with a gas barrier layer for preventing the permeation of moisture or oxygen, or an undercoat layer for improving the flatness of the substrate or the adhesion to the lower electrode. Further, a lower electrode or an insulating film may be provided on the substrate. In this case, it is preferable to form the oxide particle film (for example, a semiconductor film) of the present invention on the lower electrode or the insulating film on the substrate.
基板的厚度並無特別限制，較佳為50 μm～1000 μm，更佳為50 μm～500 μm。若基板的厚度為50 μm以上，則基板本身的平坦性提高，若基板的厚度為1000 μm以下，則基板本身的可撓性提高，例如變得更容易將薄膜用作柔性半導體單元的構成要素。The thickness of the substrate is not particularly limited, but is preferably 50 μm to 1000 μm, more preferably 50 μm to 500 μm. When the thickness of the substrate is 50 μm or more, the flatness of the substrate itself is improved, and when the thickness of the substrate is 1000 μm or less, the flexibility of the substrate itself is improved, and for example, it is easier to use the film as a constituent element of the flexible semiconductor unit. .
-塗佈- 作為將本發明的已說明的氧化物粒子分散液塗佈於基板上的方法，例如可使用旋轉塗佈、棒式塗佈、浸漬塗佈、噴塗、噴墨、分配器、網版印刷、凸版印刷或凹版印刷等液相法。- Coating - As a method of applying the above-described oxide particle dispersion of the present invention to a substrate, for example, spin coating, bar coating, dip coating, spray coating, ink jet, dispenser, or mesh can be used. Liquid phase methods such as plate printing, letterpress printing or gravure printing.
-乾燥- 將塗佈於基板上的氧化物粒子分散液加以乾燥，去除氧化物粒子分散液所含的溶劑的至少一部分，從而形成基板上含有氧化物粒子的薄膜。 乾燥可藉由對塗佈於基板上的氧化物粒子分散液吹送空氣等氣體的方法而進行。另外，相反地，亦可藉由使塗佈有氧化物粒子分散液的基板旋轉等方法來推動基板，使塗佈於基板上的氧化物粒子分散液的表面附近的空氣等氣體移動，藉此進行乾燥。作為後者的方法，例如可列舉如下方法：使用旋轉塗佈機，將氧化物粒子分散液旋轉塗佈於基板上後，進而以與旋轉塗佈時的旋轉速度相同、或不同的速度使旋轉塗佈機進行旋轉。無論何種乾燥，均亦可藉由設為經加熱的空氣等氣體環境下來縮短乾燥時間。 乾燥時的溫度並無特別限定，可為室溫，亦可為加熱乾燥。進行加熱乾燥的情形時的加熱溫度例如可列舉50℃～250℃。 另外，乾燥中的氣體環境並無特別限制，就製造成本等觀點而言，較佳為於大氣壓下、大氣中進行。- Drying - The oxide particle dispersion applied on the substrate is dried to remove at least a part of the solvent contained in the oxide particle dispersion, thereby forming a film containing oxide particles on the substrate. Drying can be carried out by blowing a gas such as air onto the oxide particle dispersion applied to the substrate. On the other hand, the substrate can be pushed by a method of rotating the substrate coated with the oxide particle dispersion, and the gas such as air in the vicinity of the surface of the oxide particle dispersion applied to the substrate can be moved. Dry. The latter method is, for example, a method in which a spin coating machine is used to spin-coat an oxide particle dispersion onto a substrate, and then spin coating is performed at the same speed or at a different speed from that at the time of spin coating. The cloth machine rotates. Regardless of the type of drying, the drying time can be shortened by using a gaseous environment such as heated air. The temperature at the time of drying is not particularly limited, and it may be room temperature or heat drying. The heating temperature in the case of performing heat drying is, for example, 50 ° C to 250 ° C. Further, the gas atmosphere during drying is not particularly limited, and it is preferably carried out under atmospheric pressure in the atmosphere from the viewpoint of production cost and the like.
為了提高形成於基板上的氧化物粒子薄膜的導電性等電特性，較佳為實施配位子去除步驟，將鍵結於塗佈所使用的氧化物粒子表面的配位子等去除。 所述配位子去除步驟的較佳的具體例包含使形成於基板上的氧化物粒子薄膜與含有極性溶劑的處理液接觸的方法。 所述極性溶劑的較佳的具體例例如包含：甲醯胺、甲基甲醯胺、二甲基甲醯胺、二甲基亞碸、乙醇、甲醇等醇類、乙腈、丙酮、乙二醇、二乙二醇等。其中，就為高極性溶劑，於進行配位子去除處理後不易殘存於半導體膜中的觀點而言，較佳為乙醇、甲醇、二甲基甲醯胺、二甲基亞碸、乙腈。 於含有氧化物粒子的分散液的情形時，存在作為分散液的溶劑而使用非極性溶劑的情形，所述氧化物粒子具有含有烴基的配位子。於將所述分散液塗佈於基板上所形成的氧化物粒子薄膜的情形時，藉由進行使氧化物粒子薄膜與含有極性溶劑的溶液接觸的處理，可藉由疏水性相互作用高效率地去除配位子的至少一部分。藉此，可拉近鄰接的氧化物粒子間的距離，進一步提高導電性等電特性。In order to improve the electrical conductivity and the like of the oxide particle film formed on the substrate, it is preferred to carry out a ligand removal step to remove a ligand or the like bonded to the surface of the oxide particle used for coating. A preferred specific example of the ligand removal step includes a method of bringing a film of an oxide particle formed on a substrate into contact with a treatment liquid containing a polar solvent. Preferred specific examples of the polar solvent include, for example, formamide, methylformamide, dimethylformamide, dimethylhydrazine, ethanol, methanol, and the like, acetonitrile, acetone, and ethylene glycol. , diethylene glycol, etc. Among them, a highly polar solvent is preferably ethanol, methanol, dimethylformamide, dimethylhydrazine or acetonitrile from the viewpoint of not easily remaining in the semiconductor film after the ligand removal treatment. In the case of a dispersion containing oxide particles, there is a case where a non-polar solvent is used as a solvent of the dispersion liquid, and the oxide particles have a ligand containing a hydrocarbon group. When the dispersion liquid is applied to the oxide particle film formed on the substrate, the treatment of bringing the oxide particle film into contact with the solution containing the polar solvent enables efficient and efficient interaction by hydrophobic interaction At least a portion of the ligand is removed. Thereby, the distance between adjacent oxide particles can be approximated, and the electrical and electrical characteristics of conductivity can be further improved.
於進行配位子去除步驟的情形時，較佳為進一步進行對氧化物粒子薄膜進行沖洗處理的沖洗步驟，將於配位子去除步驟中所脫離的配位子去除。 所述沖洗處理較佳為藉由如下方法進行：將含有與配位子去除步驟所使用的處理液所含的溶劑相同的溶劑的處理液塗佈於氧化物粒子薄膜後，利用離心力等抖落所塗佈的處理液，或將氧化物粒子薄膜浸漬於所述處理液中。In the case of performing the ligand removal step, it is preferred to further carry out a rinsing step of rinsing the oxide particle film, and the ligand removed in the ligand removal step is removed. The rinsing treatment is preferably carried out by applying a treatment liquid containing the same solvent as the solvent contained in the treatment liquid used in the ligand removal step to the oxide particle film, and then shaking off by centrifugal force or the like. The applied treatment liquid or the oxide particle film is immersed in the treatment liquid.
藉由以上步驟，可獲得氧化物粒子薄膜，但為了獲得所需的膜厚，亦可將塗佈步驟及配位子去除步驟（或配位子交換步驟）重複進行。另外，於重複進行所述步驟的情形時，每一個週期充分進行氧化物粒子薄膜的乾燥會帶來較佳的結果。By the above steps, an oxide particle film can be obtained, but in order to obtain a desired film thickness, the coating step and the ligand removal step (or the ligand exchange step) can be repeated. Further, in the case where the above steps are repeated, it is preferable to sufficiently dry the oxide particle film every cycle.
