CN118255382A - Preparation method of zinc magnesium oxide, light-emitting device and electronic equipment containing zinc magnesium oxide - Google Patents
Preparation method of zinc magnesium oxide, light-emitting device and electronic equipment containing zinc magnesium oxide Download PDFInfo
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- CN118255382A CN118255382A CN202211687323.3A CN202211687323A CN118255382A CN 118255382 A CN118255382 A CN 118255382A CN 202211687323 A CN202211687323 A CN 202211687323A CN 118255382 A CN118255382 A CN 118255382A
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- Prior art keywords
- solution
- magnesium oxide
- poly
- zinc
- oxide
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- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000002346 layers by function Substances 0.000 claims abstract description 57
- 239000011777 magnesium Substances 0.000 claims abstract description 52
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 44
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 242
- 239000010410 layer Substances 0.000 claims description 136
- 238000002347 injection Methods 0.000 claims description 113
- 239000007924 injection Substances 0.000 claims description 113
- 239000000463 material Substances 0.000 claims description 94
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 78
- 229910052757 nitrogen Inorganic materials 0.000 claims description 61
- -1 alcohol compound Chemical class 0.000 claims description 59
- 239000002096 quantum dot Substances 0.000 claims description 56
- 239000011787 zinc oxide Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- 239000002585 base Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 230000005525 hole transport Effects 0.000 claims description 23
- 239000007983 Tris buffer Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 230000007423 decrease Effects 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- 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 6
- HONWGFNQCPRRFM-UHFFFAOYSA-N 2-n-(3-methylphenyl)-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=CC=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HONWGFNQCPRRFM-UHFFFAOYSA-N 0.000 claims description 6
- 229910002601 GaN Inorganic materials 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 230000003111 delayed effect Effects 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
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- KJNZQKYSNAQLEO-UHFFFAOYSA-N 2-(4-methylphenyl)pyridine Chemical compound C1=CC(C)=CC=C1C1=CC=CC=N1 KJNZQKYSNAQLEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- VMBJUBUWNIDCSI-UHFFFAOYSA-N 2-[1-anilino-4-(4-anilinophenyl)cyclohexa-2,4-dien-1-yl]-N,N-diphenylaniline Chemical compound C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=C(C=CC=C1)C1(CC=C(C=C1)C1=CC=C(NC2=CC=CC=C2)C=C1)NC1=CC=CC=C1 VMBJUBUWNIDCSI-UHFFFAOYSA-N 0.000 claims description 3
- XSUNFLLNZQIJJG-UHFFFAOYSA-N 2-n-naphthalen-2-yl-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N(C=1C=CC=CC=1)C=1C=C2C=CC=CC2=CC=1)C1=CC=CC=C1 XSUNFLLNZQIJJG-UHFFFAOYSA-N 0.000 claims description 3
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 claims description 3
- FAPCZAUMFXUDMS-UHFFFAOYSA-N 4-bromo-3-(dibromomethyl)-2-hydroxy-2h-furan-5-one Chemical compound OC1OC(=O)C(Br)=C1C(Br)Br FAPCZAUMFXUDMS-UHFFFAOYSA-N 0.000 claims description 3
- ZNSXNNUEMWLJEV-UHFFFAOYSA-N 4-butan-2-yl-n,n-diphenylaniline Chemical compound C1=CC(C(C)CC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ZNSXNNUEMWLJEV-UHFFFAOYSA-N 0.000 claims description 3
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Chemical compound C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 claims description 3
- LZSJBLXYNYSKPJ-UHFFFAOYSA-N 9-octyl-9h-fluorene Chemical compound C1=CC=C2C(CCCCCCCC)C3=CC=CC=C3C2=C1 LZSJBLXYNYSKPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017115 AlSb Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 3
- 229910004611 CdZnTe Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910005542 GaSb Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- 229910004262 HgTe Inorganic materials 0.000 claims description 3
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 3
- 241000764773 Inna Species 0.000 claims description 3
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 claims description 3
- 229910002665 PbTe Inorganic materials 0.000 claims description 3
- 229910005642 SnTe Inorganic materials 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
- 229910007709 ZnTe Inorganic materials 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 229910001417 caesium ion Inorganic materials 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
- 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 claims description 3
- 230000005281 excited state Effects 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
- 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
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 3
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 3
- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003220 pyrenes Chemical class 0.000 claims description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 3
- 235000021286 stilbenes Nutrition 0.000 claims description 3
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
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- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910017083 AlN Inorganic materials 0.000 claims 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 14
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- 230000000052 comparative effect Effects 0.000 description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
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- 239000013078 crystal Substances 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
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- 229910007542 Zn OH Inorganic materials 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
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Abstract
The application discloses a preparation method of zinc magnesium oxide, a luminescent device and electronic equipment containing zinc magnesium oxide, wherein the preparation method is characterized in that the proportion of a first alkali and a second alkali in a system is regulated in different reaction stages to control the doping ratio of magnesium element in different reaction stages, so that the distribution condition of magnesium element in the prepared zinc magnesium oxide can be regulated and controlled, and the energy level structure of the zinc magnesium oxide can be conveniently and adaptively regulated according to the change of application scenes, wherein the first alkali is selected from lithium hydroxide, and the second alkali is selected from one or more of sodium hydroxide, potassium hydroxide and quaternary ammonium alkali; the electronic functional layer of the light-emitting device comprises the zinc magnesium oxide prepared by the preparation method of the zinc magnesium oxide, which is beneficial to improving the photoelectric property and prolonging the service life of the light-emitting device; the light-emitting device is applied to the electronic equipment, and is beneficial to improving the display effect and prolonging the service life of the electronic equipment.
Description
Technical Field
The application relates to the technical field of photoelectricity, in particular to a preparation method of zinc magnesium oxide, a light-emitting device containing zinc magnesium oxide and electronic equipment.
Background
The metal oxide refers to a compound formed by combining a metal element and an oxygen element, and is widely applied to high-efficiency catalysts, batteries, light-emitting devices, super capacitors, energy storage devices, magnetic devices and optical devices due to ideal conductivity and chemical stability, for example, zinc oxide is a common electronic functional material, and can be used for preparing an electron transport layer of the light-emitting device.
In order to further improve the performance of the metal oxide, doping the metal oxide is one of the research hotspots in the field of materials. The doped metal oxide is an oxide containing two or more different metal elements, and has the characteristics of a plurality of metal elements contained therein. The zinc oxide magnesium is a common doped metal oxide, is a transparent conductive oxide with excellent optical and electrical properties, can be used as an excellent material of an electron transport layer of a photoelectric device, has rich ZMO production resources, is green and nontoxic, and can be industrially produced. Currently, the solution-gel process is one of the main processes for preparing zinc magnesium oxide, comprising: the preparation method has the following defects that the distribution condition of magnesium element in the prepared zinc oxide magnesium cannot be regulated, so that the regulation of the energy level structure of the zinc oxide magnesium is inconvenient, and the energy level structure of the zinc oxide magnesium is not convenient to adaptively regulate according to the change of application scenes.
Therefore, how to realize the distribution of magnesium element in the prepared zinc oxide magnesium can be regulated and controlled, and has important significance for the application and development of the zinc oxide magnesium.
Disclosure of Invention
The application provides a preparation method of zinc magnesium oxide, a light-emitting device and electronic equipment containing zinc magnesium oxide, and aims to realize adjustable distribution of magnesium element in the prepared zinc magnesium oxide.
The technical scheme of the application is as follows:
In a first aspect, the application provides a method for preparing zinc magnesium oxide, comprising the following steps:
Providing a first solution comprising a zinc salt, a second solution comprising a magnesium salt, a third solution comprising a first base, and a fourth solution comprising a second base; and
Mixing the second solution, the third solution, the fourth solution and the first solution for reaction to obtain the zinc magnesium oxide;
wherein the first base is selected from lithium hydroxide, and the second base is selected from one or more of sodium hydroxide, potassium hydroxide and quaternary ammonium base.
Optionally, the mixing reaction of the second solution, the third solution, the fourth solution and the first solution includes the steps of: injecting the second solution, the third solution, and the fourth solution into the first solution;
Wherein the start time point and the end time point of injection of the second solution, the third solution, and the fourth solution are the same; in the injection process, the second solution is injected in a uniform speed mode, the sum of the total injection mole numbers of the first alkali and the second alkali at any moment is a constant value, and the injection rates of the third solution and the fourth solution are any one of the following conditions:
(a) In the injection process, the injection rate of the third solution is gradually reduced, and the injection rate of the fourth solution is gradually increased;
(b) During the injection, the injection rate of the third solution is gradually increased, and the injection rate of the fourth solution is gradually decreased.
Optionally, for case (a), the initial injection rate of the third solution is 1.5 to 3 times the final injection rate of the third solution; and/or
The final injection rate of the fourth solution is 1.5 to 3 times the initial injection rate of the fourth solution.
Optionally, for case (b), the final injection rate of the third solution is 1.5 to 3 times the initial injection rate of the third solution; and/or
The initial injection rate of the fourth solution is 1.5 times to 3 times the final injection rate of the fourth solution.
