CN113120949A - Zinc oxide nano material, preparation method thereof, thin film and photoelectric device - Google Patents
Zinc oxide nano material, preparation method thereof, thin film and photoelectric device Download PDFInfo
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- CN113120949A CN113120949A CN201911407308.7A CN201911407308A CN113120949A CN 113120949 A CN113120949 A CN 113120949A CN 201911407308 A CN201911407308 A CN 201911407308A CN 113120949 A CN113120949 A CN 113120949A
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- zinc
- lanthanide
- zinc oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 116
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010409 thin film Substances 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 80
- -1 alkaline earth metal salt Chemical class 0.000 claims abstract description 75
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 55
- 150000003751 zinc Chemical class 0.000 claims abstract description 53
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 46
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000012266 salt solution Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 4
- 229940075613 gadolinium oxide Drugs 0.000 claims description 4
- IZZTUGMCLUGNPM-UHFFFAOYSA-K gadolinium(3+);triiodide Chemical compound I[Gd](I)I IZZTUGMCLUGNPM-UHFFFAOYSA-K 0.000 claims description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 4
- 229910016859 Lanthanum iodide Inorganic materials 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 claims description 3
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- DPYXWFUVSMSNNV-UHFFFAOYSA-L europium(2+);diiodide Chemical compound [I-].[I-].[Eu+2] DPYXWFUVSMSNNV-UHFFFAOYSA-L 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 3
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 3
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- HPNURIVGONRLQI-UHFFFAOYSA-K trifluoroeuropium Chemical compound F[Eu](F)F HPNURIVGONRLQI-UHFFFAOYSA-K 0.000 claims description 3
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 38
- 150000002602 lanthanoids Chemical class 0.000 abstract description 17
- 229910052736 halogen Inorganic materials 0.000 abstract description 15
- 150000002367 halogens Chemical class 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 59
- 239000002096 quantum dot Substances 0.000 description 44
- 150000002500 ions Chemical class 0.000 description 14
- 230000005525 hole transport Effects 0.000 description 13
- 238000004528 spin coating Methods 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000005476 size effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Polymers C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 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 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
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- URRRJXFWOUCKSG-UHFFFAOYSA-M ethanol;tetramethylazanium;hydroxide Chemical compound [OH-].CCO.C[N+](C)(C)C URRRJXFWOUCKSG-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 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 description 1
- 239000002110 nanocone Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Abstract
The invention discloses a zinc oxide nano material, a preparation method thereof, a film and a photoelectric device, wherein the method comprises the following steps: mixing zinc salt, alkaline earth metal salt and alkali liquor for reaction to obtain a first solution, and adding lanthanide oxide and lanthanide halide into the first solution to prepare the zinc oxide nano material; or adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution, mixing and reacting to obtain a second solution, and adding alkaline earth metal salt into the second solution to prepare the zinc oxide nano material. According to the invention, through co-doping of lanthanide and halogen elements, the lattice distortion of the zinc oxide nanoparticles is reduced, and the integrity of the zinc oxide nanoparticles and the crystallinity of the thin film are improved, so that the electron mobility of the zinc oxide nanoparticles is enhanced.
Description
Technical Field
The invention relates to the field of photoelectric devices, in particular to a zinc oxide nano material, a preparation method thereof, a film and a photoelectric device.
Background
The zinc oxide nano-particles have a wurtzite crystal structure, have a wider band gap (3.37eV) and a stronger exciton confinement energy (60meV) at room temperature, and have a strong fluorescence emission peak in a visible green region (about 520 nm). Due to the excellent properties of zinc oxide nanoparticles, intense interest has been drawn to researchers in the new display field. At present, zinc oxide nanoparticle materials are widely used in the fields of Light Emitting Diodes (LEDs), ultraviolet photodetectors, photovoltaic devices, transparent electrodes, sensors, photocatalysis, and the like. The zinc oxide nano-particle material is popular in the novel display field, and has two main reasons, namely, the raw material for preparing the zinc oxide is low in cost, non-toxic and environment-friendly; and the film material has high light transmittance, high electron mobility, high carrier concentration and the like.