＜加熱處理（退火）步驟＞ 亦可具有加熱處理（退火）步驟，對設置於基板上的氧化物粒子薄膜進行加熱處理（退火）。 就製作更優質的氧化物粒子薄膜的觀點而言，加熱處理的溫度（最高到達溫度）較佳為150℃以上，進而較佳為200℃以上。加熱處理的溫度（最高到達溫度）的上限並無特別限制，於使用塑膠等柔性基板的情形時，考慮到基板的耐熱性，加熱處理的溫度（最高到達溫度）較佳為300℃以下。<Heat Treatment (Annealing) Step> A heat treatment (annealing) step may be employed to heat-treat (anneal) the oxide particle film provided on the substrate. From the viewpoint of producing a higher-quality oxide particle film, the temperature (highest reaching temperature) of the heat treatment is preferably 150 ° C or higher, and more preferably 200 ° C or higher. The upper limit of the temperature (the highest temperature reached) of the heat treatment is not particularly limited. When a flexible substrate such as plastic is used, the heat treatment temperature (the highest temperature reached) is preferably 300 ° C or less in consideration of the heat resistance of the substrate.
加熱處理的氣體環境並無特別限制，可為大氣環境下，亦可為含有惰性氣體（氮氣、氦氣、氬氣等）的氣體環境下。 如上文所述，本發明的製造方法即便於在大氣環境下進行加熱處理的情形時，亦可獲得特性優異的氧化物粒子薄膜。The gas atmosphere to be heated is not particularly limited, and may be in an atmosphere or an atmosphere containing an inert gas (nitrogen, helium, argon, etc.). As described above, the production method of the present invention can obtain an oxide particle film excellent in characteristics even when heat treatment is performed in an air atmosphere.
就獲得優異的電特性的觀點而言，氧化物粒子薄膜的厚度較佳為10 nm以上，更佳為50 nm以上。另外，就製造容易性的觀點而言，本發明的薄膜的厚度較佳為300 nm以下。The thickness of the oxide particle film is preferably 10 nm or more, and more preferably 50 nm or more from the viewpoint of obtaining excellent electrical characteristics. Further, the thickness of the film of the present invention is preferably 300 nm or less from the viewpoint of easiness of production.
氧化物粒子薄膜較佳為導電膜。 此處，所謂導電膜是包含半導體膜的概念。 進而，就藉由塗佈製程實現製造簡易的TOS的觀點而言，本發明的氧化物粒子薄膜更佳為半導體膜。本發明中的所謂「半導體」是指比電阻值為10-2 Ωcm以上且108 Ωcm以下。 本發明的氧化物粒子薄膜可較佳地用作電子元件所包含的一構件。 作為電子元件，例如可列舉薄膜電晶體、電容器（condenser）、二極體、感測器類（攝像元件等）等具備半導體膜及導電膜的至少一者的各種元件。The oxide particle film is preferably a conductive film. Here, the conductive film is a concept including a semiconductor film. Further, the oxide particle film of the present invention is more preferably a semiconductor film from the viewpoint of realizing the production of a simple TOS by a coating process. The term "semiconductor" as used in the present invention means a specific resistance value of 10 -2 Ωcm or more and 10 8 Ωcm or less. The oxide particle film of the present invention can be preferably used as a member included in an electronic component. Examples of the electronic component include various elements including at least one of a semiconductor film and a conductive film, such as a thin film transistor, a capacitor, a diode, and a sensor (an image sensor).
[薄膜電晶體] 本發明的薄膜電晶體具備所述本發明的氧化物粒子薄膜。 本發明的薄膜電晶體例如於本發明的氧化物粒子薄膜為導電膜（較佳為半導體膜）的情形時，作為活性層（半導體層）而可具備本發明的氧化物粒子薄膜。 另外，本發明的薄膜電晶體例如於本發明的氧化物粒子薄膜為具有高導電性的導電膜的情形時，作為閘極電極、源極電極、及汲極電極中的至少一者而亦可具備本發明的氧化物粒子薄膜。[Thin Film Transistor] The thin film transistor of the present invention comprises the oxide particle film of the present invention. In the case of the thin film transistor of the present invention, for example, when the oxide particle film of the present invention is a conductive film (preferably a semiconductor film), the oxide particle film of the present invention may be provided as an active layer (semiconductor layer). In the case where the oxide film of the present invention is a conductive film having high conductivity, for example, at least one of a gate electrode, a source electrode, and a drain electrode may be used. The oxide particle film of the present invention is provided.
以下，對具備本發明的氧化物粒子薄膜作為活性層（半導體層）的薄膜電晶體（TFT）的實施方式進行說明。 再者，作為實施方式而對頂閘極型的薄膜電晶體進行說明，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。Hereinafter, an embodiment of a thin film transistor (TFT) including the oxide particle film of the present invention as an active layer (semiconductor layer) will be described. Further, although a top gate type thin film transistor is described as an embodiment, the thin film transistor of the present invention is not limited to the top gate type, and may be a bottom gate type thin film transistor.
本發明中的TFT的元件結構並無特別限定，基於閘極電極的位置而可為所謂的反交錯結構（亦稱為底閘極型）及交錯結構（亦稱為頂閘極型）中的任一形態。另外，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，可為所謂的頂接觸型、底接觸型中的任一形態。 所謂頂閘極型是於將形成有TFT的基板設為最下層的情形時，於閘極絕緣膜的上側配置有閘極電極、於閘極絕緣膜的下側形成有活性層的形態。所謂底閘極型是於閘極絕緣膜的下側配置有閘極電極、於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-汲極電極先於活性層而形成且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先於源極-汲極電極而形成且活性層的上表面與源極-汲極電極接觸的形態。The element structure of the TFT in the present invention is not particularly limited, and may be a so-called inverted staggered structure (also referred to as a bottom gate type) and a staggered structure (also referred to as a top gate type) based on the position of the gate electrode. Any form. Further, the contact portion between the active layer and the source electrode and the drain electrode (referred to as "source-drain electrode" as appropriate) may be any of a so-called top contact type or bottom contact type. In the case where the substrate on which the TFT is formed is the lowermost layer, the top gate type has a gate electrode disposed on the upper side of the gate insulating film and an active layer formed on the lower side of the gate insulating film. The bottom gate type is a form in which a gate electrode is disposed on the lower side of the gate insulating film and an active layer is formed on the upper side of the gate insulating film. Further, the 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. The top contact type is a form in which an active layer is formed before a source-drain electrode and an upper surface of the active layer is in contact with a source-drain electrode.
圖1是表示具有頂閘極結構的頂接觸型的本發明的TFT的一例的模式圖。於圖1所示的TFT10中，所述的本發明的薄膜作為活性層14而積層於基板12的一主面上。此外，源極電極16及汲極電極18互相隔開設置於活性層14上，進而於該些上依序積層有閘極絕緣膜20、及閘極電極22。Fig. 1 is a schematic view showing an example of a top contact type TFT of the present invention having a top gate structure. In the TFT 10 shown in FIG. 1, the film of the present invention is laminated as an active layer 14 on one main surface of the substrate 12. Further, the source electrode 16 and the drain electrode 18 are provided on the active layer 14 so as to be spaced apart from each other, and the gate insulating film 20 and the gate electrode 22 are sequentially laminated on the plurality of layers.
圖2是表示具有頂閘極結構的底接觸型的本發明的TFT的一例的模式圖。於圖2所示的TFT30中，源極電極16及汲極電極18互相隔開設置於基板12的一主面上。此外，依序積層有作為活性層14的所述的本發明的薄膜、閘極絕緣膜20、及閘極電極22。Fig. 2 is a schematic view showing an example of a bottom contact type TFT of the present invention having a top gate structure. In the TFT 30 shown in FIG. 2, the source electrode 16 and the drain electrode 18 are spaced apart from each other on one main surface of the substrate 12. Further, the film of the present invention, the gate insulating film 20, and the gate electrode 22 as the active layer 14 are laminated in this order.
圖3是表示具有底閘極結構的頂接觸型的本發明的TFT的一例的模式圖。於圖3所示的TFT40中，於基板12的一主面上依序積層有閘極電極22、閘極絕緣膜20、及作為活性層14的本發明的薄膜。此外，源極電極16及汲極電極18互相隔開設置於活性層14的表面上。Fig. 3 is a schematic view showing an example of a top contact type TFT of the present invention having a bottom gate structure. In the TFT 40 shown in FIG. 3, a gate electrode 22, a gate insulating film 20, and a thin film of the present invention 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 spaced apart from each other.
圖4是表示具有底閘極結構的底接觸型的本發明的TFT的一例的模式圖。於圖4所示的TFT50中，於基板12的一主面上依序積層有閘極電極22、及閘極絕緣膜20。此外，源極電極16及汲極電極18互相隔開設置於閘極絕緣膜20的表面上，進而，於該些上積層有作為活性層14的本發明的薄膜。4 is a schematic view showing an example of a bottom contact type TFT of the present invention having a bottom gate structure. 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 so as to be spaced apart from each other, and further, the film of the present invention as the active layer 14 is laminated on the layers.