Optionally, the total time of the injection is 5min to 60min.
Optionally, in the step of mixing the second solution, the third solution, the fourth solution and the first solution for reaction, a molar ratio of magnesium element in the second solution to zinc element in the first solution is 1: (4-20), and/or the ratio of the number of moles of zinc element in the first solution to the sum of the number of moles of hydroxyl groups of the third solution and the number of moles of hydroxyl groups of the fourth solution is 1: (0.8-2), and/or the concentration of zinc salt in the first solution is 0.1mmol/mL to 0.5mmol/mL, and/or the concentration of magnesium salt in the second solution is 0.1mmol/mL to 0.5mmol/mL, and/or the concentration of the first base in the third solution is 0.1mmol/mL to 1.0mmol/mL, and/or the concentration of the second base in the fourth solution is 0.1mmol/mL to 1.0mmol/mL; and/or
The solvents of the first solution, the second solution, the third solution and the fourth solution are independently selected from one or more of alkane, aromatic hydrocarbon, halogenated alkane, alcohol compound, ether compound, furan compound, pyridine compound and amide compound, preferably, the solvents of the first solution, the second solution, the third solution and the fourth solution are independently selected from one or more of methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, dimethyl sulfoxide and N, N-dimethylformamide; and/or
The mixing reaction is carried out at 0-70 ℃; and/or
The mixing reaction time is 5 min-24 h.
In a second aspect, the present application provides a zinc magnesium oxide obtainable by a process for the preparation of zinc magnesium oxide as described in any one of the first aspects.
Optionally, the average particle size of the zinc magnesium oxide is 2 nm-20 nm; and/or
The band gap of the zinc magnesium oxide is 3.7 eV-4.5 eV; and/or
The mole percentage of the second element gradually increases or gradually decreases in the direction from the inside to the surface of the zinc magnesium oxide.
In a third aspect, the present application provides a light emitting device comprising:
An anode;
a cathode disposed opposite the anode;
a light-emitting layer disposed between the anode and the cathode; and
An electron functional layer disposed between the cathode and the light emitting layer;
Wherein the material of the electronic functional layer contains zinc magnesium oxide prepared by the preparation method of zinc magnesium oxide according to any one of the first aspect, or the material of the electronic functional layer contains zinc magnesium oxide according to any one of the second aspect.
Optionally, the material of the light emitting layer is selected from organic light emitting materials or quantum dots; Wherein the organic luminescent material is selected from one or more of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine iridium (III), 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonding, hybrid local charge transfer excited state materials and exciplex luminescent materials; The quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots and organic-inorganic hybrid perovskite quantum dots; The material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compound, group III-V compound, group IV-VI compound, or group I-III-VI compound independently of each other, wherein the group II-VI compound is selected from one or more 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 and HgZnSTe, the group III-V compound is selected from one or more 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 and InAlPSb, The IV-VI compound is selected from one or more of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe, and the I-III-VI compound is selected from one or more of CuInS, cuInSe and AgInS; The structural general formula of the inorganic perovskite quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, M is selected from one or more of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2 +、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ and Eu 2+, X is a halogen anion; The structural general formula of the organic perovskite quantum dot is CMX 3, and C is formamidino; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, and B is selected from organic amine cations; and/or
The materials of the anode and the cathode are independently selected from one or more of metals, carbon materials and metal oxide materials, wherein the metals are selected from one or more of Al, ag, cu, mo, au, ba, pt, ca and Mg, the carbon materials are selected from one or more of graphite, carbon nano tubes, graphene and carbon fibers, and the metal oxide materials are selected from one or more of indium doped tin oxide, fluorine doped tin oxide, antimony doped tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, zinc magnesium oxide and aluminum doped magnesium oxide; and/or
The light-emitting device further comprises a hole functional layer, wherein the hole functional layer is arranged between the light-emitting layer and the anode, and comprises a hole injection layer and/or a hole transport layer; for the hole functional layer including the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light emitting layer than the hole injection layer;
Wherein the material of the hole injection layer and/or the material of the hole transport layer is selected from poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 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), poly (4, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly (4, 4',4 '-tris (2-naphthylphenylamino) triphenylamine), 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, poly (4, 4' -N, N '-dicarbazolyl-biphenyl), poly (N, N' -diphenyl-N, N '-bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine), poly (4, 4 '-bis (9-carbazole) biphenyl), poly (4, 4',4" -tris (carbazole-9-yl) triphenylamine), and the like, poly (N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine), poly (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro), poly (N, N ' -bis (4- (N, N ' -diphenyl-amino) -phenyl) -N, N ' -diphenyl benzidine), poly (4, 4' -tris (N-carbazolyl) -triphenylamine), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ], poly (4-butylphenyl-diphenylamine), polyaniline, polypyrrole, poly (p-phenylene vinylene, poly (phenylene vinylene), poly (2-methoxy-5- (2-ethylhexyl) -1, 4-phenylene vinylene), poly (2-methoxy-5- (3 ',7' -dioctyl-2, 7-diyl) -1, 4-phenylene vinylene, aromatic amines, 4,4' -bis (P-carbazolyl) -1,1' -biphenyl compounds, one or more of N, N ' -tetraarylbenzidine, poly (N-vinylcarbazole) and derivatives thereof, polymethacrylate esters and derivatives thereof, poly (9, 9-octylfluorene) and derivatives thereof, poly (spirofluorene) and derivatives thereof, poly (N, N ' -bis (naphthalen-1-yl) -N, N ' -diphenylbenzidine), doped or undoped graphene, C60, doped or undoped nickel oxide, doped or undoped molybdenum oxide, doped or undoped tungsten oxide, doped or undoped vanadium oxide, doped or undoped P-gallium nitride, doped or undoped chromium oxide, doped or undoped copper oxide, transition metal sulfide, and transition metal selenide.
In a fourth aspect, the present application provides an electronic device comprising a light emitting device according to any one of the third aspects.
The application provides a preparation method of zinc magnesium oxide, a light-emitting device and electronic equipment containing zinc magnesium oxide, and the preparation method has the following technical effects:
In the preparation method of zinc oxide magnesium, the proportion of the first alkali and the second alkali in the system is regulated in different reaction stages to control the doping ratio of magnesium element in different reaction stages, so that the distribution condition of magnesium element in the prepared zinc oxide magnesium can be regulated, the prepared doped zinc oxide can show target differential distribution condition, the target energy level structure is achieved, and the energy level structure of zinc oxide magnesium can be regulated adaptively according to the change of application scenes.
In the light-emitting device, the material of the electronic functional layer comprises zinc magnesium oxide, and the zinc magnesium oxide is prepared by adopting the preparation method of the zinc magnesium oxide, so that the prepared doped zinc oxide shows target differential distribution conditions, for example, the mole percentage of magnesium is gradually reduced along the radial direction from the inside to the surface of the zinc magnesium oxide, the energy level structure of the zinc magnesium oxide can meet the requirements of the light-emitting device adaptively, and the photoelectric performance and the service life of the light-emitting device are improved.
The light-emitting device is applied to the electronic equipment, and is beneficial to improving the display effect and prolonging the service life of the electronic equipment.
Drawings
The technical solution and other advantageous effects of the present application will be made apparent by the following detailed description of the specific embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a schematic flow chart of a method for preparing zinc magnesium oxide according to an embodiment of the present application;
FIG. 2 is a schematic diagram of the structural composition of a zinc magnesium oxide provided in an embodiment of the present application;
Fig. 3 is a schematic structural view of a first light emitting device according to an embodiment of the present application;
fig. 4 is a schematic structural view of a second light emitting device according to an embodiment of the present application.
FIG. 5 is an ultraviolet absorption spectrum of zinc magnesium oxide obtained in example 1, example 2, comparative example 1 and comparative example 2.
Reference numerals:
1: light emitting device, 10: substrate, 11: anode, 12: cathode, 13: light emitting layer, 14: electronic functional layer, 15: hole functional layer, 151: hole injection layer, 152: and a hole transport layer.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The following description of the embodiments is not intended to limit the preferred embodiments. 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 ranges, 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.
In the description of the present application, the term "comprising" means "including but not limited to".
The term "at least one" means one or more, and "plurality" means two or more. The terms "at least one," "at least one of," or the like, refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c" or "at least one (individual) of a, b, and c" may each be expressed as: a. b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c, respectively, may be single or multiple.
The scope of the term "and/or" includes any one of the two or more items listed in relation to each other as well as any and all combinations of items listed in relation to each other, including any two items listed in relation to each other, any more items listed in relation to each other, or all combinations of items listed in relation to each other. For example, "a and/or B" includes A, B and three parallel schemes a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical schemes of all "logical or" connections), also include any and all combinations of A, B, C, D, i.e., the combinations of any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical schemes of all "logical and" connections).
In the present application, the description of "the a layer is formed on the side of the B layer" or "the a layer is formed on the side of the B layer away from the C layer" may mean that the a layer is directly formed on the side of the B layer or the side of the B layer away from the C layer, that is, the a layer is in direct contact with the B layer; it may also mean that the grounding between layers a is formed on one side of layer B or on one side of layer B away from layer C, i.e. other film layers may also be formed between layers a and B.