In different display devices, the required work function of the zinc oxide is not as same as the required work function of the zinc oxide, and the work function of the zinc oxide is directly related to the particle size of zinc oxide particles, so that the work function of the zinc oxide is better matched with different device materials, and the regulation and control of the particle size of the zinc oxide are indispensable. In addition, the zinc oxide material has several defects, namely oxygen vacancy, zinc vacancy, interstitial oxygen, interstitial zinc, oxygen site zinc and zinc site oxygen. Under the influence of the defects, defect energy levels are formed between the valence band and the conduction band of the zinc oxide nanoparticle material, and electrons can conduct among the defect energy levels, between the defect energy levels and the valence band and between the defect energy levels and the conduction band, so that the electron transport rate of the zinc oxide nanoparticle material is reduced.
Therefore, the prior art is still to be improved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a zinc oxide nano material, a preparation method thereof, a thin film and a photoelectric device, and aims to solve the problem that the existing zinc oxide nano particles have lattice distortion to cause poor electron transport capability.
The technical scheme of the invention is as follows:
a preparation method of a zinc oxide nano material comprises the following steps:
mixing zinc salt, alkaline earth metal salt and alkali liquor for reaction to obtain a first solution, adding lanthanide oxide and lanthanide halide into the first solution to prepare the zinc oxide nano material, wherein the mass ratio of the zinc salt to the alkaline earth metal salt to the lanthanide oxide to the lanthanide halide is (1-7): (0.05-0.1): (0.1-0.3): (0.1-0.2);
or adding alkali liquor, lanthanide oxide and lanthanide halide into a zinc salt solution, mixing and reacting to obtain a second solution, adding alkaline earth metal salt into the second solution to prepare the zinc oxide nano material, wherein the mass ratio of the zinc salt to the alkaline earth metal salt to the lanthanide oxide to the lanthanide halide is (1-7): (0.05-0.1): (0.1-0.3): (0.1-0.2).
The preparation method of the zinc oxide nano material comprises the step of preparing a zinc oxide nano material, wherein the zinc salt is one or more of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate.
The preparation method of the zinc oxide nano material comprises the step of preparing the zinc oxide nano material by using the alkaline earth metal salt, wherein the alkaline earth metal salt is one or more of magnesium acetate, sodium chloride, potassium nitrate, calcium sulfate and lithium chloride.
The preparation method of the zinc oxide nano material comprises the following steps of mixing and reacting zinc salt, alkaline earth metal salt and alkali liquor to obtain a first solution:
adding a solution of alkaline earth metal salt and alkali liquor into the solution of zinc salt under the condition of stirring, and mixing and reacting to obtain a first solution;
and/or adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution for mixing reaction to obtain a second solution, wherein the step of adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution for mixing reaction comprises the following steps:
adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution under the condition of stirring, mixing and reacting to obtain a second solution.
In the step of mixing and reacting zinc salt, alkaline earth metal salt and alkali liquor to obtain a first solution, the mass ratio of the zinc salt to an alkaline compound in the alkali liquor is (1-7) to (0.1-0.4), and the adding rate of the alkaline earth metal salt solution and the alkali liquor is 0.01-0.05 ml/min;
or adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution under the condition of stirring, mixing and reacting to obtain a second solution, wherein the mass ratio of the zinc salt in the zinc salt solution to the alkaline compound in the alkali liquor is (1-7) to (0.1-0.4), and the adding speed of the alkali liquor is 0.01-0.05 ml/min.
The preparation method of the zinc oxide nano material comprises the following steps of: adding lanthanide oxide and lanthanide halide into the first solution, and heating to obtain the zinc oxide nanomaterial at the temperature of 200-300 ℃ and/or for 1-4 h;
or the step of adding alkaline earth metal salt into the second solution to prepare the zinc oxide nano material comprises the following steps: and adding alkaline earth metal salt into the second solution and carrying out heating treatment at the temperature of 200-300 ℃ for 1-4h to prepare the zinc oxide nano material.
