CN116828949A - Preparation method of modified zinc oxide and modified zinc oxide solution and photoelectric device - Google Patents
Preparation method of modified zinc oxide and modified zinc oxide solution and photoelectric device Download PDFInfo
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- CN116828949A CN116828949A CN202210280523.0A CN202210280523A CN116828949A CN 116828949 A CN116828949 A CN 116828949A CN 202210280523 A CN202210280523 A CN 202210280523A CN 116828949 A CN116828949 A CN 116828949A
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- zinc oxide
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 166
- -1 silane amine Chemical class 0.000 claims abstract description 95
- 239000011787 zinc oxide Substances 0.000 claims abstract description 83
- 229910000077 silane Inorganic materials 0.000 claims abstract description 81
- 239000002245 particle Substances 0.000 claims abstract description 63
- 239000003446 ligand Substances 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims description 163
- 239000002243 precursor Substances 0.000 claims description 94
- 150000003751 zinc Chemical class 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000003513 alkali Substances 0.000 claims description 33
- 239000002096 quantum dot Substances 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 19
- 230000005693 optoelectronics Effects 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- AIPVRBGBHQDAPX-UHFFFAOYSA-N hydroxy(methyl)silane Chemical compound C[SiH2]O AIPVRBGBHQDAPX-UHFFFAOYSA-N 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims description 3
- FWXNJWAXBVMBGL-UHFFFAOYSA-N 9-n,9-n,10-n,10-n-tetrakis(4-methylphenyl)anthracene-9,10-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C2=CC=CC=C2C(N(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)=C2C=CC=CC2=1)C1=CC=C(C)C=C1 FWXNJWAXBVMBGL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 241000764773 Inna Species 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 3
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 3
- 102000003978 Tissue Plasminogen Activator Human genes 0.000 claims description 3
- 108090000373 Tissue Plasminogen Activator Proteins 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 229910003363 ZnMgO Inorganic materials 0.000 claims description 3
- 229910007717 ZnSnO Inorganic materials 0.000 claims description 3
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 150000002220 fluorenes Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 claims description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 150000003220 pyrenes Chemical class 0.000 claims description 3
- 235000021286 stilbenes Nutrition 0.000 claims description 3
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910016001 MoSe Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 89
- 238000004806 packaging method and process Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000004246 zinc acetate Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RROAJOQUFRGVRG-UHFFFAOYSA-L dichlorozinc;ethanol Chemical compound [Cl-].[Cl-].[Zn+2].CCO RROAJOQUFRGVRG-UHFFFAOYSA-L 0.000 description 2
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002365 hybrid physical--chemical vapour deposition Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- 229910003185 MoSx Inorganic materials 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- 229910004481 Ta2O3 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- VWTSXINFCUODBJ-UHFFFAOYSA-L zinc methanol diacetate Chemical compound [Zn++].CO.CC([O-])=O.CC([O-])=O VWTSXINFCUODBJ-UHFFFAOYSA-L 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The application discloses a preparation method of modified zinc oxide and a modified zinc oxide solution and a photoelectric device. The modified zinc oxide comprises zinc oxide particles and a silane amine ligand bonded to the surface of the zinc oxide particles. The silane amine ligand can increase the interval between zinc oxide particles, passivate the surfaces of the zinc oxide particles and reduce the generation of oxygen vacancies. Meanwhile, nitrogen atoms exist in the silane amine, so that ligands can be effectively attached to the surfaces of zinc oxide particles, the zinc oxide particles are prevented from agglomerating, and the phenomena of quenching of a luminescent layer, voltage rise of a photoelectric device, increase of leakage current of the photoelectric device and the like are effectively avoided.
Description
Technical Field
The application relates to the technical field of illumination display, in particular to a preparation method of modified zinc oxide and a modified zinc oxide solution and a photoelectric device.
Background
Quantum dot electroluminescence is a novel solid-state lighting display technology, has the advantages of low cost, light weight, high response speed, high color saturation and the like, has a wide development prospect, and quantum dot light emitting diodes (QLEDs) become one of important research directions.
At present, the electron transport layer of the QLED is generally made of zinc oxide particles, but the zinc oxide particles are easy to agglomerate due to higher surface activity of the zinc oxide particles, so that the luminescent layer is quenched. The voltage rise of the photoelectric device is easy to be caused, so that the leakage current of the photoelectric device is increased, and the QLED performance is reduced. In addition, QLED light emission generates heat, which causes zinc oxide particles to be heated unevenly and also causes quenching of the light emitting layer.
Disclosure of Invention
In view of the above, the application provides a preparation method of modified zinc oxide and a modified zinc oxide solution, and a photoelectric device, and aims to solve the technical problem that zinc oxide particles are easy to cause agglomeration in the prior art.
Embodiments of the present application are accomplished by the modified zinc oxide comprising zinc oxide particles and a silane amine ligand bound to the surface of the zinc oxide particles.
Optionally, the zinc oxide particle also comprises methyl silanol ligand and amino ligand which are combined on the surface of the zinc oxide particle
Optionally, the molar ratio of the zinc oxide particles to the silane amine ligand is 1:0.5-1:2.