In the present application, "gradually decreasing", "gradually increasing" or the like should be understood in a broad sense. The "taper" may be a stepwise taper or a continuous taper. Similarly, the "gradually increasing" may be a stepwise gradually increasing or a continuous gradually increasing.
The embodiment of the application provides a preparation method of zinc magnesium oxide, which is shown in figure 1 and comprises the following steps:
s1, providing a first solution containing zinc salt, a second solution containing magnesium salt, a third solution containing first alkali and a fourth solution containing second alkali;
s2, mixing the second solution, the third solution, the fourth solution and the first solution for reaction to obtain zinc magnesium oxide.
Wherein the first base is selected from lithium hydroxide, the second base is selected from one or more of sodium hydroxide, potassium hydroxide and a quaternary ammonium base including, but not limited to, one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and tetraalkylammonium hydroxide (TAAOH, alkyl = methyl, ethyl, propyl and butyl).
In step S1, the anions that make up the zinc salt and the anions that make up the magnesium salt include, but are not limited to, halogen ions, sulfate ions, carbonate ions, nitrate ions, phosphate ions, or carboxylate ions. Zinc salts include, but are not limited to, one or more of zinc halides, zinc acetate, zinc nitrate, and zinc sulfate. Magnesium salts include, but are not limited to, one or more of magnesium halide, magnesium acetate, magnesium nitrate, and magnesium sulfate.
In some embodiments of the application, the concentration of zinc salt in the first solution is from 0.1mmol/mL to 0.5mmol/mL, such as from 0.1mmol/mL to 0.2mmol/mL, from 0.2mmol/mL to 0.3mmol/mL, from 0.3mmol/mL to 0.4mmol/mL, or from 0.4mmol/mL to 0.5mmol/mL. The concentration of the second metal salt in the second solution is 0.1 to 0.5mmol/mL, and may be, for example, 0.1 to 0.2mmol/mL, 0.2 to 0.3mmol/mL, 0.3 to 0.4mmol/mL, or 0.4 to 0.5mmol/mL.
In some embodiments of the application, the concentration of magnesium salt in the second solution is between 0.1mmol/mL and 0.5mmol/mL, such as between 0.1mmol/mL and 0.2mmol/mL, between 0.2mmol/mL and 0.3mmol/mL, between 0.3mmol/mL and 0.4mmol/mL, or between 0.4mmol/mL and 0.5mmol/mL. The concentration of the second metal salt in the second solution is 0.1 to 0.5mmol/mL, and may be, for example, 0.1 to 0.2mmol/mL, 0.2 to 0.3mmol/mL, 0.3 to 0.4mmol/mL, or 0.4 to 0.5mmol/mL.
In some embodiments of the application, the concentration of the first base in the third solution is from 0.1mmol/mL to 1.0mmol/mL, which may be 0.1mmol/mL～0.2mmol/mL、0.2mmol/mL～0.3mmol/mL、0.3mmol/mL～0.4mmol/mL、0.4mmol/mL～0.5mmol/mL、0.5mmol/mL～0.6mmol/mL、0.6mmol/mL～0.7mmol/mL、0.7mmol/mL～0.8mmol/mL、0.8mmol/mL～0.9mmol/mL、 or from 0.9mmol/mL to 1.0mmol/mL, for example.
In some embodiments of the application, the concentration of the second base in the fourth solution is 0.1 mmol/mL-1.0 mmol/mL, which may be 0.1mmol/mL～0.2mmol/mL、0.2mmol/mL～0.3mmol/mL、0.3mmol/mL～0.4mmol/mL、0.4mmol/mL～0.5mmol/mL、0.5mmol/mL～0.6mmol/mL、0.6mmol/mL～0.7mmol/mL、0.7mmol/mL～0.8mmol/mL、0.8mmol/mL～0.9mmol/mL、 or 0.9 mmol/mL-1.0 mmol/mL, for example.
In some embodiments of the present application, the solvents of the first solution, the second solution, the third solution, and the fourth solution are selected from organic solvents, including, but not limited to, one or more of alkanes, aromatics, haloalkanes, alcohols, ethers, furans, pyridines, and amides, exemplified by one or more of methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, dimethyl sulfoxide, and N, N-dimethylformamide, independently of each other.
In order to further improve the effect of the magnesium element in the zinc oxide magnesium prepared to present the target differential distribution condition, S2 includes the steps of: injecting a second solution, a third solution and a fourth solution into the first solution, wherein the start time point and the end time point of the injection of the second solution, the third solution and the fourth solution are the same; in the whole injection process, the second solution is injected in a uniform speed mode, the sum of the total injection mole numbers of the first alkali and the second alkali at any moment is a constant value, and the injection rates of the third solution and the fourth solution are any one of the following conditions:
(a) In the whole injection process, the injection rate of the third solution is gradually reduced, and the injection rate of the fourth solution is gradually increased;
(a) The injection rate of the third solution gradually increases and the injection rate of the fourth solution gradually decreases throughout the injection process.
In the preparation method of zinc magnesium oxide, the proportion of the first alkali and the second alkali in the system is regulated in different reaction stages to control the doping ratio of magnesium element in different reaction stages, so that the magnesium element presents a target differential distribution condition in the prepared zinc magnesium oxide to achieve a target energy level structure, and the energy level structure of the zinc magnesium oxide is conveniently and adaptively regulated according to the change of application scenes.
Specifically, in the process of preparing zinc magnesium oxide, condensation reactions represented by the following reaction formulae (i) to (iii) mainly occur:
-Zn-OH+HO-Zn-→-Zn-O-Zn-+H2O(Ⅰ)
-Mg-OH+HO-Mg-→-Mg-O-Mg-+H2O(Ⅱ)
-Zn-OH+HO-Mg-→-Zn-O-Mg-+H2O(Ⅲ)
The applicant has found that in the third solution the difference between the reactivity of the magnesium element and the reactivity of the zinc element is small, whereas in the fourth solution the reactivity of the magnesium element is much greater than the reactivity of the zinc element, i.e. the reaction between the magnesium element and the second base is easier to occur than between the zinc element and the second base. When the molar amount of the second base in the system is larger than that of the first base on the premise that the total molar amount of hydroxyl groups injected into the first solution is constant in any time period, the reaction shown in the reaction formula (II) is preferentially carried out, so that the amount of HO-Mg-entering the reaction formula (III) is reduced, the occurrence of the reaction shown in the reaction formula (III) is reduced, in addition, -Mg-O-Mg-forms large-sized 'aggregates' more easily than-Zn-O-Zn-and-Zn-O-Mg-and precipitates from the solution once the 'aggregates' reach a certain size, and the reaction shown in the reaction formula (II) is further accelerated, so that the number of Mg atoms of a conversion doped crystal structure is reduced; when the molar amount of the first base is larger than the molar amount of the second base in the system, the difference between the reactivity based on the magnesium element and the reactivity based on the zinc element in the third solution is small, so that the reaction of the reaction formula (iii) is promoted to occur, so that the number of Mg atoms converted and incorporated into the crystal structure increases. Thus, the higher the mole percentage of the first base in the total amount of base in the system, the greater the number of Mg atoms converted to incorporate the crystal structure; the higher the mole percentage of the second base in the total amount of base in the system, the fewer the number of Mg atoms converted to incorporate the crystal structure.
It will be appreciated that for case (a), the structure of the zinc magnesium oxide formed is as shown in FIG. 2, with the mole percent of Mg gradually decreasing along the radius of the interior to the surface of the zinc magnesium oxide, where 1 > x > y > z > 0. For case (b), the mole percent of Mg gradually increases along the radial direction from the interior to the surface of the zinc magnesium oxide, corresponding to 1 > z > y > x.gtoreq.0 in FIG. 2.
In some embodiments of the application, for case (a), in step S2, the initial injection rate of the third solution is 1.5 to 3 times, for example, may be 1.5 to 1.8 times, 1.8 to 2.0 times, 2.0 to 2.2 times, 2.2 to 2.4 times, 2.4 to 2.6 times, 2.6 to 2.8 times, or 2.8 to 3.0 times the final injection rate of the third solution; and/or the final injection rate of the fourth solution is 1.5 to 3 times the initial injection rate of the fourth solution, which may be, for example, 1.5 to 1.8 times, 1.8 to 2.0 times, 2.0 to 2.2 times, 2.2 to 2.4 times, 2.4 to 2.6 times, 2.6 to 2.8 times, or 2.8 to 3.0 times.
In some embodiments of the application, for case (b), in step S2, the final injection rate of the third solution is 1.5 to 3 times, for example, may be 1.5 to 1.8 times, 1.8 to 2.0 times, 2.0 to 2.2 times, 2.2 to 2.4 times, 2.4 to 2.6 times, 2.6 to 2.8 times, or 2.8 to 3.0 times the initial injection rate of the third solution; and/or the initial injection rate of the fourth solution is 1.5 to 3 times, for example, 1.5 to 1.8 times, 1.8 to 2.0 times, 2.0 to 2.2 times, 2.2 to 2.4 times, 2.4 to 2.6 times, 2.6 to 2.8 times, or 2.8 to 3.0 times the final injection rate of the fourth solution.