The preparation method of the zinc oxide nano material comprises the following steps of (1) preparing a lanthanide oxide, wherein the lanthanide oxide is one or more of lanthanum oxide, cerium oxide, europium oxide and gadolinium oxide; and/or the lanthanide halide is one or more of lanthanum chloride, lanthanum fluoride, lanthanum iodide, cerium chloride, cerium fluoride, cerium iodide, europium chloride, europium fluoride, europium iodide, gadolinium chloride, gadolinium fluoride and gadolinium iodide.
The invention discloses a multi-element co-doped zinc oxide nano material, which is prepared by the preparation method of the zinc oxide nano material.
The film is made of the multielement co-doped zinc oxide nano material.
An optoelectronic device comprising an electron transport layer, said electron transport layer comprising a thin film according to the present invention.
Has the advantages that: according to the zinc oxide nano material provided by the invention, through co-doping of lanthanide and halogen elements, the lattice distortion of zinc oxide nano particles is reduced, the integrity of the zinc oxide nano particles and the crystallinity of a thin film are improved, and thus the electron mobility of the zinc oxide nano particles is enhanced.
Drawings
Fig. 1 is a flow chart of a method for preparing a zinc oxide nanomaterial in an embodiment of the present invention.
Fig. 2 is a flow chart of a method for preparing a zinc oxide nanomaterial in another embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a quantum dot light emitting diode with a front-mounted structure according to an embodiment of the present invention.
Fig. 4 is a schematic structural diagram of a quantum dot light emitting diode with a flip-chip structure according to an embodiment of the present invention.
Detailed Description
The invention provides a zinc oxide nano material, a preparation method thereof, a film and a photoelectric device, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing a zinc oxide nanomaterial, as shown in the figure, the method includes the steps of:
s10, adding a solution of alkaline earth metal salt and alkali liquor into the solution of zinc salt, and mixing and reacting to obtain the first solution;
s20, adding lanthanide oxide and lanthanide halide into the first solution to prepare the zinc oxide nano material, wherein the mass ratio of the zinc salt to the alkaline earth metal salt to the lanthanide oxide to the lanthanide halide is (1-7): (0.05-0.1): (0.1-0.3): (0.1-0.2).
In the embodiment, the energy band work function of the zinc oxide nanoparticles is adjusted by doping alkaline earth metal elements, electrons can be injected into the luminescent layer more easily, the lattice distortion of the zinc oxide nanoparticles is improved by co-doping lanthanide and halogen elements, and when two or more ions substitute oxygen atoms or zinc atoms to generate a reverse size effect, the multi-element co-doping can compensate the ionic radius difference between original ions and substituted ions, so that the crystallinity and the electron mobility of the zinc oxide nanoparticles are improved.
In this embodiment, the mass ratio of the zinc salt to the alkaline earth metal salt is (1-7): (0.05-0.1), the function of doping the alkaline earth metal is to adjust the size of the zinc oxide nano-particles, thereby changing the energy band function of the zinc oxide nano-particles. The present example selects co-doping of lanthanide and halogen to improve lattice distortion of zinc oxide nanoparticles due to: 1. the absorption spectrum of lanthanide and the low oscillation intensity of lanthanide have little influence on the optical transparency of zinc oxide nano-particles after film formation; 2. the ion radius of the lanthanide is larger than that of the zinc ions, and the doping of the lanthanide in the zinc oxide nano-particles is realized by replacing the positions of the zinc ions instead of occupying the interstitial positions of zinc oxide lattices, so that the distortion of the zinc oxide lattices can be avoided; the ionic radius of the halogen element is smaller than that of the oxygen anion, the halogen element ion has an electronegative structure which is close to or stronger than that of the oxygen anion, and the halogen element ion can be well filled into the oxygen vacancy of the zinc oxide nano-particle and replaces the oxygen anion; the doping of the lanthanide can cause the lattice spacing expansion of the zinc oxide nanoparticles, and the doping of the halogen element can reduce the interlayer spacing of the zinc oxide nanoparticles, so that the co-doping of the lanthanide and the halogen element not only improves the problem of lattice distortion of the zinc oxide nanoparticles, but also generates an inverse size effect, can not completely change the original particle size of the zinc oxide nanoparticles, and further improves the crystallinity and the electron mobility of the zinc oxide nanoparticles.
