Quantum dot light emitting device and manufacturing method therefor, and display device
View Patent ↗The present disclosure discloses a quantum dot light emitting device, a preparation method therefor and a display apparatus. In the present disclosure, at least one of one or more layers of light emitting functional layers is disposed to include at least two sub-function layers, the sub-function layers comprise ligands, and surface energies of the ligands corresponding to sub-function layers change in gradient along a transmission direction of carriers in the sub-function layers, so that energy levels of the sub-function layers change in gradient. In this way, the energy levels of the sub-function layers can be matched with the energy levels of the adjacent light emitting function layers, so that carrier transmission and balance as well as device efficiency can be improved.
1 . A quantum dot light emitting device, comprising an anode, one or more layers of light emitting functional layers and a cathode which are disposed in layer configuration; wherein, at least one layer of the light emitting functional layers comprises at least two sub-function layers, the sub-function layers comprise ligands, and surface energies of the ligands corresponding to sub-function layers change in gradient along a transmission direction of carriers in the sub-function layers, so that energy levels of the sub-function layers change in gradient;
wherein the light emitting function layer comprises an electron transport layer, a quantum dot light emitting layer and a hole transport layer, the electron transport layer is close to the cathode, and the hole transport layer is close to the anode; wherein, at least one of the electron transport layers, the quantum dot light emitting layer or the hole transport layer comprises three sub-function layers;
wherein when the electron transport layer comprises three sub-function layers, the electron transport layer comprises a first electron transport sub-layer, a second electron transport sub-layer and a third electron transport sub-layer which are disposed in layer configuration along a first direction; the first direction is a direction from the quantum dot light emitting layer to the cathode; and LUMO energy levels of the first electron transport sub-layer, the second electron transport sub-layer and the third electron transport sub-layer deepen in sequence, and the surface energies of the first electron transport sub-layer, the surface energies of the second electron transport sub-layer and the surface energies of the third electron transport sub-layer decrease in sequence.
2 . The quantum dot light emitting device according to claim 1 , wherein the at least one layer of the light emitting functional layers comprises three sub-function layers;
wherein the ligands comprise: fluorine-containing group ligands with low surface energies as well as hydrophobic amine ligands and hydrophilic amine ligands with high surface energies;
wherein, when the light emitting function layer is manufactured on a hydrophilic film layer, the surface energies of the hydrophilic amine ligands are greater than that of the hydrophobic amine ligands; and
when the light emitting function layer is manufactured on a hydrophobic film layer, the surface energies of the hydrophobic amine ligands are greater than that of the hydrophilic amine ligands;
the hydrophilic amine ligands comprise alcohol amine ligands, and the hydrophobic amine ligands comprise alkane amine ligands.
3 . The quantum dot light emitting device according to claim 2 , wherein when the electron transport layer comprises three sub-function layers, the electron transport layer comprises a first sub-function layer, a second sub-function layer and a third sub-function layer which are disposed in layer configuration, the first sub-function layer is close to the quantum dot light emitting layer, and the third sub-function layer is close to the cathode; and LUMO energy levels of the first sub-function layer, the second sub-function layer and the third sub-function layer deepen in sequence, and the surface energies of the first sub-function layer, the surface energies of the second sub-function layer and the surface energies of the third sub-function layer decrease in sequence or increase in sequence.
4 . The quantum dot light emitting device according to claim 3 , wherein when the electron transport layer is manufactured on a hydrophobic film layer, a material of the first sub-function layer is magnesium zinc oxide nanoparticles with hydrophobic amine as ligands, and a molar mass of the magnesium is 0% to 50% that of the magnesium zinc oxide; a material of the second sub-function layer is magnesium zinc oxide nanoparticles with hydrophilic amine as ligands, and a molar mass of the magnesium is 0% to 50% that of the magnesium zinc oxide; and a material of the third sub-function layer is zinc oxide nanoparticles with fluorine-containing groups as ligands, and a content of the magnesium in the first sub-function layer is greater than a content of the magnesium in the second sub-function layer; and
when the electron transport layer is manufactured on a hydrophilic film layer, a material of the first sub-function layer is magnesium zinc oxide nanoparticles with fluorine-containing groups as ligands, and a molar mass of the magnesium is 0% to 50% that of the magnesium zinc oxide; a material of the second sub-function layer is magnesium zinc oxide nanoparticles with hydrophobic amine as ligands, and a molar mass of the magnesium is 0% to 50% that of the magnesium zinc oxide; and a material of the third sub-function layer is zinc oxide nanoparticles with hydrophilic amine as ligands, and a content of the magnesium in the first sub-function layer is greater than a content of the magnesium in the second sub-function layer.
5 . The quantum dot light emitting device according to claim 2 , wherein when the electron transport layer comprises three sub-function layers, the electron transport layer comprises a first electron transport sub-layer, a second electron transport sub-layer and a third electron transport sub-layer which are disposed in layer configuration along a first direction; the first direction is a direction from the quantum dot light emitting layer to the cathode; and LUMO energy levels of the first electron transport sub-layer, the second electron transport sub-layer and the third electron transport sub-layer deepen in sequence, and the surface energies of the first electron transport sub-layer, the surface energies of the second electron transport sub-layer and the surface energies of the third electron transport sub-layer decrease in sequence.