以下的實施方式主要對圖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。The following embodiment mainly describes the top gate type thin film transistor 10 shown in FIG. 1. However, the thin film transistor of the present invention is not limited to the top gate type, and may be a bottom gate type thin film transistor. .
（活性層） 於製造本實施方式的薄膜電晶體10的情形時，首先，藉由本發明的氧化物粒子薄膜的形成方法，於基板12上形成薄膜。 薄膜的圖案化可藉由上文所述的噴墨法、分配器法、凸版印刷法、或凹版印刷法進行，亦可於形成薄膜後藉由光微影及蝕刻進行圖案化。 於藉由光微影及蝕刻進行圖案形成時，在形成薄膜後，藉由光微影於作為活性層14而殘存的部分形成抗蝕劑圖案，其後，藉由鹽酸、硝酸、稀硫酸、磷酸、或硝酸及乙酸的混合液等酸溶液進行蝕刻，藉此形成活性層14的圖案。(Active Layer) In the case of producing the thin film transistor 10 of the present embodiment, first, a film is formed on the substrate 12 by the method for forming an oxide particle film of the present invention. The patterning of the film can be carried out by the inkjet method, the dispenser method, the relief printing method, or the gravure printing method described above, or can be patterned by photolithography and etching after the film is formed. When patterning is performed by photolithography and etching, after forming a thin film, a resist pattern is formed by photolithography on a portion remaining as the active layer 14, and thereafter, by hydrochloric acid, nitric acid, dilute sulfuric acid, An acid solution such as phosphoric acid or a mixed solution of nitric acid and acetic acid is etched to form a pattern of the active layer 14.
（保護層） 較佳為於活性層14上形成於源極-汲極電極16及18的蝕刻時用來保護活性層14的保護層（未圖示）。保護層的成膜方法並無特別限定，可於形成本發明的薄膜後且進行圖案化前形成，亦可於本發明的薄膜的圖案化後形成。 另外，作為保護層，可為金屬氧化物層，亦可為樹脂之類的有機材料。再者，保護層可於形成源極電極16及汲極電極18（適當記作「源極-汲極電極」）後去除。(Protective layer) A protective layer (not shown) for protecting the active layer 14 during etching of the source-drain electrodes 16 and 18 is preferably formed on the active layer 14. The film formation method of the protective layer is not particularly limited, and it may be formed after the film of the present invention is formed and before patterning, or may be formed after patterning of the film of the present invention. Further, the protective layer may be a metal oxide layer or an organic material such as a resin. Further, the protective layer can be removed after forming the source electrode 16 and the drain electrode 18 (referred to as "source-drain electrode" as appropriate).
（源極-汲極電極） 於由本發明的氧化物粒子薄膜所形成的活性層14上形成源極-汲極電極16及18。源極-汲極電極16及18分別使用具有高導電性者，以作為電極而發揮功能，可使用如下物質而形成：Al、Mo、Cr、Ta、Ti、Au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）、In-Ga-Zn-O等金屬氧化物導電膜等。(Source-Tibial Electrode) The source-drain electrodes 16 and 18 are formed on the active layer 14 formed of the oxide particle film of the present invention. The source-drain electrodes 16 and 18 each have a high conductivity and function as an electrode, and can be formed using a material such as Al, Mo, Cr, Ta, Ti, or Au; Al-Nd, Ag. A metal oxide conductive film such as an alloy, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO) or In-Ga-Zn-O.
於形成源極-汲極電極16及18的情形時，依照考慮與所使用的材料的適應性而自如下方法中適當選擇的方法進行成膜即可：印刷方法、塗佈方法等濕式方法；真空蒸鍍法、濺鍍法、離子電鍍法等物理方法；化學氣相沈積（Chemical Vapor Deposition，CVD）、電漿CVD法等化學方法等。In the case of forming the source-drain electrodes 16 and 18, it is possible to form a film by a method appropriately selected from the following methods in consideration of adaptability to the material to be used: a wet method such as a printing method or a coating method. Physical methods such as vacuum vapor deposition, sputtering, and ion plating; chemical methods such as chemical vapor deposition (CVD) and plasma CVD.
若考慮成膜性、利用蝕刻或掀離法的圖案化性、導電性等，則源極-汲極電極16及18的膜厚較佳為設為10 nm以上且1000 nm以下，更佳為設為50 nm以上且100 nm以下。The film thickness of the source-drain electrodes 16 and 18 is preferably 10 nm or more and 1000 nm or less, more preferably in consideration of film formation property, patterning property by etching or detachment method, conductivity, and the like. Set to 50 nm or more and 100 nm or less.
源極-汲極電極16及18可於形成導電膜後，例如藉由蝕刻或掀離法圖案化為特定形狀而形成，亦可藉由噴墨法等直接進行圖案形成。此時，較佳為對源極-汲極電極16及18以及連接於該些電極的配線（未圖示）同時進行圖案化。The source-drain electrodes 16 and 18 may be formed by patterning into a specific shape by, for example, etching or lift-off after forming a conductive film, or may be directly patterned by an inkjet method or the like. At this time, it is preferable to simultaneously pattern the source-drain electrodes 16 and 18 and the wiring (not shown) connected to the electrodes.
（閘極絕緣膜） 於形成源極-汲極電極16及18以及配線（未圖示）後，形成閘極絕緣膜20。閘極絕緣膜20較佳為具有高絕緣性者，例如可為SiO2 、SiNx 、SiON、Al2 O3 、Y2 O3 、Ta2 O5 、HfO2 等絕緣膜，或含有兩種以上該些化合物的絕緣膜。 閘極絕緣膜20依照考慮與所使用的材料的適應性而自如下所述方法中適當選擇的方法進行成膜即可：印刷方法、噴墨方法、塗佈方法等濕式方法；真空蒸鍍法、濺鍍法、離子電鍍法等物理方法；CVD、電漿CVD法等化學方法。(Gate Insulation Film) After the source-drain electrodes 16 and 18 and wiring (not shown) are formed, the gate insulating film 20 is formed. The gate insulating film 20 preferably has high insulating properties, and may be, for example, an insulating film such as SiO 2 , SiN x , SiON, Al 2 O 3 , Y 2 O 3 , Ta 2 O 5 , HfO 2 , or the like. An insulating film of the above compounds. The gate insulating film 20 can be formed by a method appropriately selected from the methods described below in consideration of adaptability to the material to be used: a wet method such as a printing method, an inkjet method, or a coating method; vacuum evaporation Physical methods such as methods such as sputtering, ion plating, and chemical methods such as CVD and plasma CVD.
再者，閘極絕緣膜20需具有用以降低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，則導致驅動電壓上升。閘極絕緣膜20亦取決於材質，閘極絕緣膜20的厚度較佳為10 nm以上且10 μm以下，更佳為50 nm以上且1000 nm以下，尤佳為100 nm以上且400 nm以下。Further, the gate insulating film 20 is required to 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 is increased. The gate insulating film 20 is also dependent on the material. 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） 於形成閘極絕緣膜20後，形成閘極電極22。閘極電極22使用具有高導電性者，可使用如下物質而形成：Al、Mo、Cr、Ta、Ti、Au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）、InGaZnO等金屬氧化物導電膜等。作為閘極電極22，可將該些導電膜製成單層結構或兩層以上的積層結構而使用。(Gate Electrode) After the gate insulating film 20 is formed, the gate electrode 22 is formed. The gate electrode 22 is formed of a material having high conductivity and can be formed by using a metal such as Al, Mo, Cr, Ta, Ti, or Au; Al-Nd, Ag alloy, tin oxide, zinc oxide, indium oxide, or indium oxide. A metal oxide conductive film such as tin (ITO), indium zinc oxide (IZO) or InGaZnO. As the gate electrode 22, these conductive films can be used in a single layer structure or a laminated structure of two or more layers.