Optionally, the particle size of the zinc oxide particles is 3 nm-50 nm.
The embodiment of the application also provides a preparation method of the modified zinc oxide solution, which comprises the following steps:
providing a silane amine precursor solution, a zinc salt precursor solution and a base precursor solution;
mixing the alkali precursor solution and the zinc salt precursor solution for reaction to obtain a mixed solution;
and mixing the silane amine precursor solution and the mixed solution for reaction to obtain a modified zinc oxide solution.
Optionally, the silane amine precursor solution is obtained by mixing silane amine and dimethyl sulfoxide, or the silane amine precursor solution is obtained by mixing silane amine and dimethyl formamide, the zinc salt precursor solution is obtained by mixing zinc salt and organic alcohol, and the alkali precursor solution is obtained by mixing alkali and organic alcohol;
optionally, the silane amine is selected from at least one of hexamethyldisilazane, heptamethyldisilazane, 1, 3-dibutyl-1, 3-tetramethylsilazane.
Optionally, the volume ratio of the silane amine to the dimethyl sulfoxide is 1: (1-50).
Optionally, the volume ratio of the silane amine to the dimethylformamide is 1: (1-50).
Optionally, the molar ratio of the zinc salt to the organic alcohol is 1: (0.5-2).
Optionally, the molar ratio of the base to the organic alcohol is 1: (0.3-1.5).
Optionally, in the step of mixing the alkali precursor solution and the zinc salt precursor solution to react to obtain a mixed solution, the reaction time of the alkali precursor solution and the zinc salt precursor solution is 0.25-2 h, and the reaction temperature is 0-60 ℃; and/or, in the step of mixing and reacting the silane amine precursor solution and the mixed solution to obtain the modified zinc oxide solution, the reaction time of the silane amine precursor solution and the mixed solution is 0.25-2 h, and the reaction temperature is 0-60 ℃.
Optionally, the volume ratio of the silane amine precursor solution, the zinc salt precursor solution and the alkali precursor solution is 1: (0.5-1.2): (0.5-1.2).
Optionally, the zinc salt is selected from at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate dihydrate.
Optionally, the organic alcohol is at least one selected from isopropanol, ethanol, propanol, butanol, pentanol, hexanol and other organic solvents.
Optionally, the zinc element in the zinc salt precursor solution and the OH in the alkali precursor solution - The molar ratio of (2) is 1: (1-2).
Optionally, the base is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethyl ammonium hydroxide pentahydrate.
The embodiment of the application also provides a photoelectric device, which comprises a cathode, an electron transport layer, a light-emitting layer and an anode which are sequentially stacked, wherein the material of the electron transport layer comprises the modified zinc oxide, or the material of the electron transport layer is prepared by the preparation method of the modified zinc oxide solution.
Optionally, the photoelectric device further comprises a hole injection layer and a hole transport layer, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer and the anode are stacked in sequence.
Optionally, the materials of the anode and the cathode are selected from at least one of metal, carbon material or metal oxide independently of each other, wherein the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg; the carbon material is at least one of graphite, carbon nano tube, graphene or carbon fiber; the metal oxide is at least one selected from indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide; and/or the material of the light-emitting layer comprises an organic light-emitting material or quantum dots;
wherein the organic luminescent material is selected from at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
the quantum dot is selected from single component quantum dot and core-shell structure quantum dotAt least one of inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a core-shell structure quantum dot, the component of the quantum dot is selected from at least one of a group II-VI compound, a group III-V compound, a group IV-VI compound or a group I-III-VI compound, wherein the group II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe or HgZnSTe, the group III-V compound is selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, the group IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe or SnPbSTe, and the group I-III-VI compound is selected from CuInS 2 、CuInSe 2 Or AgInS 2 At least one of (a) and (b);
and/or the material of the electron transport layer comprises nano metal oxide;
the nano metal oxide is selected from nano ZnO and nano TiO 2 Nano SnO 2 Nano Ta 2 O 3 Nano ZrO 2 At least one of nano TiLiO, nano ZnGaO, nano ZnAlO, nano ZnMgO, nano ZnSnO, nano ZnLiO, nano InSnO, nano AlZnO, nano ZnOCl or nano ZnOF;
and/or the material of the hole transport layer is selected from at least one of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl-substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine;
and/or the material of the hole injection layer is selected from poly (3, 4-ethylenedioxythiophene): at least one of poly (styrenesulfonic acid), copper phthalocyanine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide or transition metal chalcogenide, wherein the transition metal oxide is selected from NiO x 、MoO x 、WO x 、CrO x Or CuO, the transition metal chalcogenide is selected from MoS x 、MoSe x 、WS x 、WSe x Or at least one of CuS.
Compared with the prior art, the modified zinc oxide can be used for manufacturing an electron transport layer, and the electron transport layer can be used in photoelectric devices. The silane amine ligand can increase the interval between zinc oxide particles, passivate the surfaces of the zinc oxide particles and reduce the generation of oxygen vacancies. Meanwhile, nitrogen atoms exist in the silane amine and can be combined to the surfaces of the zinc oxide particles, so that the zinc oxide particles are prevented from agglomerating, and the phenomena of quenching of a luminescent layer, voltage rise of a photoelectric device, increase of leakage current of the photoelectric device and the like are effectively avoided.