In order to further improve the performance controllability of the zinc magnesium oxide, in the step S2, the total injection time is 5min to 60min, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, or 50min to 60min.
In order to further improve the performance controllability of the zinc magnesium oxide, in the step of mixing and reacting the second solution, the third solution, the fourth solution and the first solution, the molar ratio of the magnesium element in the second solution to the zinc element in the first solution is 1: (4-20), for example, 1: (4-6), 1: (6-8), 1: (8-10), 1: (10-12), 1: (12-15), 1: (15-18), or 1: (18-20); and/or the ratio of the mole number of zinc element in the first solution to the sum of the mole numbers of hydroxyl groups of the third solution and the fourth solution is 1: (0.8 to 2), for example, 1: (0.8-1), 1: (0.8-1.2), 1: (0.8-1.5), 1: (0.8-1.8), 1: (1-2), or 1: (1.5-2).
In order to further improve the performance controllability of the zinc magnesium oxide, in the step S2, the mixing reaction is carried out at 0-70 ℃, for example, 0-10 ℃, 10-20 ℃, 20-30 ℃, 30-40 ℃, 40-50 ℃, 50-60 ℃, or 60-70 ℃; and/or the time of the mixing reaction is 5min to 24h, for example, 5min to 30min, 30min to 1h, 1h to 2h, 2h to 3h, 3h to 4h, 4h to 5h, 5h to 6h, 6h to 7h, 7h to 10h, 10h to 12h, 12h to 15h, 15h to 20h, or 20h to 24h, the example "mixing reaction" includes the steps of: stirring at 0-70 deg.c for 5 min-24 hr.
In order to enhance the obtaining of zinc magnesium oxide in solid state, in some embodiments of the present application, after the "mixing reaction" procedure of step S2, the preparation method of zinc magnesium oxide further comprises the steps of: adding a precipitant to the reaction product of the mixed reaction to generate a precipitate, and then performing solid-liquid separation to collect the precipitate, wherein the precipitate is purified zinc magnesium oxide. Wherein the precipitant includes, but is not limited to, heptane; solid-liquid separation includes, but is not limited to, one or more of sedimentation, filtration, and evaporation, including, but not limited to, one or more of gravity sedimentation, centrifugal sedimentation, and electromagnetic force sedimentation, filtration separation including, but not limited to, one or more of reverse osmosis, membrane filtration, nanofiltration, ultrafiltration, and microfiltration.
The embodiment of the application also provides zinc magnesium oxide, which is prepared by adopting any one of the preparation methods of the zinc magnesium oxide.
In the zinc oxide magnesium of the embodiment of the application, the mole percentage of magnesium gradually decreases along the radial direction from the inside to the surface of the zinc oxide magnesium; or gradually increasing the mole percentage of magnesium along the radial direction from the inside to the surface of the zinc oxide magnesium, so that the magnesium presents a target differential distribution condition in the prepared doped zinc oxide, and the energy level structure of the zinc oxide magnesium can be adjusted adaptively according to the change of application scenes.
In some embodiments of the application, the zinc magnesium oxide has an average particle size of 2nm to 20nm, such as 2nm to 5nm, 5nm to 8nm, 8nm to 10nm, 10nm to 15nm, or 15nm to 20nm; and/or the band gap of zinc magnesium oxide is 3.7 eV-4.5 eV, and can be, for example, 3.7 eV-3.8 eV, 3.8 eV-3.9 eV, 3.9 eV-4.0 eV, 4.0 eV-4.1 eV, 4.1 eV-4.2 eV, 4.2 eV-4.3 eV, 4.3 eV-4.4 eV, or 4.4 eV-4.5 eV.
The embodiment of the present application further provides a light emitting device, as shown in fig. 3, where the light emitting device 1 includes an anode 11, a cathode 12, a light emitting layer 13, and an electronic functional layer 14, where the anode 11 and the cathode 12 are disposed opposite to each other, the light emitting layer 13 is disposed between the anode 11 and the cathode 12, and the electronic functional layer 14 is disposed between the cathode 12 and the light emitting layer 13, where a material of the electronic functional layer 14 includes zinc magnesium oxide, and the zinc magnesium oxide is prepared by using the preparation method of zinc magnesium oxide as described above.
In the existing light-emitting device, zinc oxide is a common electron function material, the conduction band energy level of zinc oxide is favorable for injecting electrons from a cathode to a light-emitting layer, and zinc oxide has a deeper valence band energy level, so that the zinc oxide has a function of blocking holes. Proper amount of magnesium is doped in zinc oxide to effectively improve the fluorescence quenching phenomenon of the luminescent quantum dots, so that the current efficiency of the luminescent device is improved, but the doped magnesium can influence the energy level structure and electron mobility of the zinc oxide, the content of the magnesium is too high to cause the rising of the conduction band energy level of the zinc oxide, the injection barrier of electrons is improved, and the electron injection is not facilitated. The conventional solution-gel method is adopted to prepare zinc magnesium oxide, and comprises the following steps: the solution containing the magnesium precursor and the alkali solution are injected into the solution containing the zinc precursor to react, so that zinc magnesium oxide is obtained, and in theory, the molar percentage difference of the second metal element in the prepared zinc magnesium oxide along the radial direction from the inside to the surface is small, and the distribution condition of the magnesium in the prepared zinc magnesium oxide cannot be regulated, so that the energy level structure of the zinc magnesium oxide cannot be conveniently and adaptively regulated according to the requirements of the light-emitting device, and the photoelectric performance of the light-emitting device is not ideal.
In the light-emitting device of the embodiment of the present application, the material of the electronic functional layer 14 includes zinc magnesium oxide, which is prepared by any one of the preparation methods of zinc magnesium oxide described above, and the mole percentage of magnesium gradually decreases or increases along the radial direction from the inside to the surface of zinc magnesium oxide, so that the magnesium shows a differential distribution in the prepared doped zinc oxide, and the energy level structure of zinc magnesium oxide can adaptively meet the requirements of the light-emitting device, thereby being beneficial to improving the photoelectric performance of the light-emitting device.
As an example, the molar percentage of magnesium gradually decreases along the radial direction from the inside to the surface of zinc magnesium oxide, having the advantage of: on one hand, a variable energy level structure (such as a step-graded energy level structure) is constructed between the electronic functional layer and the cathode, so that electron injection is facilitated, and the electron injection level of the light-emitting device is improved; on the other hand, compared with zinc oxide, the band gap of zinc oxide magnesium is wider, which is more beneficial to limiting excitons to be combined in the light-emitting layer, and improves the current efficiency of the light-emitting device.
The electron functional layer 14 may have a single-layer structure or a multilayer structure, and the thickness of the electron functional layer 14 is, for example, 10nm to 100nm. When the electron functional layer 14 has a single-layer structure, the electron functional layer 14 is, for example, an electron injection layer or an electron transport layer. When the electronic functional layer 14 is in a multilayer structure, the electronic functional layer 14 includes an electron injection layer and an electron transport layer which are stacked, the electron transport layer is closer to the light emitting layer 13 than the electron injection layer, the electron injection layer is closer to the cathode 12 than the electron transport layer, and the material of the electron injection layer and/or the electron transport layer is zinc magnesium oxide, which is prepared by any one of the preparation methods of zinc magnesium oxide described above.
In the light emitting device 1 of the embodiment of the present application, materials of the anode 11, the cathode 12, and the light emitting layer 13 may be common in the art, for example:
The materials of the anode 11 and the cathode 12 are independently selected from one or more of a metal, a carbon material, and a metal oxide material. The metal is selected from one or more of Al, ag, cu, mo, au, ba, ca and Mg. The carbon material is selected from one or more of graphite, carbon nanotubes, graphene and carbon fibers. The metal oxide material may be a doped or undoped metal oxide, for example, one or more selected from Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), tin antimony oxide (ATO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), indium doped zinc oxide (IZO), and magnesium doped zinc oxide (MZO). Anode 11 or cathode 12 may also be a composite electrode of doped or undoped transparent metal oxides sandwiching a metal, including but not limited to one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2. The thickness of the anode 11 may be, for example, 20nm to 200nm, and the thickness of the cathode 12 may be, for example, 20nm to 200nm.
The material of the light emitting layer 13 may be selected from organic light emitting materials or quantum dots, and the thickness of the light emitting layer 13 may be, for example, 10nm to 50nm, corresponding to the light emitting device 1 being an OLED or QLED. The light-emitting layer 13 may have a single-layer structure or a multilayer structure, and for example, the light-emitting layer 13 may have two or more layers.
The organic luminescent material includes, but is not limited to, one or more of tris [2- (p-tolyl) iridium (III) pyridinium, 4' -tris (carbazol-9-yl) triphenylamine, tris [2- (p-tolyl) iridium pyridinium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonding, hybrid localized charge transfer excited state materials, and exciplex luminescent materials.
The quantum dots include, but are not limited to, one or more of red, green, and blue quantum dots, and the quantum dots include, but are not limited to, one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots, the average particle size of the quantum dots may be, for example, 5nm to 10nm, with the average particle size of the quantum dots exemplified by 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm.