6 . The quantum dot light emitting device according to claim 5 , wherein the first electron transport sub-layer comprises a first inorganic nanoparticle and a first ligand, the second electron transport sub-layer comprises a second inorganic nanoparticle and a second ligand, and the third electron transport sub-layer comprises a third inorganic nanoparticle and a third ligand; wherein, refractive indexes of the first inorganic nanoparticle, the second inorganic nanoparticle and the third inorganic nanoparticle decrease in turn, and surface energies of the first ligand, surface energies of the second ligand and surface energies of the third ligand decrease in turn.
7 . The quantum dot light emitting device according to claim 6 , wherein the quantum dot light emitting layer comprises quantum dots and hydrophobic ligands, the first ligand comprises an alkyl, the second ligand comprises a hydroxyl or a carboxyl, and the third ligand comprises a fluorine-containing group.
8 . The quantum dot light emitting device according to claim 7 , wherein the first ligand comprises any one of 1,3-dimethylbutylamine, n-butylamine and iso-propylamine;
the second ligand comprises any one of trihydroxymethyl aminomethane, 3-amino-1-propanol and isopropanolamine; and
the third ligand comprises any one of pentafluoropropionamide, 4-(trifluoromethyl)cyclohexylamine, 3-fluoropropylamine and 4-(trifluoromethylthio)aniline;
the quantum dot comprises a core-shell structure, and the hydrophobic ligand comprises 1-dodecanethiol.
9 . The quantum dot light emitting device according to claim 6 , wherein the quantum dot light emitting layer comprises quantum dots and hydrophilic ligands, the first ligand comprises a hydroxyl or carboxyl, the second ligand comprises an alkyl, and the third ligand comprises a fluorine-containing group;
the first ligand comprises any one of trihydroxymethyl aminomethane, 3-amino-1-propanol and isopropanolamine;
the second ligand comprises any one of 1,3-dimethylbutylamine, n-butylamine and iso-propylamine; and
the third ligand comprises any one of pentafluoropropionamide, 4-(trifluoromethyl)cyclohexylamine, 3-fluoropropylamine and 4-(trifluoromethylthio)aniline.
10 . The quantum dot light emitting device according to claim 9 , wherein the quantum dot comprises a core-shell structure, and the hydrophilic ligand comprises 1-hydroxyhexanethiol.
11 . The quantum dot light emitting device according to claim 6 , wherein a material of the first inorganic nanoparticle comprises any one of titanium dioxide, zinc selenide and zinc sulfide; a material of the second inorganic nanoparticle comprises zinc oxide or zirconium oxide; and a material of the third inorganic nanoparticle comprises any one of aluminum oxide, magnesium zinc oxide and magnesium oxide.
12 . The quantum dot light emitting device according to claim 2 , wherein when the quantum dot light emitting layer comprises three sub-function layers, the quantum dot light emitting layer comprises a fourth sub-function layer, a fifth sub-function layer and a sixth sub-function layer which are disposed in layer configuration, the fourth sub-function layer is close to the hole transport layer, and the sixth sub-function layer is close to the electron transport layer; and
HOMO energy levels of the fourth sub-function layer, the fifth sub-function layer and the sixth sub-function layer deepen in sequence, and the surface energies of the fourth sub-function layer, the surface energies of the fifth sub-function layer and the surface energies of the sixth sub-function layer decrease in sequence or increase in sequence.
13 . The quantum dot light emitting device according to claim 12 , wherein ligands of the fourth sub-function layer have triphenylamine or carbazole ligands, ligands of the fifth sub-function layer have alkane ligands, and ligands of the sixth sub-function layer have pyridine ligands;
when the quantum dot light emitting layer is manufactured on a hydrophobic film layer, the ligands of the fourth sub-function layer further have hydrophobic amine ligands, the ligands of the fifth sub-function layer further have hydrophilic amine ligands, and the ligands of the sixth sub-function layer further have fluorine-containing group ligands; and
when the quantum dot light emitting layer is manufactured on a hydrophilic film layer, the ligands of the fourth sub-function layer further have fluorine-containing group ligands, the ligands of the fifth sub-function layer further have hydrophobic amine ligands, and the ligands of the sixth sub-function layer further have hydrophilic amine ligands.
14 . The quantum dot light emitting device according to claim 2 , wherein when the quantum dot light emitting layer comprises three sub-function layers, the quantum dot light emitting layer comprises a fourth sub-function layer, a fifth sub-function layer and a sixth sub-function layer which are disposed in layer configuration, the fourth sub-function layer is close to the hole transport layer, and the sixth sub-function layer is close to the electron transport layer; and
LUMO energy levels of the fourth sub-function layer, the fifth sub-function layer and the sixth sub-function layer deepen in sequence, and the surface energies of the fourth sub-function layer, the surface energies of the fifth sub-function layer and the surface energies of the sixth sub-function layer decrease in sequence or increase in sequence.