In this embodiment, the amounts of the lanthanoid element and the halogen element doped into the alkaline earth metal-doped zinc oxide nanoparticles can be adjusted by simultaneously adding the lanthanoid oxide and the lanthanoid halide. In some specific embodiments, the mass ratio of lanthanide oxide to lanthanide halide is (0.1-0.3): (0.1-0.2).
In some embodiments, the zinc salt solution comprises an organic solvent and a zinc salt dispersed in the organic solvent. In this embodiment, the zinc salt is one or more of zinc acetate, zinc chloride, zinc nitrate, and zinc sulfate, but is not limited thereto; the organic solvent is one or more of dimethyl sulfoxide, N, N-dimethylformamide and N-hexane, but is not limited thereto.
In some embodiments, the alkaline earth metal salt solution comprises an organic solvent and an alkaline earth metal salt dispersed in the organic solvent. In this embodiment, the alkaline earth metal salt is one or more of magnesium acetate, sodium chloride, potassium nitrate, calcium sulfate, and lithium chloride, but is not limited thereto; the organic solvent is one or more of dimethyl sulfoxide, N, N-dimethylformamide and N-hexane, but is not limited thereto.
In some embodiments, the alkali solution is one or more of a tetramethylammonium hydroxide alcohol solution, a sodium hydroxide solution, or a potassium hydroxide solution, but is not limited thereto.
In some embodiments, the alkaline earth metal salt solution and the alkaline solution are added to the zinc salt solution with stirring using a syringe pump at an addition rate of 0.01 to 0.05ml/min to produce a clear and transparent alkaline earth metal doped zinc oxide nanoparticle solution. In this embodiment, the mass ratio of the zinc salt in the zinc salt solution to the alkaline earth metal salt in the alkaline earth metal salt solution is 1-7: 0.05-0.1; the mass ratio of the zinc salt in the zinc salt solution to the alkaline compound in the alkali liquor is 1-7: 0.1-0.4.
In some embodiments, lanthanide oxide and lanthanide halide are added into the alkaline earth metal doped zinc oxide nanoparticle solution and are heated and treated for 1-4h at the temperature of 200-300 ℃ to dope lanthanide and halogen elements into the alkaline earth metal doped zinc oxide nanoparticles, so as to prepare the multi-element co-doped zinc oxide nanoparticle. In the embodiment, the doping proportion of lanthanide and halogen elements can be adjusted by controlling the addition of lanthanide oxide and lanthanide halide, so as to obtain the multi-element co-doped zinc oxide nano material with different doping proportions.
In some embodiments, the lanthanide oxide is one or more of lanthanum oxide, cerium oxide, europium oxide, and gadolinium oxide, but is not limited thereto.
In some embodiments, the lanthanide halide is one or more of lanthanum chloride, lanthanum fluoride, lanthanum iodide, cerium chloride, cerium fluoride, cerium iodide, europium chloride, europium fluoride, europium iodide, gadolinium chloride, gadolinium fluoride, and gadolinium iodide, but is not limited thereto.
In some embodiments, there is also provided a method for preparing a zinc oxide nanomaterial, wherein, as shown in fig. 2, the method comprises the steps of:
s100, adding alkali liquor, lanthanide oxide and lanthanide halide into a zinc salt solution, and mixing and reacting to obtain a second solution;
s200, adding alkali liquor, lanthanide oxide and lanthanide halide into a zinc salt solution, mixing and reacting to obtain a second solution, adding alkaline earth metal salt into the second solution to prepare the zinc oxide nano material, wherein the mass ratio of zinc salt to alkaline earth metal salt to lanthanide oxide to lanthanide halide is (1-7): (0.05-0.1): (0.1-0.3): (0.1-0.2).