閘極電極22是依照考慮與所使用的材料的適應性而自如下所述的方法中適當選擇的方法進行成膜：印刷方法、塗佈方法等濕式方法；真空蒸鍍法、濺鍍法、離子電鍍法等物理方法；CVD（化學氣相蒸鍍法：Chemical Vapor Deposition）、電漿CVD法等化學方法等。 若考慮成膜性、藉由蝕刻或掀離法的圖案化性、導電性等，則用來形成閘極電極22的金屬膜的膜厚較佳為設為10 nm以上且1000 nm以下，更佳為設為50 nm以上且200 nm以下。 成膜後，可藉由蝕刻或掀離法進行圖案化，藉此形成閘極電極22，亦可藉由噴墨法等直接進行圖案形成。此時，較佳為對閘極電極22及閘極配線（未圖示）同時進行圖案化。The gate electrode 22 is formed by a method appropriately selected from the following methods in consideration of adaptability to the material to be used: a wet method such as a printing method or a coating method; a vacuum evaporation method, and a sputtering method. Physical methods such as ion plating; chemical methods such as CVD (Chemical Vapor Deposition) and plasma CVD. The film thickness of the metal film for forming the gate electrode 22 is preferably 10 nm or more and 1000 nm or less, in consideration of film formation property, patterning property by etching or detachment method, conductivity, and the like. Good is set to 50 nm or more and 200 nm or less. After the film formation, the gate electrode 22 can be formed by patterning by etching or lift-off, and pattern formation can be directly performed by an inkjet method or the like. At this time, it is preferable to simultaneously pattern the gate electrode 22 and the gate wiring (not shown).
[電子元件] 本發明的電子元件具備所述本發明的薄膜電晶體。 所述本發明的薄膜電晶體可較佳地用作本發明的電子元件中的驅動元件。 作為電子元件，可列舉：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；X射線感測器、影像感測器等各種感測器；微機電系統（MEMS，Micro Electro Mechanical System）等。[Electronic Component] The electronic component of the present invention comprises the thin film transistor of the present invention. The thin film transistor of the present invention can be preferably used as a driving element in the electronic component of the present invention. Examples of the electronic component include a liquid crystal display device, an organic EL (Electro Luminescence) display device, and a display device such as an inorganic EL display device; various sensors such as an X-ray sensor and an image sensor; and a microelectromechanical system (MEMS). Micro Electro Mechanical System), etc.
＜液晶顯示裝置＞ 對於作為本發明的電子元件的一實施方式的液晶顯示裝置，將其一部分的概略截面圖示於圖5，將電配線的概略構成圖示於圖6。<Liquid Crystal Display Device> A schematic cross-sectional view of a part of the liquid crystal display device as an embodiment of the electronic component of the present invention is shown in FIG. 5 , and a schematic configuration of the electric wiring is shown in FIG. 6 .
如圖5所示，液晶顯示裝置100是如下構成：其具備：TFT10，其為圖1所示的頂閘極結構且為頂接觸型；液晶層108，其位於TFT10的由鈍化層102所保護的閘極電極22上，由像素下部電極104及其對向上部電極106所夾持；及R（紅）G（綠）B（藍）的彩色濾光片110，其用來對應各像素而發出不同的顏色，且於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 is configured to include a TFT 10 which is a top gate structure as shown in FIG. 1 and is a top contact type, and a liquid crystal layer 108 which is protected by a passivation layer 102 of the TFT 10. The gate electrode 22 is sandwiched by the pixel lower electrode 104 and its upper electrode 106; and R (red) G (green) B (blue) color filter 110 is used for each pixel. Different colors are emitted, 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，液晶顯示裝置100具備互相平行的多條閘極配線112、及與閘極配線112交叉的互相平行的資料配線114。此處，閘極配線112與資料配線114為電性絕緣。於閘極配線112與資料配線114的交叉部附近具備TFT10。Further, as shown in FIG. 6 , the liquid crystal display device 100 includes a plurality of gate wirings 112 that are parallel to each other and data wirings 114 that are parallel to each other and that intersect with the gate wirings 112 . Here, the gate wiring 112 and the data wiring 114 are electrically insulated. The TFT 10 is provided in the vicinity of the intersection of the gate wiring 112 and the data wiring 114.
TFT10的閘極電極22與閘極配線112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（將導電體埋入至接觸孔116中）而與像素下部電極104連接。該像素下部電極104與接地的對向上部電極106一併構成電容器118。The gate electrode 22 of the TFT 10 is connected to the gate wiring 112, and the source electrode 16 of the TFT 10 is connected to the data wiring 114. Further, the drain electrode 18 of the TFT 10 is connected to the pixel lower electrode 104 via a contact hole 116 provided in the gate insulating film 20 (the conductor is buried in the contact hole 116). The pixel lower electrode 104 and the grounded pair upper electrode 106 together constitute a capacitor 118.
＜有機EL顯示裝置＞ 對於本發明的電子元件的一實施方式的主動矩陣型有機EL顯示裝置，將一部分的概略截面圖示於圖7，將電配線的概略構成圖示於圖8。<Organic EL display device> An active matrix organic EL display device according to an embodiment of the electronic component of the present invention is a schematic cross-sectional view of a part of Fig. 7 and a schematic configuration of the electric wiring.
主動矩陣型有機EL顯示裝置200採用如下所述的構成：其於具備鈍化層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TFT10a及開關用TFT10b，於TFT10a及TFT10b上具備包含由下部電極208及上部電極210所夾持的有機發光層212的有機EL發光元件214，且上表面亦由鈍化層216所保護。The active matrix organic EL display device 200 has a configuration in which the TFT 10 having the top gate structure shown in FIG. 1 is provided on the substrate 12 including the passivation layer 202 as the driving TFT 10a and the switching TFT 10b, and the TFT 10a and the TFT 10b. The organic EL light-emitting element 214 including the organic light-emitting layer 212 sandwiched by the lower electrode 208 and the upper electrode 210 is provided thereon, and the upper surface is also protected by the passivation layer 216.
另外，如圖8所示，有機EL顯示裝置200具備互相平行的多條閘極配線220、以及與閘極配線220相交的互相平行的資料配線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為電性絕緣。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將驅動用TFT10a保持為運行狀態。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。Further, as shown in FIG. 8 , the organic EL display device 200 includes a plurality of gate wirings 220 that are parallel to each other, and data wirings 222 and driving wirings 224 that are parallel to each other and intersect with 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 10b is connected to the gate wiring 220, and the source electrode 16 of the switching TFT 10b is connected to the data wiring 222. Further, 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 maintained in an operating state by using the capacitor 226. The source electrode 16 of the driving TFT 10a is connected to the driving wiring 224, and the drain electrode 18 is connected to the organic EL light emitting element 214.
再者，於圖7所示的有機EL顯示裝置中，可將上部電極210製成透明電極而製成頂部發光型，亦可藉由將下部電極208及TFT的各電極製成透明電極而製成底部發光型。Further, in the organic EL display device shown in FIG. 7, the upper electrode 210 can be made into a transparent electrode to form a top emission type, and the lower electrode 208 and each electrode of the TFT can be made into a transparent electrode. It is a bottom-emitting type.
＜X射線感測器＞ 對於作為本發明的電子元件的一實施方式的X射線感測器，將其一部分的概略截面圖示於圖9，將其電配線的概略構成圖示於圖10。<X-ray sensor> A schematic cross-sectional view of a part of the X-ray sensor as an embodiment of the electronic component of the present invention is shown in FIG. 9 , and a schematic configuration of the electric wiring is shown in FIG. 10 .
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、及上部電極306而構成。於TFT10上設置有鈍化膜308。The X-ray sensor 300 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 disposed on the TFT 10.
電容器310採用以電容器用下部電極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中的任一者（於圖9中為汲極電極18）連接。The capacitor 310 has a structure in which the insulating film 316 is sandwiched between the capacitor lower electrode 312 and the capacitor upper electrode 314. The capacitor upper electrode 314 is connected to any one of the source electrode 16 and the drain electrode 18 of the TFT 10 (the drain electrode 18 in FIG. 9) via a contact hole 318 provided in the insulating film 316.
電荷收集用電極302是設置於電容器310中的電容器用上部電極314上，與電容器用上部電極314相接。 X射線轉換層304是含有非晶硒的層，以覆蓋TFT10及電容器310的方式而設置。 上部電極306是設置於X射線轉換層304上，與X射線轉換層304相接。The charge collection electrode 302 is provided on the capacitor upper electrode 314 provided in the capacitor 310, and is in contact with the capacitor upper electrode 314. The X-ray conversion layer 304 is a layer containing amorphous selenium and is provided to cover the TFT 10 and the capacitor 310. The upper electrode 306 is provided on the X-ray conversion layer 304 and is in contact with the X-ray conversion layer 304.