15 . The quantum dot light emitting device according to claim 14 , wherein:
when the quantum dot light emitting layer is manufactured on a hydrophobic film layer, the ligands of the fourth sub-function layer have hydrophobic amine ligands, the ligands of the fifth sub-function layer further have hydrophilic amine ligands, and the ligands of the sixth sub-function layer have fluorine-containing group ligands; and
when the quantum dot light emitting layer is manufactured on a hydrophilic film layer, the ligands of the fourth sub-function layer further have fluorine-containing group ligands, the ligands of the fifth sub-function layer further have hydrophobic amine ligands, and the ligands of the sixth sub-function layer have hydrophilic amine ligands.
16 . The quantum dot light emitting device according to claim 2 , wherein when the hole transport layer comprises three sub-function layers, the hole transport layer comprises a seventh sub-function layer, an eighth sub-function layer and a ninth sub-function layer which are disposed in layer configuration, the seventh sub-function layer is close to the anode, and the ninth sub-function layer is close to the quantum dot light emitting layer; and HOMO energy levels of the seventh sub-function layer, the eighth sub-function layer and the ninth sub-function layer deepen in sequence, and the surface energies of the seventh sub-function layer, the surface energies of the eighth sub-function layer and the surface energies of the ninth sub-function layer decrease in sequence or increase in sequence.
17 . The quantum dot light emitting device according to claim 16 , wherein when the hole transport layer is manufactured on a hydrophilic film layer, a material of the seventh sub-function layer is nickel oxide nanoparticles with hydrophilic amine as ligands; a material of the eighth sub-function layer is nickel cesium oxide nanoparticles with hydrophobic amine as ligands, and a molar mass of the cesium is 0% to 50% that of the nickel cesium oxide; and a material of the ninth sub-function layer is nickel cesium oxide nanoparticles with fluorine-containing groups as ligands, a molar mass of the cesium is 0% to 50% that of the nickel cesium oxide, and a content of the cesium in the ninth sub-function layer is greater than a content of the cesium in the eighth sub-function layer; and
when the hole transport layer is manufactured on a hydrophobic film layer, a material of the seventh sub-function layer is nickel oxide nanoparticles with fluorine-containing groups as ligands; a material of the eighth sub-function layer is nickel cesium oxide nanoparticles with hydrophilic amine as ligands, and a molar mass of the cesium is 0% to 50% that of the nickel cesium oxide; and a material of the ninth sub-function layer is nickel cesium oxide nanoparticles with hydrophobic amine as ligands, a molar mass of the cesium is 0% to 50% that of the nickel cesium oxide, and a content of the cesium in the ninth sub-function layer is greater than a content of the cesium in the eighth sub-function layer.
18 . A display apparatus, comprising the quantum dot light emitting device according to claim 1 .
19 . A preparation method of a quantum dot light emitting device, comprising:
forming an anode, one or more layers of light emitting functional layers and a cathode which are disposed in layer configuration; wherein, at least one layer of the light emitting functional layers is formed through a one-time spin-coating process, and comprises at least two sub-function layers; wherein, the sub-function layers comprise ligands, and surface energies of the ligands corresponding to sub-function layers change in gradient along a transmission direction of carriers in the sub-function layers, so that energy levels of the sub-function layers change in gradient;
wherein the light emitting function layer comprises an electron transport layer, a quantum dot light emitting layer and a hole transport layer, the electron transport layer is close to the cathode, and the hole transport layer is close to the anode; wherein, at least one of the electron transport layers, the quantum dot light emitting layer or the hole transport layer comprises three sub-function layers;
wherein when the electron transport layer comprises three sub-function layers, the electron transport layer comprises a first electron transport sub-layer, a second electron transport sub-layer and a third electron transport sub-layer which are disposed in layer configuration along a first direction; the first direction is a direction from the quantum dot light emitting layer to the cathode; and LUMO energy levels of the first electron transport sub-layer, the second electron transport sub-layer and the third electron transport sub-layer deepen in sequence, and the surface energies of the first electron transport sub-layer, the surface energies of the second electron transport sub-layer and the surface energies of the third electron transport sub-layer decrease in sequence.
20 . The preparation method according to claim 19 , wherein the step of forming the light emitting function layers comprises:
preparing three function layer materials with surface energies and energy levels of the ligands changing in gradient;
mixing the three function layer materials to form a mixed solution; and
spin-coating the mixed solution by adopting a spin-coating method to form the light emitting function layers;
when the mixed solution is spin-coated on a hydrophilic film layer, surface energies of hydrophilic amine ligands are greater than that of hydrophobic amine ligands; and
when the mixed solution is spin-coated on a hydrophobic film layer, the surface energies of the hydrophobic amine ligands are greater than that of the hydrophilic amine ligands.