For single component quantum dots and core-shell structured quantum dots, the material of the single component quantum dot, the material of the core-shell structured quantum dot, or the material of the shell of the core-shell structured quantum dot includes, but is not limited to, at least one of a group II-VI compound selected from one or more 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 and HgZnSTe, a group III-V compound selected from one or more 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 and InAlPSb, and a group IV-VI compound selected from one or more of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe, a group IV-VI compound selected from one or more of CuInS, cuInSe and AgInS. The chemical formula provided for the material of the single component quantum dot, the material of the core of the quantum dot of the core-shell structure, or the material of the shell of the quantum dot of the core-shell structure shows only the elemental composition, and the content of each element is not shown, for example: cdZnSe is only composed of three elements Cd, zn and Se, and if the content of each element is expressed, the corresponding value is Cd xZn1-x Se,0< x <1.
For inorganic perovskite quantum dots, the structural formula of the inorganic perovskite quantum dots is AMX 3, wherein A is Cs + ion, M is divalent metal cation, M comprises, but is not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ or Eu 2+, and X is halogen anion, including, but not limited to, cl -、Br- or I -.
For organic perovskite quantum dots, the structural formula hey CMX 3 of the organic perovskite quantum dots, wherein C is a formamidino group, M is a divalent metal cation, M includes but is not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ or Eu 2+, and X is a halogen anion, including but not limited to Cl -、Br- or I -.
For the organic-inorganic hybrid perovskite quantum dots, the structural general formula of the organic-inorganic hybrid perovskite quantum dots is BMX 3, wherein B is selected from organic amine cations, the organic amine cations comprise but are not limited to CH 3(CH2)n-2NH3+ (n is more than or equal to 2) or NH 3(CH2)nNH3 2+ (n is more than or equal to 2), M is a divalent metal cation, M comprises but is not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ or Eu 2+, and X is a halogen anion, including but not limited to Cl -、Br- or I -.
It is understood that when the material of the light emitting layer comprises quantum dots, the material of the light emitting layer further comprises a ligand attached to the surface of the quantum dots, the ligand comprises, but is not limited to, at least one of an amine ligand, a carboxylic acid ligand, a thiol ligand, (oxy) phosphine ligand, a phospholipid, a soft phospholipid or a polyvinylpyridine, the amine ligand is, for example, at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, tributylamine or trioctylamine, the carboxylic acid ligand is, for example, at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, dodecylic acid, hexadecanoic acid, octadecanoic acid, oleic acid or benzoic acid, the thiol is, for example, at least one of methyl mercaptan, ethyl mercaptan, butanethiol, pentanethiol, hexanethiol, hexadecane, hexadecanethiol, octadecanethiol or benzylphosphine, (the ligand is, for example, methyl phosphine, n-octyl phosphine, trioctylphosphine or trioctylphosphine).
In order to further improve the overall performance of the light emitting device, in some embodiments of the present application, with continued reference to fig. 3, the light emitting device 1 further includes a hole function layer 15, the hole function layer 15 being disposed between the light emitting layer 13 and the anode 11.
The hole function layer 15 may have a single-layer structure or a multilayer structure, and the thickness of the hole function layer 15 is, for example, 10nm to 100nm. In some embodiments of the present application, the hole-functional layer 15 is a single-layer structure, and the hole-functional layer 15 is, for example, a hole-injecting layer or a hole-transporting layer.
In other embodiments of the present application, the hole-functional layer 15 is a multilayer structure, and the hole-functional layer 15 includes a hole-injecting layer and a hole-transporting layer that are stacked, the hole-injecting layer being closer to the anode 11 than the hole-transporting layer, and the hole-transporting layer being closer to the light-emitting layer 13 than the hole-injecting layer.
The material of the hole injection layer and/or the material of the hole transport layer is selected from poly (3, 4-ethylenedioxythiophene) selected from poly (styrenesulfonic acid), copper phthalocyanine, titanylphthalocyanine, 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), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), Poly (4, 4 '-tris (2-naphthylphenylamino) triphenylamine), 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, poly (4, 4' -N, N '-dicarbazolyl-biphenyl), poly (N, N' -diphenyl-N, N '-bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine), poly (4, 4 '-bis (9-carbazole) biphenyl), poly (4, 4',4" -tris (carbazole-9-yl) triphenylamine), poly (N, N '-diphenyl-N, N' -bis (3-methylphenyl) - (1, 1 '-biphenyl) -4,4' -diamine), Poly (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro), poly (N, N ' -bis (4- (N, N ' -diphenyl-amino) phenyl) -N, N ' -diphenyl benzidine), poly (4, 4' -tris (N-carbazolyl) -triphenylamine), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ], poly (4-butylphenyl-diphenylamine), polyaniline, polypyrrole, Poly (p-phenylenevinylene), poly (2-methoxy-5- (2-ethylhexyl oxy) -1, 4-phenylenevinylene), poly (2-methoxy-5- (3 ',7' -dimethyloctyl oxy) -1, 4-phenylenevinylene), aromatic tertiary amine, 4 '-bis (p-carbazolyl) -1,1' -biphenyl compound, N, N, N ', N' -tetraarylbenzidine, poly (N-vinylcarbazole) and its derivatives, polymethacrylate and its derivatives, poly (9, 9-octylfluorene) and its derivatives, 3-hexyl-substituted polythiophene, poly (spirofluorene) and its derivatives, Poly (N, N '-di (naphthalen-1-yl) -N, N' -diphenyl benzidine), doped or undoped graphene, C60, doped or undoped nickel oxide, doped or undoped molybdenum oxide, doped or undoped tungsten oxide, doped or undoped vanadium oxide, doped or undoped P-type gallium nitride, doped or undoped chromium oxide, doped or undoped copper oxide, doped or undoped transition metal sulfide, and one or more of transition metal selenide, wherein the transition metal sulfide includes, but is not limited to, one or more of molybdenum sulfide, tungsten sulfide, and copper sulfide, and the transition metal selenide includes, but is not limited to, one or more of molybdenum selenide and tungsten selenide. Wherein, the doped or undoped nickel oxide is exemplified by NiO; an example of doped or undoped molybdenum oxide is MoO 3; an example of doped or undoped tungsten oxide is WO 3; an example of doped or undoped vanadium oxide is V 2O5; an example of doped or undoped chromium oxide is CrO 3; Examples of doped or undoped copper oxide are one or more of CuO and Cu 2 O.
It should be noted that, the preparation method of each film layer in the light emitting device may be implemented by using conventional technologies in the art, including, but not limited to, a solution method and a deposition method, where the solution method includes, but is not limited to, one or more of spin coating, printing, inkjet printing, doctor blading, printing, dip-coating, dipping, spraying, roll coating, casting, slit coating, and bar coating; the deposition method includes a chemical method including, but not limited to, one or more of chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation, and a physical method including, but not limited to, one or more of thermal vapor deposition, electron beam vapor deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. When the film layer is prepared by a solution method, a drying treatment process is added to convert the wet film into a dry film.
It will be appreciated that the method of manufacturing a light emitting device may also include other steps, such as: after each film layer of the light emitting device is prepared, the light emitting device needs to be packaged.
The embodiment of the application also provides electronic equipment, which comprises the light-emitting device. The electronic device may be, for example, any electronic product with display function, including but not limited to, a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle display, a television set, or an electronic book reader, where the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, or the like.
The technical solutions and effects of the present application will be described in detail by way of specific examples, comparative examples and experimental examples, which are only some examples of the present application, and are not intended to limit the present application in any way.
Example 1
The embodiment provides a preparation method of zinc magnesium oxide and the prepared zinc magnesium oxide, wherein the mole percentage of magnesium element is gradually reduced along the radial direction from the inside to the surface of the zinc magnesium oxide.
The preparation method of the zinc magnesium oxide in the embodiment comprises the following steps:
S1.1, preparing a first solution: 0.24mmol of zinc acetate was dissolved in 60mL of dimethyl sulfoxide and stirred at room temperature for 2h to obtain a first solution;
S1.2, preparing a second solution: 0.06mmol of magnesium acetate was dissolved in 60mL of dimethyl sulfoxide and stirred at room temperature for 2h to obtain a second solution;
s1.3, preparing a third solution: dispersing 0.18mmol of lithium hydroxide in 50mL of ethanol, and stirring at room temperature for 2h to obtain a third solution;
S1.4, preparing a fourth solution: dispersing 0.18mmol of potassium hydroxide in 50mL of ethanol, and stirring at room temperature for 2h to obtain a fourth solution;
S1.5, preparing zinc magnesium oxide: simultaneously and continuously injecting 60mL of second solution, 50mL of third solution and 50mL of fourth solution into 60mL of first solution within 60min, wherein the starting time point and the ending time point of the injection of the second solution, the third solution and the fourth solution are identical, in the injection process, the second solution is injected in a uniform speed mode, the injection rate of the second solution is 60mL/h, the third solution is injected in a uniform speed reducing mode, the initial injection rate of the third solution is 67mL/h, the acceleration is-33 mL/h 2, the initial injection rate of the fourth solution is 33mL/h, the acceleration is 33mL/h 2, and the reaction product is obtained by stirring for 4h at room temperature after the injection is finished;
s1.6, adding heptane into the reaction product to generate a precipitate, centrifuging to collect the precipitate, cleaning the precipitate, and drying to obtain the purified zinc magnesium oxide.