The silane amine ligand contains nitrogen atoms, which is favorable for the extension of charges on the whole molecular chain, and the electron transfer purpose of the molecules is achieved due to the electron offset of the nitrogen atoms, so that the conductivity of the modified zinc oxide can be adjusted according to different proportions of the silane amine ligand and different types of the silane amine ligand, namely different selection of alkali sources, thereby enabling the electron transfer layer prepared from the modified zinc oxide to be more matched with the conductivity of the luminescent layer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a modified zinc oxide solution according to an embodiment of the present application;
FIG. 2 is a schematic structural diagram of an optoelectronic device according to an embodiment of the present application;
FIG. 3 is a flowchart of a method for fabricating a front-mounted optoelectronic device according to an embodiment of the present application;
fig. 4 is a flowchart of a method for fabricating a flip-chip optoelectronic device according to another embodiment of the present application;
fig. 5 is a performance test chart of examples 1 to 3 and comparative example 1.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application based on the embodiments of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application. In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2,3, 4,5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
Embodiments of the present application provide a modified zinc oxide comprising zinc oxide particles and a silane amine ligand bound to the surface of the zinc oxide particles.
The modified zinc oxide of this embodiment can be used to make electron transport layers that can be used in optoelectronic devices. The silane amine ligand can increase the interval between zinc oxide particles, passivate the surfaces of the zinc oxide particles and reduce the generation of oxygen vacancies. Meanwhile, nitrogen atoms are arranged in the silane amine, and the silane amine can coordinate to the surfaces of the zinc oxide particles through the nitrogen atoms, so that the zinc oxide particles are prevented from agglomerating, and the phenomena of quenching of a luminescent layer, voltage rise of a photoelectric device, increase of leakage current of the photoelectric device and the like are effectively avoided.
The silane amine ligand contains nitrogen atoms, which is favorable for the extension of charges on the whole molecular chain, and the electron transfer purpose of the molecules is achieved due to the electron offset of the nitrogen atoms, so that the conductivity of the modified zinc oxide can be adjusted according to different proportions of the silane amine ligand and different types of the silane amine ligand, namely different selection of alkali sources, thereby enabling the electron transfer layer prepared from the modified zinc oxide to be more matched with the conductivity of the luminescent layer.
The silanol ligand can also exist in the form of methyl silanol and amino ligand, and the modified zinc oxide also comprises methyl silanol ligand and amino ligand which are combined on the surface of the zinc oxide particles. Methyl silanol and amino ligand can be combined with dangling bonds of zinc in zinc oxide particles to form silane type and amino ligand with compact structure, so as to achieve the aim of protecting zinc oxide particles. Because methyl silanol forms an obvious skeleton structure, the corrosion of water and oxygen to zinc oxide particles can be effectively isolated. At this time, the surface of the zinc oxide particles includes methyl silanol ligand and amino ligand in addition to the silane amine ligand. Wherein the amino ligand mainly comprises an organic amino group.
When the photoelectric device generates heat, methyl silanol and organic amino can react with each other in an endothermic way to form silane amine, so that the impact of the heat on zinc oxide particles is counteracted, and the quenching of the luminous layer is avoided. When the optoelectronic device cools, the methyl silanol cools, and the methyl silanol and the organic amino groups in turn form the silanol ligands. Wherein the methyl silanol mainly comprises trimethyl silanol and heptamethyl silanol.
In one embodiment, the molar ratio of zinc oxide particles to silane amine ligands is 1:0.5 to 1:2. When the molar ratio of the zinc oxide particles to the silane amine ligand is 1:0.5-1:2, the silane amine ligand can be effectively prevented from being enriched on the surfaces of the zinc oxide particles in a large amount, the conduction distance between the zinc oxide particles is prevented from being prolonged, and the conduction effect of the zinc oxide particles is reduced. And sufficient silane amine ligand coordinates to the zinc oxide particles to achieve the desired utility.
In one embodiment, the zinc oxide particles have a particle size of 3nm to 50nm. Preferably, the particle size of the zinc oxide particles is 3nm to 10nm. When the particle diameter of the zinc oxide particles is 3nm to 10nm, the particle diameter of the modified zinc oxide particles which is generally produced is 5nm to 50nm.
Referring to fig. 1, the embodiment of the application further provides a preparation method of the modified zinc oxide solution, which includes:
s1, providing a silane amine precursor solution, a zinc salt precursor solution and a base precursor solution;
s2, mixing the alkali precursor solution and the zinc salt precursor solution for reaction to obtain a mixed solution;
s3, mixing and reacting the silane amine precursor solution and the mixed solution to obtain a modified zinc oxide solution.