如圖10所示，本實施方式的X射線感測器300具備互相平行的多條閘極配線320、及與閘極配線320交叉的互相平行的多條資料配線322。此處，閘極配線320與資料配線322為電性絕緣。於閘極配線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 of the present embodiment includes a plurality of gate wirings 320 that are parallel to each other, and a plurality of data wirings 322 that are parallel to each other and intersect with the gate wirings 320. Here, the gate wiring 320 and the data wiring 322 are electrically insulated. The TFT 10 is provided in the vicinity of 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，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. Further, the drain electrode 18 of the TFT 10 is connected to the charge collection electrode 302, and the charge collection electrode 302 is connected to the capacitor 310.
於X射線感測器300中，圖9中X射線自上部電極306側入射，於X射線轉換層304中產生電子-電洞對。藉由利用上部電極306對X射線轉換層304預先施加高電場，所產生的電荷累積於電容器310中，藉由依序掃描TFT10而被讀取。In the X-ray sensor 300, X-rays are incident from the side of the upper electrode 306 in FIG. 9, and an electron-hole pair is generated in the X-ray conversion layer 304. By applying a high electric field to the X-ray conversion layer 304 by the upper electrode 306, the generated charges are accumulated in the capacitor 310, and are read by sequentially scanning the TFT 10.
再者，於所述實施方式的液晶顯示裝置100、有機EL顯示裝置200、及X射線感測器300中，是製成具備頂閘極結構的TFT者，但TFT並不限定於此，亦可為圖2～圖4所示的結構的TFT。 [實施例]Further, in the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 of the above-described embodiment, a TFT having a top gate structure is formed, but the TFT is not limited thereto. The TFT of the structure shown in FIGS. 2 to 4 can be used. [Examples]
以下，對實施例進行說明，但本發明並不受該些實施例任何限定。Hereinafter, the examples are described, but the present invention is not limited to the examples.
[實施例1] ＜氧化物粒子分散液1的製備＞ 藉由以下的方法製備氧化銦（In2 O3 ）奈米粒子分散液。 於三口燒瓶中加入30 mL的十八烯（沸點：315℃）、乙酸銦（In(Ac)3 ）（1.2 mmol）、3.6 mL的油酸、及4.8 mL的油胺，於氮氣氣流、150℃下進行加熱攪拌，使原料充分溶解，並進行1小時的脫氣。 其次，將燒瓶升溫至270℃，並維持150分鐘。於加熱中確認到溶液著色、形成粒子的情況。 將所獲得的溶液冷卻至室溫後，加入乙醇，進行離心分離，從而使粒子沈澱。廢棄上清液後，使其分散於己烷溶劑中。 由此製備氧化物粒子分散液1（氧化物粒子：In2 O3 微粒子、配位子：油酸＋油胺、溶劑：己烷、氧化物粒子的濃度：25 mg/ml）。[Example 1] <Preparation of oxide particle dispersion 1> An indium oxide (In 2 O 3 ) nanoparticle dispersion was prepared by the following method. Add 30 mL of octadecene (boiling point: 315 ° C), indium acetate (In (Ac) 3 ) (1.2 mmol), 3.6 mL of oleic acid, and 4.8 mL of oleylamine to a three-necked flask. The mixture was heated and stirred at ° C to sufficiently dissolve the raw material, and degassed for 1 hour. Next, the flask was heated to 270 ° C and maintained for 150 minutes. It was confirmed that the solution was colored and particles were formed during heating. After cooling the obtained solution to room temperature, ethanol was added and centrifugation was carried out to precipitate particles. After discarding the supernatant, it was dispersed in a hexane solvent. Thus, an oxide particle dispersion 1 (oxide particles: In 2 O 3 fine particles, ligand: oleic acid + oleylamine, solvent: hexane, concentration of oxide particles: 25 mg/ml) was prepared.
[實施例2] ＜氧化物粒子分散液2的製備＞ 藉由以下的方法製備In2 O3 奈米粒子分散液。 於三口燒瓶中加入30 mL的十八烯、In(Ac)3 （1.2 mmol）、3.6 mL的油酸、及4.8 mL的油胺，於氮氣氣流、150℃下進行加熱攪拌，使原料充分溶解，並進行1小時的脫氣。 其次，將燒瓶升溫至230℃，並保持150分鐘。於加熱中確認到溶液著色、形成粒子的情況。 將所獲得的溶液冷卻至室溫後，加入乙醇，進行離心分離，從而使粒子沈澱。廢棄上清液後，使其分散於己烷溶劑中。 由此製備氧化物粒子分散液2（氧化物粒子：In2 O3 微粒子、配位子：油酸＋油胺、溶劑：己烷、氧化物粒子的濃度：25 mg/ml）。[Example 2] <Preparation of oxide particle dispersion 2> An In 2 O 3 nanoparticle dispersion was prepared by the following method. Add 30 mL of octadecene, In(Ac) 3 (1.2 mmol), 3.6 mL of oleic acid, and 4.8 mL of oleylamine to a three-necked flask, and heat and stir at 150 ° C to dissolve the raw materials. And carry out 1 hour of degassing. Next, the flask was heated to 230 ° C and held for 150 minutes. It was confirmed that the solution was colored and particles were formed during heating. After cooling the obtained solution to room temperature, ethanol was added and centrifugation was carried out to precipitate particles. After discarding the supernatant, it was dispersed in a hexane solvent. Thus, oxide particle dispersion 2 (oxide particles: In 2 O 3 fine particles, ligand: oleic acid + oleylamine, solvent: hexane, concentration of oxide particles: 25 mg/ml) was prepared.
[實施例3] ＜氧化物粒子分散液3的製備＞ 藉由以下的方法製備In-Sn-O奈米粒子分散液。 於三口燒瓶中加入30 mL的十八烯、In(Ac)3 （1.19 mmol）、乙酸錫（Sn(Ac)2 ）（0.012 mmol）、3.6 mL的油酸、4.8 mL的油胺，於氮氣氣流、150℃下進行加熱攪拌，使原料充分溶解，並進行1小時的脫氣。 其次，將燒瓶升溫至270℃，並保持150分鐘。於加熱中確認到溶液著色、形成粒子的情況。 將所獲得的溶液冷卻至室溫後，加入乙醇，進行離心分離，從而使粒子沈澱。廢棄上清液後，使其分散於己烷溶劑中。 由此製備氧化物粒子分散液3（氧化物粒子：In-Sn-O微粒子（Sn相對於In的含量：1莫耳%）、配位子：油酸＋油胺、溶劑：己烷、氧化物粒子的濃度：25 mg/ml）。[Example 3] <Preparation of oxide particle dispersion 3> An In-Sn-O nanoparticle dispersion was prepared by the following method. Add 30 mL of octadecene, In(Ac) 3 (1.19 mmol), tin acetate (Sn(Ac) 2 ) (0.012 mmol), 3.6 mL of oleic acid, 4.8 mL of oleylamine to nitrogen in a three-neck flask. The gas stream was heated and stirred at 150 ° C to sufficiently dissolve the raw material, and degassed for 1 hour. Next, the flask was heated to 270 ° C and held for 150 minutes. It was confirmed that the solution was colored and particles were formed during heating. After cooling the obtained solution to room temperature, ethanol was added and centrifugation was carried out to precipitate particles. After discarding the supernatant, it was dispersed in a hexane solvent. Thus, an oxide particle dispersion 3 (oxide particles: In-Sn-O fine particles (content of Sn relative to In: 1 mol%), ligand: oleic acid + oleylamine, solvent: hexane, oxidation Concentration of particles: 25 mg/ml).
[比較例1] ＜氧化物粒子分散液4的製備＞ 藉由以下的方法製備In2 O3 奈米粒子分散液。 於三口燒瓶中加入30 mL的十八烯、In(Ac)3 （1.2 mmol）、3.6 mL的油酸、4.8 mL的油胺，於氮氣氣流、150℃下進行加熱攪拌，使原料充分溶解，並進行1小時的脫氣。 其次，將燒瓶升溫至315℃，並保持60分鐘。於加熱中確認到溶液著色、形成粒子的情況。 將所獲得的溶液冷卻至室溫後，加入乙醇，進行離心分離，從而使粒子沈澱。廢棄上清液後，使其分散於己烷溶劑中。 由此製備氧化物粒子分散液4（氧化物粒子：In2 O3 微粒子、配位子：油酸＋油胺、溶劑：己烷、濃度：25 mg/ml）。[Comparative Example 1] <Preparation of oxide particle dispersion 4> An In 2 O 3 nanoparticle dispersion was prepared by the following method. 30 mL of octadecene, In(Ac) 3 (1.2 mmol), 3.6 mL of oleic acid, and 4.8 mL of oleylamine were added to a three-necked flask, and the mixture was heated and stirred under a nitrogen gas stream at 150 ° C to fully dissolve the raw materials. And degas for 1 hour. Next, the flask was heated to 315 ° C and held for 60 minutes. It was confirmed that the solution was colored and particles were formed during heating. After cooling the obtained solution to room temperature, ethanol was added and centrifugation was carried out to precipitate particles. After discarding the supernatant, it was dispersed in a hexane solvent. Thus, an oxide particle dispersion 4 (oxide particles: In 2 O 3 fine particles, a ligand: oleic acid + oleylamine, solvent: hexane, concentration: 25 mg/ml) was prepared.