In this embodiment, doping of lanthanide and halogen elements on zinc oxide particles is first achieved, and then doping of alkaline earth metal elements is achieved, so as to prepare the multi-element co-doped zinc oxide nanomaterial. Similarly, the lattice distortion of the zinc oxide nanoparticles is improved by the co-doping of the lanthanide and the halogen, and when two or more ions substitute oxygen atoms or zinc atoms to generate an inverse size effect, the multi-element co-doping can compensate the ionic radius difference between the original ions and the substituted ions, so that the crystallinity and the electron mobility of the zinc oxide nanoparticles are improved; through the doping of the alkaline earth metal element, the energy band work function of the zinc oxide nano-particles can be adjusted, and electrons can be injected into the luminescent layer more easily.
In some examples, in the step of adding alkali solution, lanthanide oxide and lanthanide halide to the zinc salt solution and performing the heat treatment, the mass ratio of the zinc salt in the zinc salt solution to the basic compound in the alkali solution is (1-7): (0.1-0.4), and the addition rate of the alkali solution is 0.01-0.05 ml/min.
The selection of the types of the zinc salt, the alkaline earth metal salt, the lanthanide oxide and the lanthanide halide in the preparation method for preparing the zinc oxide nanomaterial in fig. 2 can refer to the selection of the types of the zinc salt, the alkaline earth metal salt, the lanthanide oxide and the lanthanide halide in the preparation method for preparing the zinc oxide nanomaterial in fig. 1 in this application, and will not be described in detail herein.
In some examples, in the step of adding alkali solution, lanthanide oxide and lanthanide halide to the zinc salt solution and performing the heat treatment, the heat treatment temperature can be 200-300 ℃, or the heat treatment time can be 1-4 h. In other examples, in the step of adding alkali solution, lanthanide oxide and lanthanide halide to the zinc salt solution and performing the heat treatment, the heat treatment temperature may be 200-300 ℃, and the heat treatment time may be 1-4 h.
The preparation method of the zinc oxide nanomaterial is described in detail by the following examples:
example 1
1) 0.1g of zinc acetate is dissolved in 10g of dimethyl sulfoxide, 0.005g of magnesium acetate is dissolved in the same mass of dimethyl sulfoxide, and the magnesium acetate solution and 0.01g of tetramethylammonium hydroxide ethanol solution are respectively added into the zinc acetate solution by a syringe pump at the rate of 0.01mg/ml under the condition of vigorous stirring by a magnetic stirrer to obtain Zn0.95Mg0.05O solution;
2) to the Zn prepared in the step 1)0.95Mg0.05Adding 0.01g of lanthanum oxide and 0.02g of lanthanum fluoride into the O solution, and reacting for 1 hour at 200 ℃;
3) washing and centrifugally separating the solution obtained in the step 2) to obtain Zn0.71Mg0.05La0.21O0.8F0.2Ternary doped zinc oxide nanomaterials.
Example 2
1) 0.7g of zinc chloride was dissolved in 20g N, N-dimethylformamide and 0.01g of sodium chloride was dissolved in the same mass of N, N-dimethylformamide, and the sodium chloride solution and 0.04g of ethanol solution of tetramethylammonium hydroxide were added to the zinc chloride solution at a rate of 0.05mg/ml, respectively, with vigorous stirring by a magnetic stirrer using a syringe pump. Obtaining Zn0.98Na0.02O solution;
2) to the Zn prepared in the step 1)0.98Na0.020.03g of an oxidizing agent was added to the O solutionCerium and 0.01g of cerium chloride was added. The reaction time was 4 hours at 300 ℃.
3) Washing and centrifugally separating the solution obtained in the step 2) to obtain Zn0.92Na0.02Ce0.06O0.98Cl0.02Ternary doped zinc oxide nanomaterials.
Example 3
1) 0.5g of zinc nitrate was dissolved in 15g of dimethyl sulfoxide, and 0.008g of potassium nitrate was dissolved in the same mass of dimethyl sulfoxide, and a potassium nitrate solution and 0.02g of an ethanol solution of tetramethylammonium hydroxide were added to the zinc nitrate solution at a rate of 0.03mg/ml with vigorous stirring by a magnetic stirrer using a syringe pump, respectively. Obtaining Zn0.97K0.03O solution;
2) to the Zn prepared in the step 1)0.97K0.030.02g of gadolinium oxide and 0.02g of gadolinium iodide were added to the O solution. Reacting for 2 hours at 260 ℃;
3) washing and centrifugally separating the solution obtained in the step 2) to obtain Zn0.9K0.02Ga0.08O0.92I0.08Ternary doped zinc oxide nanomaterials.