When the silane amine enters the alcohol solution, alcoholysis can be carried out to form methyl silanol and organic amino, and the methyl silanol and the organic amino can be combined with dangling bonds of zinc in zinc oxide particles to form silane type and amino type ligands with compact structures, so that the aim of protecting the zinc oxide particles is fulfilled. And finally, part of the silane amine exists in the form of methyl silanol and organic amino in the modified zinc oxide.
The ratio of the zinc salt precursor solution to the alkali precursor solution is the same, the zinc salt precursor solution and the alkali precursor solution react to generate zinc oxide, namely the mixed solution contains zinc oxide, when the silane amine precursor solution and the mixed solution react in a mixed mode, a modified zinc oxide solution is generated, and zinc oxide particles in the modified zinc oxide solution are coordinated with silane amine ligands.
The modified zinc oxide solution prepared by the preparation method of the modified zinc oxide solution of this embodiment also has the above advantages, and will not be described here again.
In an embodiment, the silane amine precursor solution is obtained by mixing silane amine and dimethyl sulfoxide, or the silane amine precursor solution is obtained by mixing silane amine and dimethyl formamide, the zinc salt precursor solution is obtained by mixing zinc salt and organic alcohol, and the alkali precursor solution is obtained by mixing alkali and organic alcohol. In one embodiment, the silane amine is selected from at least one of hexamethyldisilazane, heptamethyldisilazane, 1, 3-dibutyl-1, 3-tetramethylsilazane. According to different selection of the silane amine, the nitrogen source is different, so that the conductivity of the electron transport layer can be adjusted, and the conductivity of the electron transport layer and the luminous layer are more suitable.
In one embodiment, the volume ratio of the silane amine to the dimethyl sulfoxide is 1: (1-50). The volume ratio of the silane amine to the dimethylformamide is 1: (1-50). Wherein the silane amine and the dimethyl sulfoxide are liquid at normal temperature, the concentration of the silane amine is more than 98%, and the concentration of the dimethyl sulfoxide (DMSO) and the dimethyl formamide (DMF) is more than 99%. Both dimethyl sulfoxide and dimethylformamide are used for dissolving the silane amine, if the ratio of dimethyl sulfoxide to dimethylformamide is too high, the subsequent reaction rate is affected, and if the ratio of dimethyl sulfoxide to dimethylformamide is too low, the silane amine is precipitated, and the silane amine cannot be completely dissolved.
In one embodiment, the molar ratio of the zinc salt to the organic alcohol is 1: (0.5-2). If the organic alcohol is too much, the reaction rate is lowered in the subsequent reaction, and if the organic alcohol is too little, the zinc salt cannot be completely dissolved.
In one embodiment, the molar ratio of the base to the organic alcohol is 1: (0.3-1.5). If the organic alcohol is too much, the reaction rate is lowered in the subsequent reaction, and if the organic alcohol is too little, the alkali cannot be completely dissolved.
In one embodiment, the alkali precursor solution and the zinc salt precursor solution are mixed and reacted to obtain a mixed solution; and mixing the silane amine precursor solution and the mixed solution for reaction to obtain a modified zinc oxide solution, namely, in the step S2 and the step S3, the step S2 and the step S3 are one reaction, and silane amine ligands are generated on the surfaces of zinc oxide particles while the zinc oxide particles are generated, and the silane amine ligands are coordinated to the zinc oxide particles in a coordination bond mode. So the reaction time of the step S2 and the step S3 is 0.25 h-2 h, and the reaction temperature is 0-60 ℃. If the reaction temperature is too high, the reaction is too fast, the agglomeration of the zinc oxide nano material is accelerated, and zinc oxide particles cannot be generated. If the reaction temperature is too low, the reaction rate is too slow to reach the reaction proceeding condition. If the reaction time is too long, zinc oxide particles are agglomerated and cannot be generated; if the reaction time is too short, the reaction conditions cannot be satisfied.
In one embodiment, the volume ratio of the silane amine precursor solution, the zinc salt precursor solution, and the base precursor solution is 1: (0.5-1.2): (0.5-1.2). Wherein, the proportion of the zinc salt precursor solution and the alkali precursor solution is the same, and the zinc salt precursor solution and the alkali precursor solution react to generate zinc oxide. If the ratio of the zinc salt precursor solution to the alkali precursor solution is too large, zinc hydroxide precipitate may be formed, and if the ratio of the zinc salt precursor solution to the alkali precursor solution is too small, the reaction cannot be performed.
In one embodiment, the zinc salt is selected from at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate dihydrate.
In one embodiment, the organic alcohol is at least one selected from isopropanol, ethanol, propanol, butanol, pentanol, hexanol, and other organic solvents.
In one embodiment, the zinc element in the zinc salt precursor solution and theOH in the alkali precursor solution - The molar ratio of (2) is 1: (1-2). If the zinc element is excessive, zn and OH are caused - Free state substances of Zn (OH) are formed, and zinc oxide is difficult to be formed. If the zinc element is too small, the OH is excessive, and Zn and OH - A large amount of reaction, and the Zn (OH) is generated too quickly 2 Cannot form zinc oxide.
Zinc element in zinc salt precursor solution and OH in alkali precursor solution - The molar ratio of (2) is 1: in the case of (1-2), zinc oxide may be produced by alcoholysis, wherein the amount of zinc element is determined by the amount of zinc salt added.