關於所述的氧化物粒子分散液1～氧化物粒子分散液4，將粒子組成、合成溫度、粒子尺寸、及粒子形狀記載於下述表1中。The particle composition, the synthesis temperature, the particle size, and the particle shape of the oxide particle dispersion 1 to the oxide particle dispersion 4 are described in Table 1 below.
進而，將所獲得的氧化物粒子分散液1～氧化物粒子分散液4所含的各氧化物粒子的穿透式電子顯微鏡照片分別示於圖12～圖15。Further, a transmission electron micrograph of each oxide particle contained in the obtained oxide particle dispersion liquid 1 to oxide particle dispersion liquid 4 is shown in FIG. 12 to FIG. 15 , respectively.
如表1、及圖12～圖14所示，可知本發明的氧化物粒子具有特定形狀。再者，將依照所述橢圓近似的方法、及長度A、長度B的測定方法進行的橢圓近似、以及長度A、長度B的測定的一例示於圖12～圖14上。確認到實施例1～實施例3的氧化物粒子均滿足A＞B/2。另一方面，如圖15所示，可知比較例1的氧化物粒子為球狀或不定形，並不具有如本發明的特定形狀。As shown in Table 1 and FIG. 12 to FIG. 14, it is understood that the oxide particles of the present invention have a specific shape. In addition, an elliptical approximation and a measurement of the length A and the length B according to the elliptical approximation method and the length A and length B measurement methods are shown in FIGS. 12 to 14 . It was confirmed that the oxide particles of Examples 1 to 3 all satisfy A>B/2. On the other hand, as shown in Fig. 15, it is understood that the oxide particles of Comparative Example 1 are spherical or amorphous, and do not have a specific shape as in the present invention.
[實施例4～實施例10、及比較例2] ＜半導體膜的形成＞ 將所述所獲得的氧化物粒子分散液1、氧化物粒子分散液2、氧化物粒子分散液4、及以下述方式所製備的氧化物粒子分散液5分別旋轉塗佈（1500 rpm、15秒）於基板上，藉此形成厚度為70 nm的氧化物粒子薄膜（半導體膜）。作為形成半導體膜的基板，使用形成有厚度為100 nm的熱氧化膜的高濃度摻雜p-Si基板。 於氧化物粒子表面配位有作為分散劑而添加的化合物（油酸＋油胺）。於對該配位子進行去除或交換的處理（配位子去除處理）的情形時，進行以下操作。 操作1：將氧化物粒子分散液滴加至基板上後，以1500 rpm進行15秒的旋轉塗佈。 操作2：僅將甲醇、或於甲醇中溶解特定的配位子（2-胺基乙醇、硫氰酸鉀）而成的溶液塗佈於氧化物微粒子薄膜上，靜置1分鐘，藉此進行配位子的去除、或交換為特定配位子的處理。其後，於1500 rpm、15秒的條件下進行旋轉乾燥。 操作3：僅將甲醇塗佈於氧化物微粒子薄膜上，於1500 rpm、15秒的條件下進行旋轉乾燥（沖洗處理1） 操作4：僅將己烷塗佈於氧化物微粒子薄膜上，於1500 rpm、15秒的條件下進行旋轉乾燥（沖洗處理2） 此處，對於未進行配位子去除處理的樣品，不進行所述的操作2～操作4的操作。[Example 4 to Example 10 and Comparative Example 2] <Formation of a semiconductor film> The obtained oxide particle dispersion liquid 1, oxide particle dispersion liquid 2, oxide particle dispersion liquid 4, and the following The oxide particle dispersion 5 prepared in the manner was spin-coated (1500 rpm, 15 seconds) on the substrate, thereby forming an oxide particle film (semiconductor film) having a thickness of 70 nm. As the substrate on which the semiconductor film is formed, a high-concentration doped p-Si substrate formed with a thermal oxide film having a thickness of 100 nm is used. A compound (oleic acid + oleylamine) added as a dispersing agent is coordinated to the surface of the oxide particles. In the case of the process of removing or exchanging the ligand (coordination removal process), the following operation is performed. Operation 1: After the oxide particles were dispersed and dropped onto the substrate, spin coating was performed at 1500 rpm for 15 seconds. Operation 2: A solution obtained by dissolving a specific ligand (2-aminoethanol or potassium thiocyanate) in methanol or methanol was applied to the oxide fine particle film and allowed to stand for 1 minute. The removal, or exchange, of a ligand is a treatment of a particular ligand. Thereafter, spin drying was carried out at 1500 rpm for 15 seconds. Operation 3: Only methanol was applied to the oxide fine particle film, and spin drying was performed at 1500 rpm for 15 seconds (rinsing treatment 1). Operation 4: Only hexane was applied to the oxide fine particle film at 1500. Spin drying under rpm and 15 seconds (rinsing treatment 2) Here, the operations of the above operations 2 to 4 were not performed for the sample in which the ligand removal treatment was not performed.
＜氧化物粒子分散液5的製備＞ 藉由以下的方法製備In-Ga-O奈米粒子分散液。 於三口燒瓶中加入30 mL的十八烯、In(Ac)3 （1.19 mmol）、乙醯丙酮鎵（Ga(AcAc)3 ）（0.012 mmol）、3.6 mL的油酸、4.8 mL的油胺，於氮氣氣流、150℃下進行加熱攪拌，使原料充分溶解，並進行1小時的脫氣。 其次，將燒瓶升溫至270℃，並維持150分鐘。於加熱中確認到溶液著色、形成粒子的情況。 將所獲得的溶液冷卻至室溫後，加入乙醇，進行離心分離，從而使粒子沈澱。廢棄上清液後，使其分散於己烷溶劑中。 由此製備氧化物粒子分散液5（氧化物粒子：In-Ga-O微粒子（Ga相對於In的含量：1莫耳%）、配位子：油酸＋油胺、溶劑：己烷、濃度：25 mg/ml）。確認到氧化物粒子分散液5的氧化物粒子亦滿足A＞B/2。<Preparation of Oxide Particle Dispersion 5> An In-Ga-O Nanoparticle dispersion liquid was prepared by the following method. Add 30 mL of octadecene, In(Ac) 3 (1.19 mmol), gallium acetylacetonate (Ga(AcAc) 3 ) (0.012 mmol), 3.6 mL of oleic acid, 4.8 mL of oleylamine to a three-neck flask. The mixture was heated and stirred at 150 ° C in a nitrogen gas stream to sufficiently dissolve the raw material, and degassed for 1 hour. Next, the flask was heated to 270 ° C and maintained for 150 minutes. It was confirmed that the solution was colored and particles were formed during heating. After cooling the obtained solution to room temperature, ethanol was added and centrifugation was carried out to precipitate particles. After discarding the supernatant, it was dispersed in a hexane solvent. Thus, an oxide particle dispersion 5 was prepared (oxide particles: In-Ga-O fine particles (content of Ga relative to In: 1 mol%), ligand: oleic acid + oleylamine, solvent: hexane, concentration : 25 mg/ml). It was confirmed that the oxide particles of the oxide particle dispersion 5 also satisfy A>B/2.
＜氧化物粒子分散液6＞ 以7比3的質量比例將氧化物微粒子液1與氧化物微粒子液4加以混合，製備具有特定形狀的粒子成為總粒子質量的30質量%的氧化物粒子分散液6。<Oxide particle dispersion liquid 6> The oxide fine particle liquid 1 and the oxide fine particle liquid 4 are mixed at a mass ratio of 7 to 3 to prepare an oxide particle dispersion having a specific shape of particles of 30% by mass of the total particle mass. 6.