In some embodiments, the invention also provides a multi-element co-doped zinc oxide nano material prepared by the preparation method of the zinc oxide nano material.
In some embodiments, a thin film is also provided, and the material of the thin film is the multielement co-doped zinc oxide nanomaterial provided by the invention.
In some embodiments, there is also provided an optoelectronic device comprising an electron transport layer, said electron transport comprising a thin film according to the present invention. By way of example, the optoelectronic device may be a quantum dot light emitting diode or an organic light emitting diode.
The following describes the quantum dot light emitting diode including the electron transport layer and the method for manufacturing the same in detail:
in some embodiments, the quantum dot light emitting diode comprises an anode, a quantum dot light emitting layer, an electron transport layer and a cathode, which are stacked, wherein the electron transport layer is the thin film of the present invention.
In some specific embodiments, the quantum dot light emitting diode includes an anode, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode, which are stacked, wherein the electron transport layer is the thin film of the present invention.
It should be noted that the invention is not limited to the quantum dot light emitting diode with the above structure, and may further include an interface functional layer or an interface modification layer, including but not limited to one or more of an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer. The quantum dot light emitting diode can be partially packaged, fully packaged or not packaged.
The quantum dot light emitting diode can be divided into a quantum dot light emitting diode with a forward mounting structure and a quantum dot light emitting diode with an inverted mounting structure according to different light emitting types of the quantum dot light emitting diode.
As one embodiment, when the quantum dot light emitting diode is a forward-mounted structure, as shown in fig. 3, the QLED device includes an anode 2 (the anode 2 is stacked on a substrate 1), a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, and a cathode 6, where the electron transport layer 5 is a thin film according to the present invention.
In another embodiment, when the quantum dot light emitting diode is a flip-chip structure, as shown in fig. 4, the QLED device includes a cathode 6 (the cathode 6 is stacked on a substrate 1), an electron transport layer 5, a quantum dot light emitting layer 4, a hole transport layer 3, and an anode 2, where the electron transport layer 5 is a thin film according to the present invention.
In some embodiments, the material of the anode is selected from doped metal oxides; wherein the doped metal oxide includes, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO).
In some embodiments, the material of the hole transport layer is selected from organic materials having good hole transport ability, such as but not limited to Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK), Poly (N, N 'bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD), Poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4', 4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1, one or more of 1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, C60, F8, copper oxide, nickel oxide, tungsten trioxide, and molybdenum trioxide.
In some embodiments, the material of the quantum dot light emitting layer is selected from one or more of red quantum dots, green quantum dots, blue quantum dots, and may also be selected from yellow quantum dots. Specifically, the material of the quantum dot light emitting layer is selected from one or more of CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe and various core-shell structure quantum dots or alloy structure quantum dots. The quantum dots of the present invention can be selected from cadmium-containing or cadmium-free quantum dots. The quantum dot light emitting layer of the material has the characteristics of wide and continuous excitation spectrum distribution, high emission spectrum stability and the like.
In some embodiments, the material of the cathode is selected from one or more of a conductive carbon material, a conductive metal oxide material, and a metallic material; wherein the conductive carbon material includes, but is not limited to, one or more of doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, and porous carbon; the conductive metal oxide material includes, but is not limited to, one or more of ITO, FTO, ATO, and AZO; metallic materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein, the metal material has a form including but not limited to one or more of a compact film, a nanowire, a nanosphere, a nanorod, a nanocone and a hollow nanosphere.