In one embodiment, the base is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethyl ammonium hydroxide pentahydrate.
The embodiment of the application also provides an optoelectronic device, which comprises an electron transport layer, wherein the material of the electron transport layer comprises the modified zinc oxide, or the material of the electron transport layer is prepared by the preparation method of the modified zinc oxide solution.
The photovoltaic device of this embodiment also has the above advantages, and will not be described in detail herein.
Referring to fig. 2, in an embodiment, the optoelectronic device further includes an anode 10, a hole injection layer 20, a hole transport layer 30, a light emitting layer 40, and a cathode 60, wherein the cathode 60, the electron transport layer 50, the light emitting layer 40, the hole transport layer 30, the hole injection layer 20, and the anode 10 are stacked in sequence.
The materials of the anode 10 and the cathode 60 are independently selected from at least one of metal, carbon material, or metal oxide, wherein the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg; among the metals, the morphology includes, but is not limited to, one or more of dense films, nanowires, nanospheres, nanorods, nanopyramids, and nanohollow spheres. The carbon material is at least one of graphite, carbon nano tube, graphene or carbon fiber; the metal oxide is at least one selected from indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide;
and/or the material of the light emitting layer 40 includes an organic light emitting material or quantum dots;
wherein the organic luminescent material is selected from at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
the quantum dots are selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a core-shell structure quantum dot, the component of the quantum dot is selected from at least one of a group II-VI compound, a group III-V compound, a group IV-VI compound or a group I-III-VI compound, wherein the group II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe or HgZnSTe, the group III-V compound is selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, the group IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe or SnPbSTe, and the group I-III-VI compound is selected from at least one of CuInS2, cuInSe2 or AgInS 2;
and/or the material of the electron transport layer 50 includes nano metal oxide;
the nano metal oxide is at least one of nano ZnO, nano TiO2, nano SnO2, nano Ta2O3, nano ZrO2, nano TiLiO, nano ZnGaO, nano ZnAlO, nano ZnMgO, nano ZnSnO, nano ZnLiO, nano InSnO, nano AlZnO, nano ZnOCl or nano ZnOF;
and/or the material of the hole transport layer 30 is selected from at least one of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl-substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine;
and/or the hole injection layer 20 is made of a material selected from poly (3, 4-ethylenedioxythiophene): at least one of poly (styrenesulfonic acid), copper phthalocyanine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide, or transition metal chalcogenide, wherein the transition metal oxide is selected from at least one of NiOx, moOx, WOx, crOx or CuO, and the transition metal chalcogenide is selected from at least one of MoSx, moSex, WSx, WSex or CuS.
In addition to the above functional layers, the optoelectronic device may further include some functional layers conventionally used in the optoelectronic device to help improve performance of the optoelectronic device, such as an electron blocking layer, a hole blocking layer, an electron injection layer, an interface modification layer, and the like. It will be appreciated that the materials and thicknesses of the various layers of the optoelectronic device may be tailored to the lighting requirements of the optoelectronic device.
Referring to fig. 3, in an embodiment, a method for manufacturing a front-mounted optoelectronic device includes:
a1, providing a substrate containing an anode 10;
a2, forming a hole injection layer 20 on the anode 10
A3, forming a hole transport layer 30 on the hole injection layer 20;
a4, forming a light emitting layer 40 on the hole transport layer 30;
a5, forming an electron transport layer 50 on the light-emitting layer 40, wherein the electron transport layer 50 is prepared from the modified zinc oxide or the modified zinc oxide solution in the embodiment;
a6, forming a cathode 60 on the electron transport layer 50.
It can be appreciated that the method for manufacturing the forward-mounted photoelectric device can further comprise a packaging step, wherein the packaging material can be acrylic resin or epoxy resin, the packaging can be machine packaging or manual packaging, ultraviolet curing glue packaging can be adopted, and the concentration of oxygen and water in the environment where the packaging step is carried out is lower than 0.1ppm so as to ensure the stability of the photoelectric device. The packaging mode of the photoelectric device comprises frame glue and dispensing.
In one embodiment, the step of preparing the electron transport layer 50 on the light emitting layer 40 specifically includes: the substrate on which the light-emitting layer 40 has been prepared is placed on a spin coater, and the modified zinc oxide solution is spin-coated onto the light-emitting layer 40. And annealed at 100 c to prepare the electron transport layer 50.
In one embodiment, the step of preparing the cathode 60 on the electron transport layer 50 specifically includes: the substrate on which each functional layer is deposited is placed in an evaporation bin, a layer of 15-30 nm metal silver or aluminum and the like is thermally evaporated through a mask plate to serve as a cathode 60, or a nano Ag wire or Cu wire and the like are used, and the material has small resistance, so that carriers can be smoothly injected.