＜TFT製作及評價＞ 形成半導體膜後，使用真空蒸鍍法，形成Ti 10 nm/Au 40 nm的電極。電極形成是使用遮陰罩進行，製作通道長L/通道寬W＝180 μm/1000 μm的TFT。於形成TFT後，在大氣中、200℃的條件下進行1小時的退火處理。 對於所述TFT，使用半導體參數分析儀（安捷倫科技（Agilent Technology）公司製造），於施加10 V的汲極電壓的狀態下，於-40 V～40 V之間掃描施加閘極電壓，藉此測定傳輸特性，計算出載子移動率。 將實施例4～實施例10、及比較例2所使用的氧化物粒子分散液、粒子組成、合成溫度、粒子形狀、有無配位子的去除操作與操作內容、及載子移動率示於下述表2。<Preparation and Evaluation of TFT> After forming a semiconductor film, an electrode of Ti 10 nm/Au 40 nm was formed by a vacuum deposition method. The electrode formation was performed using a shadow mask, and a TFT having a channel length L/channel width W = 180 μm / 1000 μm was fabricated. After the TFT was formed, annealing treatment was performed for 1 hour in the air at 200 ° C. For the TFT, a gate voltage was scanned between -40 V and 40 V while applying a drain voltage of 10 V using a semiconductor parameter analyzer (manufactured by Agilent Technologies). The transmission characteristics were measured and the carrier mobility was calculated. The oxide particle dispersion liquid, the particle composition, the synthesis temperature, the particle shape, the presence or absence of the ligand, the operation content, and the carrier mobility of the examples 4 to 10 and the comparative example 2 are shown below. Table 2.
根據表2的結果，可知本發明的氧化物粒子薄膜顯示出高載子移動率。From the results of Table 2, it is understood that the oxide particle film of the present invention exhibits a high carrier mobility.
[實施例11、實施例12、及比較例3] ＜導電膜的製作及評價＞ 以與實施例4所記載的半導體膜的形成方法相同的方式，於Si基板上形成同樣的氧化物粒子膜。於大氣中、300℃下對所形成的氧化物粒子膜進行1小時的退火處理，藉此獲得顯示出簡並傳導（degenerate conduction）的導電膜。於所獲得的導電膜形成2端子電極，進行電阻測定，計算出比電阻[單位：Ωcm]。 將結果示於表3。[Example 11, Example 12, and Comparative Example 3] <Preparation and Evaluation of Conductive Film> The same oxide particle film was formed on the Si substrate in the same manner as the method of forming the semiconductor film described in Example 4. . The formed oxide particle film was annealed in the air at 300 ° C for 1 hour to obtain a conductive film showing degenerate conduction. A two-terminal electrode was formed on the obtained conductive film, and resistance measurement was performed to calculate a specific resistance [unit: Ωcm]. The results are shown in Table 3.
根據表3的結果可知，藉由使用具有三股形狀、四股形狀的氧化物粒子，作為導電膜可實現低比電阻值。According to the results of Table 3, it is understood that a low specific resistance value can be realized as a conductive film by using oxide particles having a three-strand shape and a four-stripe shape.
本發明的具體形態的記述是以記述與說明為目的而提供。確實無意將本發明限定於所揭示的該實施方式，或無意進行籠統概括。明顯地，本領域技術人員可進行多種修飾或變形，此不言自明。該形態是為了最充分地說明本發明的概念或其實際應用而選定者，是為了藉此使本領域其他技術人員理解本發明，以使本領域其他技術人員可為了使之適合於所期望的特定用途而完成各種形態或各種變形。The description of the specific embodiments of the present invention is provided for the purpose of description and description. The invention is not intended to be limited to the disclosed embodiments, or to be construed in a general. Obviously, many modifications or variations can be made by those skilled in the art. This configuration is intended to best explain the concept of the invention or its application, and is intended to enable other persons skilled in the art to understand the invention. Various forms or variations are accomplished for a particular use.
將於2014年6月2日提出申請的日本專利申請案第2014-114435號公報的揭示整體作為參照文獻而引入至此。 於指定本說明書所記述的各刊行物或專利申請案、及技術標準作為引用文獻而特別且個別地引入的情形時，該些全部刊行物或專利申請案、及技術標準是於與該引用文獻相同的限定範圍內併入於此。本發明的範圍欲由下述申請專利的範圍及其等價物而決定。The disclosure of Japanese Patent Application No. 2014-114435, filed on Jun. 2, 2014, is hereby incorporated by reference in its entirety herein. In the case where the publications or patent applications and technical standards described in the specification are specifically and individually introduced as citations, all such publications or patent applications, and technical standards are associated with the cited documents. The same limited scope is incorporated herein. The scope of the invention is intended to be determined by the scope of the claims
10、30、40、50‧‧‧薄膜電晶體（TFT）
10a‧‧‧驅動用TFT
10b‧‧‧開關用TFT
12‧‧‧基板
14‧‧‧活性層
16‧‧‧源極電極
18‧‧‧汲極電極
20‧‧‧閘極絕緣膜
22‧‧‧閘極電極
60‧‧‧雙股形狀的氧化物粒子
62‧‧‧三股形狀的氧化物粒子
63‧‧‧四股形狀的氧化物粒子
100‧‧‧液晶顯示裝置
102、202、216‧‧‧鈍化層
104‧‧‧像素下部電極
106‧‧‧對向上部電極
108‧‧‧液晶層
110‧‧‧RGB彩色濾光片
112、220、320‧‧‧閘極配線
112a、112b‧‧‧偏光板
114、222、322‧‧‧資料配線
116、318‧‧‧接觸孔
200‧‧‧有機EL顯示裝置
208‧‧‧下部電極
210、306‧‧‧上部電極
212‧‧‧有機發光層
214‧‧‧有機EL發光元件
224‧‧‧驅動配線
226、310‧‧‧電容器
300‧‧‧X射線感測器
302‧‧‧電荷收集用電極
304‧‧‧X射線轉換層
308‧‧‧鈍化膜
312‧‧‧電容器用下部電極
314‧‧‧電容器用上部電極
316‧‧‧絕緣膜
611、612、621、622、623、631、632、633、634、‧‧‧突出部
615、625、626、627、635、636、637、638‧‧‧凹部
621S‧‧‧包圍突出部
621‧‧‧的區域
623S‧‧‧包圍突出部
623‧‧‧的區域10, 30, 40, 50‧‧‧ Film Transistor (TFT)
10a‧‧‧Drive TFT
10b‧‧‧Switching TFT
12‧‧‧Substrate
14‧‧‧Active layer
16‧‧‧Source electrode
18‧‧‧汲electrode
20‧‧‧gate insulating film
22‧‧‧gate electrode
60‧‧‧ Double-stranded oxide particles
62‧‧‧Three-strand oxide particles
63‧‧‧ four-shaped oxide particles
100‧‧‧Liquid crystal display device
102, 202, 216‧‧ ‧ passivation layer
104‧‧‧pixel lower electrode
106‧‧‧for the upper electrode
108‧‧‧Liquid layer
110‧‧‧RGB color filter
112, 220, 320‧‧‧ gate wiring
112a, 112b‧‧‧ polarizing plate
114, 222, 322‧‧‧ data wiring
116, 318‧‧‧ contact holes
200‧‧‧Organic EL display device
208‧‧‧lower electrode
210, 306‧‧‧ upper electrode
212‧‧‧Organic light-emitting layer
214‧‧‧Organic EL light-emitting elements
224‧‧‧Drive wiring
226, 310‧‧‧ capacitors
300‧‧‧X-ray sensor
302‧‧‧Electrical electrodes for charge collection
304‧‧‧X-ray conversion layer
308‧‧‧passivation film
312‧‧‧The lower electrode for capacitors
314‧‧‧Upper electrode for capacitor
316‧‧‧Insulation film
611, 612, 621, 622, 623, 631, 632, 633, 634, ‧ ‧ protrusions
615, 625, 626, 627, 635, 636, 637, 638 ‧ ‧ recesses
621S‧‧‧ Surrounding the protrusion
Area of 621‧‧
623S‧‧‧ Surrounding the protrusion
Area of 623‧‧
圖1 是表示藉由本發明所製造的薄膜電晶體的一例（ 頂閘極-頂接觸（top gate-top contact） 型） 的構成的概略圖。圖2 是表示藉由本發明所製造的薄膜電晶體的一例（ 頂閘極-底接觸（top gate-bottom contact） 型） 的構成的概略圖。圖3 是表示藉由本發明所製造的薄膜電晶體的一例（ 底閘極-頂接觸（bottom gate-top contact） 型） 的構成的概略圖。圖4 是表示藉由本發明所製造的薄膜電晶體的一例（ 底閘極-底接觸（bottom gate-bottom contact） 型） 的構成的概略圖。圖5 是表示實施方式的液晶顯示裝置的一部分的概略截面圖。圖6 是圖5 的液晶顯示裝置的電配線的概略構成圖。圖7 是表示實施方式的有機電致發光（Electroluminescence，EL） 顯示裝置的一部分的概略截面圖。圖8 是圖7 的有機EL 顯示裝置的電配線的概略構成圖。圖9 是表示實施方式的X 射線感測器陣列的一部分的概略截面圖。圖10 是圖9 的X 射線感測器陣列的電配線的概略構成圖。圖11A 是表示本發明的具有兩個突出部的氧化物粒子的形狀的示意平面圖。圖11B 是表示本發明的具有三個突出部的氧化物粒子的形狀的示意平面圖。圖11C 是表示本發明的具有四個突出部的氧化物粒子的形狀的示意平面圖。圖12 是實施例1 的氧化物粒子的穿透式電子顯微鏡圖像（TEM（Transmission Electron Microscope） 圖像）。圖13 是實施例2 的氧化物粒子的穿透式電子顯微鏡圖像（TEM 圖像）。圖14 是實施例3 的氧化物粒子的穿透式電子顯微鏡圖像（TEM 圖像）。圖15 是比較例1 的氧化物粒子的穿透式電子顯微鏡圖像（TEM 圖像）。圖16 是用以說明本發明的氧化物粒子的形狀的概念圖。Fig. 1 is a schematic view showing a configuration of an example of a thin film transistor (top gate-top contact type) manufactured by the present invention. Fig. 2 is a schematic view showing a configuration of an example of a thin film transistor (top gate-bottom contact type) manufactured by the present invention. 3 is a schematic view showing a configuration of an example of a thin film transistor (bottom gate-top contact type) manufactured by the present invention. 