The invention also provides a preparation method of the quantum dot light-emitting diode with the forward mounting structure, which comprises the following steps:
providing a substrate containing an anode, and preparing a hole transport layer on the anode;
preparing a quantum dot light emitting layer on the hole transport layer;
preparing an electron transport layer on the quantum dot light-emitting layer, wherein the electron transport layer is the film;
and preparing a cathode on the electron transport layer to obtain the quantum dot light-emitting diode.
As one embodiment, taking ITO conductive glass as an example of a substrate, in order to obtain a high-quality thin film, the ITO conductive glass needs to undergo a pretreatment process, and the basic specific processing steps include: etching the ITO conductive glass into narrow bands, then respectively ultrasonically cleaning the narrow bands in deionized water, acetone, absolute ethyl alcohol and deionized water in sequence to remove impurities existing on the surfaces, drying the narrow bands, and cleaning the narrow bands by using an ultraviolet cleaning machine to obtain the ITO anode.
As one embodiment, the prepared solution of the hole transport material is coated on the ITO by spinning to form a film; controlling the film thickness by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then carrying out thermal annealing treatment at a proper temperature to obtain a hole transport layer; spin-coating the prepared solution of the hole transport material on ITO to form a film; and spin-coating a prepared quantum dot solution with a certain concentration on the hole transport layer to form a film, controlling the thickness of the quantum dot light-emitting layer to be about 20-60 nm by adjusting the concentration, the spin-coating speed and the spin-coating time of the solution, and drying at a proper temperature.
As one embodiment, the step of preparing the electron transport layer on the quantum dot light emitting layer specifically includes: spin coating the prepared multi-element co-doped zinc oxide nano material solution with a certain concentration on the quantum dot light emitting layer to form a film, controlling the thickness of the electron transmission layer to be about 20-60 nm by adjusting the concentration, the spin coating speed and the spin coating time of the multi-element co-doped zinc oxide nano material solution, and then annealing to form the film.
In some embodiments, the spin speed is 3000 and 5000 rpm.
As one embodiment, the step of preparing the cathode on the electron transport layer specifically includes: the substrate deposited with the functional layers is placed in an evaporation bin, a layer of 15-30nm metal silver or aluminum and the like is thermally evaporated through a mask plate to be used as a cathode, or a nano Ag wire or a Cu wire and the like are used, and the materials have low resistance so that carriers can be smoothly injected.
The invention also provides a preparation method of the quantum dot light-emitting diode with the flip structure, which comprises the following steps:
providing a substrate containing a cathode, and preparing an electron transport layer on the cathode, wherein the electron transport layer is the film disclosed by the invention;
preparing a quantum dot light-emitting layer on the electron transport layer;
preparing a hole transport layer on the quantum dot light emitting layer;
and preparing an anode on the hole transport layer to obtain the quantum dot light-emitting diode.
As one embodiment, the step of preparing the electron transport layer on the cathode specifically includes: spin coating the prepared multi-element co-doped zinc oxide nano material solution with a certain concentration on the quantum dot light emitting layer to form a film, controlling the thickness of the electron transmission layer to be about 20-60 nm by adjusting the concentration, the spin coating speed and the spin coating time of the multi-element co-doped zinc oxide nano material solution, and then annealing to form the film.
The invention also comprises the following steps: and carrying out packaging treatment on the obtained quantum dot light-emitting diode, wherein the packaging treatment can adopt common machine packaging or manual packaging. Preferably, in the environment of the packaging treatment, the oxygen content and the water content are both lower than 0.1ppm so as to ensure the stability of the quantum dot light-emitting diode.