Example 2
The embodiment provides a preparation method of zinc magnesium oxide and the prepared zinc magnesium oxide, wherein the mole percentage of magnesium element is gradually increased along the radial direction from the inside to the surface of the zinc magnesium oxide.
The difference between the preparation method of zinc magnesium oxide in this example compared with the preparation method of zinc magnesium oxide in example 1 is that: and replacing the step S1.5 with 'injecting 60mL of the second solution, 50mL of the third solution and 50mL of the fourth solution into 60mL of the first solution simultaneously and continuously in 60 min', wherein the initial time point and the end time point of the injection of the second solution, the third solution and the fourth solution are identical, the second solution is injected in a uniform speed mode, the injection rate of the second solution is 60mL/h, the third solution is injected in a uniform acceleration mode, the initial injection rate of the third solution is 33mL/h, the acceleration is 33mL/h 2, the initial injection rate of the fourth solution is 67mL/h, the acceleration is-33 mL/h 2, and stirring is carried out for 4h at room temperature after the injection is finished, so as to obtain a reaction product.
Example 3
The embodiment provides a light emitting device and a preparation method thereof, wherein the light emitting device is a quantum dot light emitting diode with a forward structure, as shown in fig. 4, in a bottom-up direction, the light emitting device 1 includes a substrate 10, an anode 11, a hole functional layer 15, a light emitting layer 13, an electron functional layer 14 and a cathode 12, which are sequentially stacked, wherein the hole functional layer 15 is composed of a hole injection layer 151 and a hole transport layer 152 which are stacked, the hole injection layer 151 is closer to the anode 11 than the hole transport layer 152, and the hole transport layer 152 is closer to the light emitting layer 13 than the hole injection layer 151.
The materials and thicknesses of the respective layers in the light emitting device 1 are as follows:
The material of the substrate 10 is glass, and the thickness of the substrate 10 is 2mm;
the anode 11 is made of ITO, and the thickness of the anode 11 is 80nm;
The cathode 12 is made of Ag, and the thickness of the cathode 12 is 100nm;
The luminescent layer 13 is made of CdSe (core)/ZnS (shell) quantum dots, the luminescent color is blue, and the thickness of the luminescent layer 13 is 30nm;
the material of the electron function layer 14 was zinc magnesium oxide prepared in example 1, and the thickness of the electron function layer 14 was 30nm;
The hole injection layer 151 is made of PEDOT PSS, and the thickness of the hole injection layer 151 is 25nm;
the material of the hole transport layer 152 is TFB, and the thickness of the hole transport layer 152 is 25nm.
The preparation method of the light-emitting device in the embodiment comprises the following steps:
S3.1, providing a substrate, sputtering ITO on one side of the substrate to obtain an ITO layer, dipping a small amount of soapy water on the surface of the ITO layer by using a cotton swab to wipe the surface of the ITO layer so as to remove impurities visible to the naked eyes on the surface, sequentially ultrasonically cleaning the substrate comprising the ITO by using deionized water, acetone for 15min, ethanol for 15min and isopropanol for 15min, and performing ultraviolet-ozone surface treatment for 15min after drying to obtain the substrate comprising an anode;
S3.2, spin-coating PEDOT/PSS aqueous solution on one side of the anode far from the substrate in an air environment at normal temperature and normal pressure, and then placing the substrate at a constant temperature of 150 ℃ for heat treatment for 30min to obtain a hole injection layer;
s3.3, spin-coating a TFB-chlorobenzene solution with the concentration of 8mg/mL on one side of the hole injection layer far away from the anode in a nitrogen environment at normal temperature and normal pressure, and then performing constant-temperature heat treatment for 30min at 150 ℃ to obtain a hole transport layer;
S3.4, spin-coating CdSe/ZnS quantum dot-n-octane solution with the concentration of 25mg/mL on one side of the hole transport layer far away from the hole injection layer in a nitrogen environment at normal temperature and normal pressure, and then performing constant-temperature heat treatment at 60 ℃ for 5min to obtain a luminescent layer;
S3.5, dispersing the zinc magnesium oxide prepared in the embodiment 1 in ethanol to prepare a zinc magnesium oxide-ethanol solution with the concentration of 30mg/mL, spin-coating the zinc magnesium oxide-ethanol solution on one side of the luminescent layer far away from the hole transport layer in a nitrogen environment with normal temperature and normal pressure, and then placing the solution at a constant temperature of 60 ℃ for heat treatment for 10min to obtain an electronic functional layer;
s3.6, placing the prefabricated device containing the electronic functional layer in an evaporation bin with the air pressure of 4 multiplied by 10 -6 mbar, thermally evaporating Ag on one side of the electronic transmission layer, which is far away from the light-emitting layer, through a mask plate to obtain a cathode, and then packaging the cathode by adopting epoxy resin glue and a cover glass to obtain the light-emitting device.
Example 4
The present embodiment provides a light emitting device and a method for manufacturing the same, which differ from the light emitting device of embodiment 3 only in that: the material of the electron functional layer was replaced with the doped metal oxide prepared in example 2.
The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 3 in that: the step S3.5 is replaced by "the zinc magnesium oxide prepared in the example 1 is dispersed in ethanol to prepare a zinc magnesium oxide-ethanol solution with the concentration of 30mg/mL, the zinc magnesium oxide-ethanol solution is spin-coated on the side of the luminescent layer far away from the hole transport layer under the nitrogen environment of normal temperature and normal pressure, and then the solution is subjected to constant temperature heat treatment at 60 ℃ for 10min, so as to obtain the electronic functional layer.
Comparative example 1
The comparative example provides a preparation method of zinc magnesium oxide and the prepared zinc magnesium oxide, and the preparation method of the zinc magnesium oxide in the comparative example comprises the following steps:
S10.1, preparing and obtaining a first solution by referring to the step S1.1;
S10.2, preparing and obtaining a second solution by referring to the step S1.2;
S10.3, preparing alkali liquor: dispersing 0.36mmol of potassium hydroxide in 100mL of ethanol, and stirring at room temperature for 2h to obtain alkali liquor;
S10.4, preparing zinc magnesium oxide: simultaneously and continuously injecting 60mL of second solution and 100mL of alkali liquor into 60mL of first solution within 60min, wherein the starting time point and the ending time point of the injection of the second solution and the alkali liquor are identical, the second solution is injected in a uniform manner in the injection process, the injection rate of the second solution is 60mL/h, the alkali liquor is injected in a uniform manner, and the injection rate of the alkali liquor is 100mL/h;
s10.5, refer to step S1.6.
Comparative example 2
The comparative example provides a preparation method of zinc magnesium oxide and the prepared zinc magnesium oxide, and the preparation method of the zinc magnesium oxide in the comparative example comprises the following steps:
s11.1, preparing a first solution according to the step S1.1;
s11.2, preparing a second solution according to the step S1.2;
s11.3, preparing alkali liquor: dispersing 0.36mmol of lithium hydroxide in 100mL of ethanol, and stirring at room temperature for 2h to obtain alkali liquor;
S11.4, preparing zinc magnesium oxide: simultaneously and continuously injecting 60mL of second solution and 100mL of alkali liquor into 60mL of first solution within 60min, wherein the starting time point and the ending time point of the injection of the second solution and the alkali liquor are identical, the second solution is injected in a uniform manner in the injection process, the injection rate of the second solution is 60mL/h, the alkali liquor is injected in a uniform manner, and the injection rate of the alkali liquor is 100mL/h;
S11.5, refer to step S1.6.
Comparative example 3
The present comparative example provides a light emitting device and a method of manufacturing the same, which differs from the light emitting device of example 3 only in that: the material of the electron functional layer was replaced with zinc magnesium oxide prepared in comparative example 1.
The manufacturing method of the light emitting device in this comparative example is different from that of the light emitting device in example 3 in that: the step S3.5 is replaced by dispersing the zinc magnesium oxide prepared in the comparative example 1 in ethanol to prepare a zinc magnesium oxide-ethanol solution with the concentration of 30mg/mL, spin-coating the zinc magnesium oxide-ethanol solution on the side of the luminescent layer far away from the hole transport layer in a nitrogen environment at normal temperature and normal pressure, and then placing the solution at a constant temperature of 60 ℃ for heat treatment for 10min to obtain an electronic functional layer.
Comparative example 4
The present comparative example provides a light emitting device and a method of manufacturing the same, which differs from the light emitting device of example 3 only in that: the material of the electron functional layer was replaced with zinc magnesium oxide prepared in comparative example 2.