4 is a schematic view showing a configuration of an example of a thin film transistor (bottom gate-bottom contact type) manufactured by the present invention. Fig. 5 is a schematic cross-sectional view showing a part of a liquid crystal display device of the embodiment. Fig. 6 is a schematic configuration diagram of electrical wiring of the liquid crystal display device of Fig. 5; Fig. 7 is a schematic cross-sectional view showing a part of an organic electroluminescence (EL) display device according to an embodiment. Fig. 8 is a schematic configuration diagram of electrical wiring of the organic EL display device of Fig. 7; Fig. 9 is a schematic cross-sectional view showing a part of an X-ray sensor array of the embodiment. Fig. 10 is a schematic block diagram showing electrical wiring of the X-ray sensor array of Fig. 9; Fig. 11A is a schematic plan view showing the shape of oxide particles having two protrusions of the present invention. Fig. 11B is a schematic plan view showing the shape of oxide particles having three projections of the present invention. Fig. 11C is a schematic plan view showing the shape of oxide particles having four projections of the present invention. Fig. 12 is a transmission electron microscope image (TEM (Transmission Electron Microscope) image) of the oxide particles of Example 1. Fig. 13 is a transmission electron microscope image (TEM image) of the oxide particles of Example 2. Fig. 14 is a transmission electron microscope image (TEM image) of the oxide particles of Example 3. 15 is a transmission electron microscope image (TEM image) of the oxide particles of Comparative Example 1. Fig. 16 is a conceptual diagram for explaining the shape of the oxide particles of the present invention.
62‧‧‧三股形狀的氧化物粒子 62‧‧‧Three-strand oxide particles
621、622、623‧‧‧突出部 621, 622, 623‧‧ ‧ protruding parts
625、626、627‧‧‧凹部 625, 626, 627‧‧ ‧ recess
Claims (29)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014114435 | 2014-06-02 | ||
| JP2014-114435 | 2014-06-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201545988A true TW201545988A (en) | 2015-12-16 |
| TWI686355B TWI686355B (en) | 2020-03-01 |
Family
ID=54766646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104117083A TWI686355B (en) | 2014-06-02 | 2015-05-28 | Production method of oxide particles, oxide particles dispersion liquid, and thin film layer production method of oxide particles |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6363706B2 (en) |
| KR (1) | KR101900175B1 (en) |
| TW (1) | TWI686355B (en) |
| WO (1) | WO2015186573A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI759290B (en) * | 2016-03-31 | 2022-04-01 | 日商迪睿合股份有限公司 | Anisotropic conductive connection structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111601774B (en) | 2018-01-15 | 2023-03-28 | 国立大学法人东北大学 | ITO particles, dispersion liquid, and method for producing ITO film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5445697A (en) * | 1977-09-17 | 1979-04-11 | Sumitomo Metal Mining Co | Manufacture of indium oxide |
| JP3336148B2 (en) * | 1995-02-20 | 2002-10-21 | 石原産業株式会社 | Needle-like conductive antimony-containing tin oxide fine powder and method for producing the same |
| JP4301589B2 (en) * | 1998-04-03 | 2009-07-22 | 株式会社トクヤマ | Composite tin oxide powder and method for producing the same |
| JP2008195560A (en) * | 2007-02-09 | 2008-08-28 | Sumitomo Metal Mining Co Ltd | Method for producing powder containing indium oxide as main component |
| JP2011124289A (en) * | 2009-12-08 | 2011-06-23 | Sekisui Chem Co Ltd | Metal oxide semiconductor particle dispersed composition |
| JP2012036060A (en) * | 2010-08-11 | 2012-02-23 | Mitsui Mining & Smelting Co Ltd | Tin/antimony-doped indium oxide particle and method for producing the same |
| JP5861415B2 (en) * | 2011-11-30 | 2016-02-16 | 東ソー株式会社 | Metal oxide fine particle dispersion and transparent conductive film using the same |
-
2015
- 2015-05-26 WO PCT/JP2015/065122 patent/WO2015186573A1/en active Application Filing
- 2015-05-26 KR KR1020167033787A patent/KR101900175B1/en active IP Right Grant
- 2015-05-26 JP JP2016525783A patent/JP6363706B2/en active Active
- 2015-05-28 TW TW104117083A patent/TWI686355B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI759290B (en) * | 2016-03-31 | 2022-04-01 | 日商迪睿合股份有限公司 | Anisotropic conductive connection structure |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015186573A1 (en) | 2015-12-10 |
| JP6363706B2 (en) | 2018-07-25 |
| TWI686355B (en) | 2020-03-01 |
| JPWO2015186573A1 (en) | 2017-04-20 |
| KR20170003616A (en) | 2017-01-09 |
| KR101900175B1 (en) | 2018-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI613826B (en) | Method of producing thin film transistor, thin film transistor, display device, image sensor, and x-ray sensor | |
| TWI569451B (en) | Thin film transistor, method of manufacturing the same, and device having the same | |
| JP5497417B2 (en) | THIN FILM TRANSISTOR, MANUFACTURING METHOD THEREOF, AND APPARATUS HAVING THE THIN FILM TRANSISTOR | |
| JP5606787B2 (en) | Thin film transistor manufacturing method, thin film transistor, image sensor, X-ray sensor, and X-ray digital imaging apparatus | |
| CN105706243B (en) | Metal-oxide semiconductor (MOS) film, thin film transistor (TFT), display device, imaging sensor and X ray sensor | |
| JP6117124B2 (en) | Oxide semiconductor film and manufacturing method thereof | |
| JP5955305B2 (en) | Semiconductor film, semiconductor film manufacturing method, solar cell, light emitting diode, thin film transistor, and electronic device | |
| TW201139266A (en) | Deposition of nanoparticles | |
| JP2022530420A (en) | Stabilized inks containing semiconductor particles and their use | |
| TW201545988A (en) | Oxide particles, production method of the same, oxide particles dispersion liquid, thin film layer production method of oxide particles, thin film transistor and electron element using the same | |
| JP6275441B2 (en) | Semiconductor film, oxide fine particle dispersion, method of manufacturing semiconductor film, and thin film transistor | |
| JP6177713B2 (en) | Thin film manufacturing method | |
| TWI648795B (en) | Method of producing metal oxide film | |
| JP6250481B2 (en) | Metal oxide film, metal oxide film manufacturing method, thin film transistor, and electronic device | |
| KR101967564B1 (en) | Method for producing metal oxide semiconductor film, metal oxide semiconductor film, thin film transistor and electronic device | |
| KR20180048236A (en) | Organic semiconductor layer contained CNT, Preparing thereof and Thin-film transistor using the same | |
| JP6291311B2 (en) | Oxide particles and method for producing the same | |
| KR20190079819A (en) | Thin film transistor comprising double semiconductor | |
| JP2018093199A (en) | Semiconductor film and semiconductor element using the same, and manufacturing method of semiconductor film |