Referring to fig. 4, in an embodiment, a method for fabricating a flip-chip optoelectronic device includes:
b1, providing a substrate containing a cathode 60;
b2, forming an electron transport layer 50 on the cathode 60, wherein the electron transport layer 50 is made of the modified zinc oxide or the modified zinc oxide solution according to the embodiment;
b3, forming a light emitting layer 40 on the electron transport layer 50;
b4, forming a hole transport layer 30 on the light emitting layer 40;
b5, forming a hole injection layer 20 on the hole transport layer 30;
b6, forming the anode 10 on the hole injection layer 20.
It can be appreciated that the preparation method of the flip-chip photoelectric device can further comprise a packaging step, wherein the packaging material can be acrylic resin or epoxy resin, the packaging can be machine packaging or manual packaging, ultraviolet curing glue packaging can be adopted, and the concentration of oxygen and water in the environment where the packaging step is carried out is lower than 0.1ppm so as to ensure the stability of the photoelectric device. The packaging mode of the photoelectric device comprises frame glue and dispensing.
In one embodiment, the step of preparing the electron transport layer 50 on the cathode 60 specifically includes: the substrate on which the light emitting layer 40 has been prepared is placed on a spin coater, and the modified zinc oxide solution is spin-coated onto the substrate. And annealed at 100 c to prepare the electron transport layer 50.
Preferably, the thickness of the light emitting layer 40 is 20 to 60nm. If the luminescent layer 40 is too thin, electrons will break down the luminescent layer 40, so that the purpose of recombination at the quantum dots cannot be achieved; if the light emitting layer 40 is too thick, exciton recombination is not uniform, thereby reducing the possibility of exciton recombination.
Preferably, the thickness of the electron transport layer 50 is 70 to 90nm. If the electron transport layer 50 is too thick, electron conduction is blocked, which reduces electron conduction efficiency and eventually increases voltage; if the electron transport layer 50 is too thin, electrons cannot cross the energy level barrier, and are directly concentrated between the electron transport layer 50 and the cathode 60, reducing exciton recombination efficiency.
Preferably, the thickness of the cathode 60 is 15 to 30nm. If the thickness of the cathode 60 is too thin, the cathode 60 will break down and electrons will not conduct; if the cathode 60 is too thick, electron conduction is blocked, and electron conduction efficiency is further lowered.
The preparation method of each layer can be a chemical method or a physical method, wherein the chemical method comprises one or more of a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic 10 oxidation method, an electrolytic deposition method and a coprecipitation method; physical methods include, but are not limited to, physical plating methods or solution methods, wherein the solution methods include, but are not limited to, spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slot coating, bar coating; physical plating methods include, but are not limited to, one or more of thermal vapor plating, electron beam vapor plating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
It will be appreciated that the embodiments of the application as shown herein relate to one or more interlayer materials, the positional relationship between layers being expressed using terms such as "lamination" or "forming" or "applying" or "setting", as will be appreciated by those skilled in the art: any terms such as "laminating" or "forming" or "applying" may cover all manner, kinds and techniques of "laminating". Such as sputtering, electroplating, molding, chemical vapor deposition (ChemicalVapor Deposition, CVD), physical vapor deposition (Physical Vapor Deposition, PVD), evaporation, hybrid Physical-chemical vapor deposition (HPCVD), plasma-enhanced chemical vapor deposition (Plasma Enhanced Chemical Vapor Deposition, PECVD), low pressure chemical vapor deposition (Low Pressure Chemical Vapor Deposition, LPCVD), and the like.
The technical scheme and effect of the present application will be described in detail by the following specific examples and comparative example 1, which are only some examples of the present application, and are not intended to limit the present application in any way.
Example 1
A method for preparing a modified zinc oxide solution, comprising:
first, a proper amount of hexamethyldisilazane was added to 10ml of dimethyl sulfoxide solution to prepare a silane amine precursor solution of 0.8 mol/L.
And weighing a proper amount of zinc acetate into 30ml of methanol solution to prepare 1mol/L zinc acetate methanol solution, so as to obtain zinc salt precursor solution.
Weighing a proper amount of potassium hydroxide into 30ml of methanol solution to prepare 1.05mol/L potassium hydroxide methanol solution, thereby obtaining alkali precursor solution.
Mixing potassium hydroxide solution with zinc acetate solution, stirring for 0.5h to obtain mixed solution, adding silane amine precursor solution, and stirring for 0.25h at 25 ℃ to obtain modified zinc oxide solution.
Example 2
A method for preparing a modified zinc oxide solution, comprising:
a proper amount of heptamethyldisilazane was first added to 10ml of dimethyl sulfoxide solution to prepare a 0.5mol/L solution of a silane amine precursor.
And weighing a proper amount of zinc chloride into 30ml of ethanol solution to prepare 1mol/L zinc chloride ethanol solution, so as to obtain zinc salt precursor solution.
Weighing a proper amount of sodium hydroxide into 30ml of methanol solution to prepare 1.3mol/L potassium hydroxide methanol solution, thereby obtaining alkali precursor solution.
Mixing a potassium hydroxide solution with a zinc acetate solution, stirring for 1h to obtain a mixed solution, adding a silane amine precursor solution, and stirring for 1h at 25 ℃ to obtain a modified zinc oxide solution.