The manufacturing method of the light emitting device in this comparative example is different from that of the light emitting device in example 3 in that: the step S3.5 is replaced by dispersing the zinc magnesium oxide prepared in the comparative example 2 in ethanol to prepare a zinc magnesium oxide-ethanol solution with the concentration of 30mg/mL, spin-coating the zinc magnesium oxide-ethanol solution on the side of the luminescent layer far away from the hole transport layer in a nitrogen environment at normal temperature and normal pressure, and then placing the solution at a constant temperature of 60 ℃ for heat treatment for 10min to obtain the electronic functional layer.
Experimental example 1
The absorption spectra of the zinc magnesium oxides produced in example 1, example 2, comparative example 1 and comparative example 2 were respectively tested using ultraviolet-visible spectrophotometry, and fig. 5 shows ultraviolet absorption spectra of the zinc magnesium oxides produced in example 1, example 2, comparative example 1 and comparative example 2, and optical band gaps of the zinc magnesium oxides produced in example 1, example 2, comparative example 1 and comparative example 2 were calculated using the Tauc plot method.
The optical band gap of each zinc magnesium oxide is shown in table 1 below:
Table 1 optical band gap list of zinc magnesium oxide prepared in example 1, example 2, comparative example 1 and comparative example 2
As can be seen from table 1, the optical band gap of the zinc magnesium oxide in comparative example 2 is the widest, followed by example 2, and again example 1, and the optical band gap of the zinc magnesium oxide in comparative example 1 is the narrowest, probably because: in the preparation process of zinc magnesium oxide in comparative example 2, the injected alkali solution is lithium hydroxide, the number of magnesium atoms which are converted and doped into the zinc oxide crystal structure is the largest, and the optical band gap of the prepared zinc magnesium oxide is the widest. In the preparation process of zinc magnesium oxide in comparative example 1, the injected alkali solution is potassium hydroxide, the number of magnesium atoms converted and doped into the zinc oxide crystal structure is minimum, and the optical band gap of the prepared zinc magnesium oxide is the narrowest. In the preparation process of zinc magnesium oxide in example 1, the injected alkali solution is lithium hydroxide and potassium hydroxide, the mole percentage of lithium hydroxide in the total alkali gradually decreases and the mole percentage of potassium hydroxide in the total alkali gradually increases as the alkali solution injection proceeds, and the number of magnesium atoms converted to be doped into the zinc oxide crystal structure gradually decreases as the mole percentage of potassium hydroxide gradually increases, so that the optical band gap of zinc magnesium oxide in example 1 is wider than that of zinc magnesium oxide in comparative example 1 and narrower than that of zinc magnesium oxide in comparative example 2. In the preparation process of zinc magnesium oxide in example 2, the injected alkali solution is lithium hydroxide and potassium hydroxide, the mole percentage of lithium hydroxide in the total alkali gradually increases and the mole percentage of potassium hydroxide in the total alkali gradually decreases as the alkali solution injection proceeds, and the number of magnesium atoms converted and doped into the zinc oxide crystal structure gradually increases as the mole percentage of lithium hydroxide gradually increases, so that the optical band gap of zinc magnesium oxide in example 2 is wider than that of zinc magnesium oxide in comparative example 1 and narrower than that of zinc magnesium oxide in comparative example 2.
Further, as can be seen from fig. 5, the maximum absorption peak wavelength of the zinc magnesium oxide in example 1, example 2 and comparative example 1 all show a different degree of "red shift" compared with the maximum absorption peak wavelength of the zinc magnesium oxide in comparative example 2, wherein the "red shift" phenomenon of the maximum absorption peak wavelength of the zinc magnesium oxide in comparative example 1 is most remarkable, and the degree of "red shift" of the maximum absorption peak wavelength of the zinc magnesium oxide in example 1 and example 2 is not much different. The more obvious the red shift phenomenon is, the less magnesium element is doped into the zinc oxide crystal structure, so that the content of the magnesium element of the zinc oxide magnesium in the comparative example 1 is the least, and the content of the magnesium element of the zinc oxide magnesium in the comparative example 2 is the most, thus proving that in the preparation process of the zinc oxide magnesium, the proportion of the first alkali and the second alkali in the system is regulated in different reaction stages, the doping ratio of the magnesium element in different reaction stages can be controlled, and the magnesium element shows the target differential distribution condition in the prepared doped zinc oxide, thereby achieving the target energy level structure, and being convenient for adaptively regulating the energy level structure of the zinc oxide magnesium according to the change of application scenes.
Experimental example 2
The electron mobility and the current density value are tested by adopting a single-electron device, the single-electron device consists of a substrate, an anode, a luminescent layer, an electronic functional layer and a cathode which are sequentially arranged, 4 single-electron devices to be tested are arranged in total, the structure compositions of the substrate, the anode, the luminescent layer and the cathode in the first single-electron device to the fourth single-electron device are respectively the same as the structure compositions of the corresponding film layers in the embodiment 3, the materials of the electronic functional layers in the first single-electron device to the fourth single-electron device are respectively zinc magnesium oxide prepared in the embodiment 1, the embodiment 2, the comparative example 1 and the comparative example 2, for example, the materials of the electronic functional layers in the first single-electron device are zinc magnesium oxide prepared in the embodiment 1, the materials of the electronic functional layers in the second single-electron device are zinc magnesium oxide prepared in the embodiment 2, and the like.
The specific test method comprises the following steps: a set of QLED efficiency testing system is built by controlling QE PRO and Keithley 2400 through LabView, the system is used for testing the current density-voltage characteristic curve of each single-electron device, and the current density value (J, mA/cm 2) of each single-electron device under the working voltage of 8V is taken and compared. Acquiring a Space Charge Limited Current (SCLC) region in a current density-voltage curve of each single-electron device, and then calculating according to a formula J= (9/8) epsilon rε0μeV2/d3 to obtain electron mobility, wherein J represents current density, and the unit is mA/cm 2;εr and represents relative dielectric constant; epsilon 0 represents the vacuum dielectric constant; mu e represents hole mobility in cm 2/V.s; v represents a driving voltage, and the unit is V; d represents the thickness of the electron functional layer in nm.
The performance test results of the individual single-electron devices are shown in table 2 below:
Table 2 list of performance test results for the first to fourth single electronic devices
As can be seen from table 1, the first single-electron device has the best electrical performance, the first single-electron device uses the zinc magnesium oxide in example 1 as the material of the electron functional layer, the zinc magnesium oxide in example 1 gradually decreases in mole percentage along the inner to surface aspect, and a step-graded energy level structure is formed between the electron functional layer and the cathode, which is beneficial to electron injection.
The second single-electron device adopts zinc magnesium oxide in the embodiment 2 as a material of the electron functional layer, the mole percentage of magnesium element in the aspect from the inside to the surface in the embodiment 2 is gradually increased, and although a step-gradient energy level structure is formed between the electron functional layer and the cathode, the mole percentage of magnesium element in one surface of the electron functional layer close to the cathode is more, so that the conduction band energy level of the surface is increased, the electron injection barrier is improved, and the electron injection difficulty is caused, so that the electrical performance of the second single-electron device is not as good as that of the first single-electron device.
In the preparation process of the zinc magnesium oxide in the comparative example 1, the injected alkali liquor is potassium hydroxide, so that the quantity of magnesium atoms converted and doped into a zinc oxide crystal structure is small, and the optical band gap of the zinc magnesium oxide in the comparative example 1 is narrow, so that the electrical performance of the third electronic device is not ideal.
In the fourth electronic device, zinc magnesium oxide in comparative example 2 is used as a material of the electronic functional layer, and in the preparation process of zinc magnesium oxide in comparative example 2, the injected alkali solution is lithium hydroxide, so that the quantity of magnesium atoms converted and doped into a zinc oxide crystal structure is large, but magnesium elements cannot present target differential distribution in the prepared zinc magnesium oxide, so that a stepped and gradual energy level structure cannot be formed between the electronic functional layer and the cathode, and the electrical performance of the third single electronic device is also not ideal.
Experimental example 3
The light emitting devices in example 3, example 4, comparative example 3 and comparative example 4 were subjected to performance tests, and the performance test items were as follows:
(1) Detection of current efficiency
The luminance value of the light emitting device in the range of 0V to 8V is intermittently collected by setting the light emitting area to be 2mm multiplied by 2 mm=4mm 2, the voltage value of the initial collected luminance is 3V, the luminance value collected every 0.2V is divided by the corresponding current density to obtain the current efficiency of the light emitting device under the condition of the collection, and the maximum current efficiency (C.E max, cd/A) of each light emitting device is obtained.
(2) Detection of lifetime T95@1000nit
Under the driving of constant current (2 mA), carrying out electroluminescence service life analysis on each light emitting device by adopting a 128-channel QLED service life testing system, recording the time (T95, h) required for each light emitting device to decay from the maximum brightness to 95%, and calculating the time (T95@1000nit, h) required for each light emitting device to decay from 100% to 95% under the brightness of 1000nit by a decay fitting formula.
The performance test data for each light emitting device is detailed in table 3 below:
Table 3 list of performance test data of light emitting devices in example 3, example 4, comparative example 3 and comparative example 4
As can be seen from table 2, the overall performance of the light emitting device in example 3 was optimal. Taking the light emitting devices of example 3 and comparative example 3 as examples, C.E max of the light emitting device of example 3 was 3 times as large as C.E max of the light emitting device of comparative example 3, and t95@1000nit of the light emitting device of example 3 was 2.5 times as large as t95@1000nit of the light emitting device of comparative example 3.