The preparation method of each layer can be a chemical method or a physical method, wherein the chemical method comprises one or more of but not limited to a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method and a coprecipitation method; physical methods include, but are not limited to, physical coating methods or solution methods, wherein 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 coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
In summary, the invention firstly adjusts the energy band work function of the zinc oxide nanoparticles by doping alkaline earth metal elements, so that electrons can be injected into the luminescent layer more easily, then improves the lattice distortion of the zinc oxide nanoparticles by co-doping lanthanide and halogen elements, and when two or more ions substitute oxygen atoms or zinc atoms to generate an inverse size effect, multi-element co-doping can compensate the ionic radius difference between original ions and substituted ions, thereby improving the crystallinity and electron mobility of the zinc oxide nanoparticles.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a zinc oxide nano material is characterized by comprising the following steps:
mixing zinc salt, alkaline earth metal salt and alkali liquor for reaction to obtain a first solution, adding lanthanide oxide and lanthanide halide into the first solution to prepare the zinc oxide nano material, wherein the mass ratio of the zinc salt to the alkaline earth metal salt to the lanthanide oxide to the lanthanide halide is (1-7): (0.05-0.1): (0.1-0.3): (0.1-0.2);
or adding alkali liquor, lanthanide oxide and lanthanide halide into a zinc salt solution, mixing and reacting to obtain a second solution, adding alkaline earth metal salt into the second solution to prepare the zinc oxide nano material, wherein the mass ratio of the zinc salt to the alkaline earth metal salt to the lanthanide oxide to the lanthanide halide is (1-7): (0.05-0.1): (0.1-0.3): (0.1-0.2).
2. The method for preparing the zinc oxide nanomaterial according to claim 1, wherein the zinc salt is one or more of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate.
3. The method for preparing zinc oxide nano-material according to claim 1, wherein the alkaline earth metal salt is one or more of magnesium acetate, sodium chloride, potassium nitrate, calcium sulfate and lithium chloride.
4. The method for preparing the zinc oxide nanomaterial according to claim 1, wherein the step of mixing and reacting the zinc salt, the alkaline earth metal salt and the alkaline solution to obtain the first solution comprises:
adding a solution of alkaline earth metal salt and alkali liquor into the solution of zinc salt under the condition of stirring, and mixing and reacting to obtain a first solution;
and/or adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution for mixing reaction to obtain a second solution, wherein the step of adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution for mixing reaction comprises the following steps:
adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution under the condition of stirring, mixing and reacting to obtain a second solution.
5. The method for preparing zinc oxide nanomaterial according to claim 4, wherein in the step of mixing zinc salt, alkaline earth metal salt and alkaline solution for reaction to obtain the first solution, the mass ratio of the zinc salt to the alkaline compound in the alkaline solution is (1-7) to (0.1-0.4), and the addition rate of the alkaline earth metal salt solution and the alkaline solution is 0.01-0.05 ml/min;
or adding alkali liquor, lanthanide oxide and lanthanide halide into the zinc salt solution under the condition of stirring, mixing and reacting to obtain a second solution, wherein the mass ratio of the zinc salt in the zinc salt solution to the alkaline compound in the alkali liquor is (1-7) to (0.1-0.4), and the adding speed of the alkali liquor is 0.01-0.05 ml/min.
6. The method for preparing the zinc oxide nanomaterial according to claim 1, wherein the step of adding a lanthanide oxide and a lanthanide halide to the first solution to obtain the zinc oxide nanomaterial comprises: adding lanthanide oxide and lanthanide halide into the first solution, and heating to obtain the zinc oxide nanomaterial at the temperature of 200-300 ℃ and/or for 1-4 h;
or the step of adding alkaline earth metal salt into the second solution to prepare the zinc oxide nano material comprises the following steps: and adding alkaline earth metal salt into the second solution and carrying out heating treatment at the temperature of 200-300 ℃ for 1-4h to prepare the zinc oxide nano material.
7. The method for preparing the zinc oxide nanomaterial according to claim 1, wherein the lanthanide oxide is one or more of lanthanum oxide, cerium oxide, europium oxide and gadolinium oxide; and/or the lanthanide halide is one or more of lanthanum chloride, lanthanum fluoride, lanthanum iodide, cerium chloride, cerium fluoride, cerium iodide, europium chloride, europium fluoride, europium iodide, gadolinium chloride, gadolinium fluoride and gadolinium iodide.
8. A zinc oxide nano-material, which is characterized by being prepared by the preparation method of the zinc oxide nano-material in any one of claims 1 to 7.
9. A thin film, characterized in that the material of the thin film is the zinc oxide nanomaterial according to claim 8.
10. An optoelectronic device comprising an electron transport layer, said electron transport layer comprising the film of claim 9.
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