Example 3
A method for preparing a modified zinc oxide solution, comprising:
firstly, adding a proper amount of 1, 3-dibutyl-1, 3-tetramethylsilazane into 10ml of dimethyl sulfoxide solution to prepare 0.2mol/L of silane amine precursor solution.
Weighing a proper amount of zinc sulfate into 30ml of methanol solution to prepare 0.9mol/L zinc chloride ethanol solution, so as to obtain zinc salt precursor solution.
Weighing a proper amount of potassium hydroxide into 30ml of ethanol solution to prepare 1.2mol/L potassium hydroxide ethanol solution, thereby obtaining alkali precursor solution.
Mixing potassium hydroxide solution with zinc acetate solution, stirring for 0.5h to obtain mixed solution, adding silane amine precursor solution, and stirring for 0.5h at 25 ℃ to obtain modified zinc oxide solution.
Comparative example 1
A method for preparing a zinc oxide solution, comprising:
firstly, adding a proper amount of zinc acetate into 50ml of ethanol solution to prepare 1mol/L zinc acetate ethanol solution, and stirring and dissolving at 70 ℃ to obtain a precursor solution 1. According to Zn and OH - Weighing potassium hydroxide in a molar ratio of 1:1.1, and adding the potassium hydroxide to 50mAnd (3) preparing 1.1mol/L potassium hydroxide solution in ethanol solution, and stirring and dissolving to obtain a precursor solution 2.
And injecting the precursor solution 1 into the precursor solution 2 for reaction at the injection rate of 10mL/min to obtain an impurity-containing zinc oxide solution, and then cleaning the impurity-containing zinc oxide solution to obtain a pure zinc oxide solution.
The modified zinc oxide solutions of examples 1 to 3 and the zinc oxide solution of comparative example 1 were used to prepare photovoltaic devices, respectively, and performance tests were performed on the prepared photovoltaic devices, namely QLED, which were prepared in examples 1 to 3 and comparative example 1, and the parameters of the QLED performance test were the maximum external quantum efficiency (EQEmax,%) of QLED at a luminance of 1000 nit; the time required for the QLED to decay from 100% to 95% at a luminance of 1000nit (T95-1 Knit, h).
The efficiency test equipment is an efficiency test system built by LabView control QEPRO spectrometer, keithley2400 and Keithley6485, mainly measures parameters such as voltage, current, brightness, luminescence spectrum and the like, and calculates to obtain the maximum external quantum dot efficiency.
The life test equipment is mainly a life test system built by Keithley2400, CS-160 brightness meters and a photodiode detector, and the main principle is as follows: the brightness of the QLED is tested and calibrated by a brightness meter, the QLED is driven by a constant current 2mA source in a test box, the service life of the QLED is simulated and calculated by measuring the brightness change of the QLED, a photodiode detector converts an optical signal into an electric signal, a corresponding voltage value is obtained after the photoelectric signal passes through an amplifying circuit, and the brightness change of the QLED is simulated by the voltage value.
The performance test results are shown in fig. 5, where the external quantum efficiency can represent the luminous efficiency of the QLED. The external quantum efficiency is the ratio of the number of photons emitted to the outside to the number of charges passing through the QD.
T95-1K (h) represents the time required for the QLED to decay from 100% to 95% at a luminance of 1000nit (T95-1 Knit, h). The larger the T95-1K (h) value, the longer the life of the QLED.
As can be seen from fig. 5, the maximum external quantum efficiency of the QLEDs prepared in examples 1 to 3 is greater than that of comparative example 1, indicating that the light emission efficiency of the QLED to which the modified zinc oxide is added is higher.
The maximum external quantum efficiency of the QLEDs prepared in examples 1 to 3 was greater than that of comparative example 1, indicating that the lifetime of the QLED added with the modified zinc oxide was longer.
From this, it can be explained that the QLED added with the modified zinc oxide of this embodiment avoids the aggregation of zinc oxide particles, and effectively avoids the phenomena of quenching of the light emitting layer 40, voltage rise of the QLED, and increase of leakage current of the photovoltaic device, so that the overall performance parameter of the QLED is better.
From examples 1 to 3, it is evident that the maximum external quantum efficiency and T95 to 1K (h) are different, and it is demonstrated that adjusting the types of the silane amine precursor solution, the zinc salt precursor solution, and the alkali precursor solution has a certain effect on the maximum external quantum efficiency and T95 to 1K (h).
The preparation methods of the modified zinc oxide and the modified zinc oxide solution and the photoelectric device provided by the embodiment of the application are described in detail, and specific examples are applied to the description of the principle and the implementation mode of the application, and the description of the above examples is only used for helping to understand the method and the core idea of the application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (14)
1. A modified zinc oxide comprising zinc oxide particles and a silane amine ligand bound to the surface of the zinc oxide particles.
2. The modified zinc oxide of claim 1, further comprising methyl silanol ligands and amino ligands bound to the surface of the zinc oxide particles.
3. The modified zinc oxide of claim 1, wherein the molar ratio of zinc oxide particles to silane amine ligands is from 1:0.5 to 1:2.