In summary, zinc magnesium oxide is used as the material of the electronic functional layer, and the mole percentage of magnesium element gradually decreases along the radial direction from the inside to the surface of the zinc magnesium oxide, which is beneficial to further improving the current efficiency of the light emitting device, probably because: on one hand, a step-gradient energy level structure is formed between the electronic functional layer and the cathode, and the mole percentage of magnesium element in one surface of the electronic functional layer close to the cathode is lower, so that an electron injection barrier is effectively reduced, electron injection is promoted, and the electron injection level of the light-emitting device is improved; on the other hand, compared with zinc oxide, the band gap of zinc oxide magnesium is wider, which is more beneficial to limiting excitons to be combined in the light-emitting layer, and improves the current efficiency of the light-emitting device.
The preparation method of zinc oxide magnesium, the light-emitting device and the electronic equipment containing zinc oxide magnesium provided by the embodiment of the application are described in detail. The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is only for aiding in the understanding of the technical solution of the present application and its core ideas; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the scope of the corresponding technical solutions of the embodiments of the present application.
Claims (11)
1. The preparation method of the zinc magnesium oxide is characterized by comprising the following steps:
Providing a first solution comprising a zinc salt, a second solution comprising a magnesium salt, a third solution comprising a first base, and a fourth solution comprising a second base; and
Mixing the second solution, the third solution, the fourth solution and the first solution for reaction to obtain the zinc magnesium oxide;
wherein the first base is selected from lithium hydroxide, and the second base is selected from one or more of sodium hydroxide, potassium hydroxide and quaternary ammonium base.
2. The method for preparing zinc magnesium oxide according to claim 1, wherein said mixing the second solution, the third solution, the fourth solution and the first solution for reaction comprises the steps of: injecting the second solution, the third solution, and the fourth solution into the first solution;
Wherein the start time point and the end time point of injection of the second solution, the third solution, and the fourth solution are the same; in the injection process, the second solution is injected in a uniform speed mode, the sum of the total injection mole numbers of the first alkali and the second alkali at any moment is a constant value, and the injection rates of the third solution and the fourth solution are any one of the following conditions:
(a) In the injection process, the injection rate of the third solution is gradually reduced, and the injection rate of the fourth solution is gradually increased;
(b) During the injection, the injection rate of the third solution is gradually increased, and the injection rate of the fourth solution is gradually decreased.
3. The method of producing zinc magnesium oxide according to claim 2, wherein for case (a), the initial injection rate of the third solution is 1.5 to 3 times the final injection rate of the third solution; and/or
The final injection rate of the fourth solution is 1.5 to 3 times the initial injection rate of the fourth solution.
4. The method of preparing zinc magnesium oxide according to claim 2, wherein for case (b), the final injection rate of the third solution is 1.5 to 3 times the initial injection rate of the third solution; and/or
The initial injection rate of the fourth solution is 1.5 times to 3 times the final injection rate of the fourth solution.
5. The method for preparing zinc magnesium oxide according to claim 2, wherein the total injection time is 5min to 60min.
6. The method according to any one of claims 1 to 5, wherein in the step of mixing and reacting the second solution, the third solution, the fourth solution, and the first solution, a molar ratio of magnesium element in the second solution to zinc element in the first solution is 1: (4-20), and/or the ratio of the number of moles of zinc element in the first solution to the sum of the number of moles of hydroxyl groups of the third solution and the number of moles of hydroxyl groups of the fourth solution is 1: (0.8-2), and/or the concentration of zinc salt in the first solution is 0.1mmol/mL to 0.5mmol/mL, and/or the concentration of magnesium salt in the second solution is 0.1mmol/mL to 0.5mmol/mL, and/or the concentration of the first base in the third solution is 0.1mmol/mL to 1.0mmol/mL, and/or the concentration of the second base in the fourth solution is 0.1mmol/mL to 1.0mmol/mL; and/or
The solvents of the first solution, the second solution, the third solution and the fourth solution are independently selected from one or more of alkane, aromatic hydrocarbon, halogenated alkane, alcohol compound, ether compound, furan compound, pyridine compound and amide compound, preferably, the solvents of the first solution, the second solution, the third solution and the fourth solution are independently selected from one or more of methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, dimethyl sulfoxide and N, N-dimethylformamide; and/or
The mixing reaction is carried out at 0-70 ℃; and/or
The mixing reaction time is 5 min-24 h.
7. A zinc magnesium oxide, characterized by being produced by the process for producing a zinc magnesium oxide as claimed in any one of claims 1 to 6.
8. The zinc magnesium oxide according to claim 7, wherein the zinc magnesium oxide has an average particle diameter of 2nm to 20nm; and/or
The band gap of the zinc magnesium oxide is 3.7 eV-4.5 eV; and/or
The mole percentage of the second element gradually increases or gradually decreases in the direction from the inside to the surface of the zinc magnesium oxide.
9. A light emitting device, comprising:
An anode;
a cathode disposed opposite the anode;
a light-emitting layer disposed between the anode and the cathode; and
An electron functional layer disposed between the cathode and the light emitting layer;
Wherein the material of the electronic functional layer contains zinc magnesium oxide produced by the method for producing zinc magnesium oxide as claimed in any one of claims 1 to 6, or the material of the electronic functional layer contains zinc magnesium oxide as claimed in claim 7 or 8.
10. The light-emitting device according to claim 9, wherein the material of the light-emitting layer is selected from an organic light-emitting material or quantum dots; Wherein the organic luminescent material is selected from one or more of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine iridium (III), 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonding, hybrid local charge transfer excited state materials and exciplex luminescent materials; The quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots and organic-inorganic hybrid perovskite quantum dots; The material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compound, group III-V compound, group IV-VI compound, or group I-III-VI compound independently of each other, wherein the group II-VI compound is selected from one or more 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 and HgZnSTe, the group III-V compound is selected from one or more 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 and InAlPSb, The IV-VI compound is selected from one or more of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe, and the I-III-VI compound is selected from one or more of CuInS, cuInSe and AgInS; The structural general formula of the inorganic perovskite quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, M is selected from one or more of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ and Eu 2+, X is a halogen anion; The structural general formula of the organic perovskite quantum dot is CMX 3, and C is formamidino; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, and B is selected from organic amine cations; and/or
The materials of the anode and the cathode are independently selected from one or more of metals, carbon materials and metal oxide materials, wherein the metals are selected from one or more of Al, ag, cu, mo, au, ba, pt, ca and Mg, the carbon materials are selected from one or more of graphite, carbon nano tubes, graphene and carbon fibers, and the metal oxide materials are selected from one or more of indium doped tin oxide, fluorine doped tin oxide, antimony doped tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, zinc magnesium oxide and aluminum doped magnesium oxide; and/or
The light-emitting device further comprises a hole functional layer, wherein the hole functional layer is arranged between the light-emitting layer and the anode, and comprises a hole injection layer and/or a hole transport layer; for the hole functional layer including the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light emitting layer than the hole injection layer;
Wherein the material of the hole injection layer and/or the material of the hole transport layer is selected from poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 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), poly (4, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly (4, 4',4 '-tris (2-naphthylphenylamino) triphenylamine), 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, poly (4, 4' -N, N '-dicarbazolyl-biphenyl), poly (N, N' -diphenyl-N, N '-bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine), poly (4, 4 '-bis (9-carbazole) biphenyl), poly (4, 4',4" -tris (carbazole-9-yl) triphenylamine), and the like, poly (N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine), poly (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro), poly (N, N ' -bis (4- (N, N ' -diphenyl-amino) -phenyl) -N, N ' -diphenyl benzidine), poly (4, 4' -tris (N-carbazolyl) -triphenylamine), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ], poly (4-butylphenyl-diphenylamine), polyaniline, polypyrrole, poly (p-phenylene vinylene, poly (phenylene vinylene), poly (2-methoxy-5- (2-ethylhexyl) -1, 4-phenylene vinylene), poly (2-methoxy-5- (3 ',7' -dioctyl-2, 7-diyl) -1, 4-phenylene vinylene, aromatic amines, 4,4' -bis (P-carbazolyl) -1,1' -biphenyl compounds, one or more of N, N ' -tetraarylbenzidine, poly (N-vinylcarbazole) and derivatives thereof, polymethacrylate esters and derivatives thereof, poly (9, 9-octylfluorene) and derivatives thereof, poly (spirofluorene) and derivatives thereof, poly (N, N ' -bis (naphthalen-1-yl) -N, N ' -diphenylbenzidine), doped or undoped graphene, C60, doped or undoped nickel oxide, doped or undoped molybdenum oxide, doped or undoped tungsten oxide, doped or undoped vanadium oxide, doped or undoped P-gallium nitride, doped or undoped chromium oxide, doped or undoped copper oxide, transition metal sulfide, and transition metal selenide.
11. An electronic device, characterized in that the electronic device comprises the light emitting device according to claim 9 or 10.
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