4. The modified zinc oxide of claim 1, wherein the zinc oxide particles have a particle size of from 3nm to 50nm.
5. A method for preparing a modified zinc oxide solution, comprising:
providing a silane amine precursor solution, a zinc salt precursor solution and a base precursor solution;
mixing the alkali precursor solution and the zinc salt precursor solution for reaction to obtain a mixed solution;
and mixing the silane amine precursor solution and the mixed solution for reaction to obtain a modified zinc oxide solution.
6. The method for producing a modified zinc oxide solution according to claim 5, wherein the silane amine precursor solution is obtained by mixing silane amine and dimethyl sulfoxide, or the silane amine precursor solution is obtained by mixing silane amine and dimethylformamide;
the zinc salt precursor solution is obtained by mixing zinc salt and organic alcohol;
the alkali precursor solution is obtained by mixing alkali and organic alcohol.
7. The method for producing a modified zinc oxide solution according to claim 6, wherein the silane amine is at least one selected from hexamethyldisilazane, heptamethyldisilazane, 1, 3-dibutyl-1, 3-tetramethylsilazane;
and/or the organic alcohol is at least one selected from isopropanol, ethanol, propanol, butanol, amyl alcohol, hexanol and other organic solvents;
and/or the organic alcohol is at least one selected from isopropanol, ethanol, propanol, butanol, amyl alcohol, hexanol and other organic solvents;
and/or the alkali is at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide and tetramethyl ammonium hydroxide pentahydrate.
8. The method for preparing a modified zinc oxide solution according to claim 6, wherein the volume ratio of the silane amine to the dimethyl sulfoxide is 1: (1-50);
and/or the volume ratio of the silane amine to the dimethylformamide is 1: (1-50);
and/or the molar ratio of the zinc salt to the organic alcohol is 1: (0.5-2);
and/or the molar ratio of the base to the organic alcohol is 1: (0.3-1.5).
9. The method for preparing a modified zinc oxide solution according to claim 5, wherein in the step of mixing the alkali precursor solution and the zinc salt precursor solution to react to obtain a mixed solution, the reaction time of the alkali precursor solution and the zinc salt precursor solution is 0.25h to 2h, and the reaction temperature is 0 ℃ to 60 ℃; and/or, in the step of mixing and reacting the silane amine precursor solution and the mixed solution to obtain the modified zinc oxide solution, the reaction time of the silane amine precursor solution and the mixed solution is 0.25-2 h, and the reaction temperature is 0-60 ℃.
10. The method for preparing a modified zinc oxide solution according to claim 5, wherein the volume ratio of the silane amine precursor solution, the zinc salt precursor solution, and the base precursor solution is 1: (0.5-1.2): (0.5-1.2).
11. The method of preparing a modified zinc oxide solution according to claim 5, wherein the molar ratio of zinc element in the zinc salt precursor solution to hydroxyl in the alkali precursor solution is 1: (1-2).
12. An optoelectronic device comprising a cathode, an electron transport layer, a light emitting layer and an anode stacked in this order, wherein the electron transport layer comprises the modified zinc oxide of any one of claims 1 to 4, or the electron transport layer is made of the modified zinc oxide solution produced by the method for producing a modified zinc oxide solution of any one of claims 5 to 11.
13. The optoelectronic device of claim 12, further comprising a hole injection layer and a hole transport layer, wherein the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode are stacked in that order.
14. The optoelectronic device of claim 13, wherein the materials of the anode and the cathode are selected from at least one of a metal, a carbon material, or a metal oxide independently of each other, wherein the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg; the carbon material is at least one of graphite, carbon nano tube, graphene or carbon fiber; the metal oxide is at least one selected from indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide;
and/or the material of the light-emitting layer comprises an organic light-emitting material or quantum dots;
wherein the organic luminescent material is selected from at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
the quantum dots are selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a core-shell structure quantum dot, the component of the quantum dot is selected from at least one of II-VI compound, III-V compound, IV-VI compound or I-III-VI compound, wherein the II-VI compound is selected from CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe. CdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe or HgZnSTe, said III-V compound being selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, said IV-VI compound being selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe or SnPbSTe, said I-III-VI compound being selected from CuInS 2 、CuInSe 2 Or AgInS 2 At least one of (a) and (b);
and/or the material of the electron transport layer comprises nano metal oxide;
the nano metal oxide is selected from nano ZnO and nano TiO 2 Nano SnO 2 Nano Ta 2 O 3 Nano ZrO 2 At least one of nano TiLiO, nano ZnGaO, nano ZnAlO, nano ZnMgO, nano ZnSnO, nano ZnLiO, nano InSnO, nano AlZnO, nano ZnOCl or nano ZnOF;
and/or the material of the hole transport layer is selected from at least one of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl-substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine;
and/or the material of the hole injection layer is selected from poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6At least one of 7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide or transition metal chalcogenide, wherein the transition metal oxide is selected from NiO x 、MoO x 、WO x 、CrO x Or CuO, the transition metal chalcogenide is selected from MoS x 、MoSe x 、WS x 、WSe x Or at least one of CuS.
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