US-12628553-B2 - Quantum dot material comprising quantum dot and first ligand connected to surface of quantum dot, light-emitting device comprising inner group of quantum dot material and manufacturing method therefor, and display apparatus

US12628553B2US 12628553 B2US12628553 B2US 12628553B2US-12628553-B2

Abstract

Disclosed in embodiments of the present invention are a quantum dot material, a light-emitting device and a manufacturing method therefor, and a display apparatus. The quantum dot material comprises: a quantum dot and at least one first ligand connected to the surface of the quantum dot. The first ligand comprises: an inner group connected to the quantum dot, a first photosensitive group connected to the inner group, and an outer group connected to the first photosensitive group, the inner group being configured to adsorb the quantum dot material on the surface of a carrier film layer, the first photosensitive group being configured to break under the irradiation of ultraviolet light, such that the outer group is separated from the inner group, and the outer group being configured to ionize in an aqueous solution to make the quantum dot material electropositive or electronegative.

Inventors

Zhuo Li

Assignees

BOE TECHNOLOGY GROUP CO., LTD.

Dates

Publication Date: 20260512
Application Date: 20201225

Claims (20)

1 . A quantum dot material, comprising: a quantum dot and at least one first ligand connected to a surface of the quantum dot, wherein the first ligand comprises: an inner group connected to the quantum dot, a first photosensitive group connected to the inner group, and an outer group connected to the first photosensitive group; and the inner group is configured to adsorb the quantum dot material on a surface of a carrier film layer, the first photosensitive group is configured to break under irradiation of ultraviolet light, such that the outer group is separated from the inner group, and the outer group is configured to ionize in an aqueous solution to make the quantum dot material electropositive or electronegative.
2 . The quantum dot material according to claim 1 , wherein a structural formula of the inner group is R 1 -R 2 -R 3 , wherein, R 1 comprises —S, —NH, —P or —PO 2 , R 2 comprises polyethylene oxide or polyethylene glycol, R 3 is a group obtained after a high-effective and specific chemical reaction of a first group, and the first group comprises an azide group, a mercapto group, an amino group, a carboxyl group, an alkyne group, an olefin group, a succinimidyl ester group, a maleimide group, an isothiocyanic acid group, a tetrafluorophenyl ester group, a sulfonated tetrafluorophenyl ester group, a diamide group, a hydroxylamine group or a carbodiimide group.
3 . The quantum dot material according to claim 2 , wherein a structural formula of the first photosensitive group is wherein, R 3 ′ is a group obtained after a high-effective and specific chemical reaction between a second group and the first group, and the second group comprises an alkyne group, an olefin group, a succinimidyl ester group, a maleimide group, an isothiocyanic acid group, a tetrafluorophenyl ester group, a sulfonated tetrafluorophenyl ester group, a diamide group, a hydroxylamine group or a carbodiimide group, an azide group, a mercapto group, an amino group or a carboxyl group; and R 4 is a group obtained after a polymerization reaction initiated by alkane with halogen atoms as an initiator.
4 . The quantum dot material according to claim 3 , wherein in the alkane with the halogen atoms, carbon atoms connected to the halogen atoms are further at least connected to two methyl groups.
5 . The quantum dot material according to claim 4 , wherein the alkane with the halogen atoms comprises bromopropane.
6 . The quantum dot material according to claim 3 , wherein the outer group comprises polyacrylate or derivatives thereof, derivatives of polystyrene, or polyvinylpyridine.
7 . The quantum dot material according to claim 6 , wherein when the outer group comprises the polyacrylate or the derivatives thereof, the outer group is wherein, n≥3, R 5 is H or an alkane group, R 6 is H, or R 6 is or derivatives thereof, and X − is F − , Cl − , Br − , I − , ClO 4 − , SCN − or HSO 3 − ; when the outer group is the derivatives of the polystyrene, the outer group is wherein, n≥3, R 5 is H or an alkane group, and R 7 is Li, Na, K, Rb, or Cs; or when the outer group is the polyvinylpyridine, the outer group is wherein, R 5 is H or an alkane group, and n≥3.
8 . The quantum dot material according to claim 7 , wherein the first ligand comprises: X − is F − , Cl − , Br − , I − , ClO 4 − , SCN − or HSO 3 − , or R 7 is Li, Na, K, Rb or Cs, or wherein, 2≤m≤20.
9 . The quantum dot material according to claim 1 , wherein the quantum dot comprises at least one of CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPbI 3 , CdS/ZnS, CdSe/ZnS, CdSe/ZnSe, InP/ZnS, PbS/ZnS, CsPbCl 3 /ZnS, CsPbBr 3 /ZnS, CsPbI 3 /ZnS, or ZnTeSe/ZnSe.
10 . A manufacturing method for a light-emitting device, comprising: forming a first electrode on a substrate; forming a carrier film layer on the first electrode, wherein a surface of the carrier film layer having a first electrical polarity; forming a quantum dot film layer on the carrier film layer by using the quantum dot material according to claim 1 , wherein the first ligand of the quantum dot material is configured to ionize in an aqueous solution to cause the quantum dot material to present a second electrical polarity, and the second electrical polarity is the same as the first electrical polarity; irradiating a target area of the quantum dot film layer by using ultraviolet light to cause a first photosensitive group in a first ligand of the target area to break, such that an outer group in the first ligand of the target area is separated from an inner group in the first ligand of the target area; cleaning the quantum dot film layer irradiated by the ultraviolet light by using an aqueous solution to form a patterned quantum dot layer in the target area; and forming a second electrode on the quantum dot layer.
11 . The manufacturing method according to claim 10 , wherein the forming the carrier film layer on the first electrode, the surface of the carrier film layer having the first electrical polarity, specifically is as follows: forming the carrier film layer, the surface itself having the first electrical polarity, on the first electrode; or forming the carrier film layer on the first electrode, and treating the surface of the carrier film layer to make the surface of the carrier film layer have the first electrical polarity.
12 . The manufacturing method according to claim 10 , wherein the cleaning the quantum dot film layer irradiated by the ultraviolet light by using the aqueous solution to form the patterned quantum dot layer in the target area, specifically is as follows: ionizing a first ligand of a non-target area not irradiated by the ultraviolet light in the aqueous solution, to cause a quantum dot material in the non-target area to present a second electrical polarity, washing off the quantum dot material in the non-target area by the aqueous solution through an electrostatic repulsion effect between the quantum dot material in the non-target area and the carrier film layer, and adsorbing, by the inner group of the quantum dot material in the target area, the quantum dot material in the target area on the surface of the carrier film layer, so as to form the patterned quantum dot layer in the target area.
13 . The manufacturing method according to claim 10 , wherein the irradiating the target area of the quantum dot film layer by using the ultraviolet light, specifically comprises: blocking the quantum dot film layer by using a mask, wherein the mask comprises a light transmittance area and a light blocking area, the light transmittance area corresponds to the target area in the quantum dot film layer, and the light blocking area corresponds to the non-target area in the quantum dot film layer.
14 . A light-emitting device, comprising a substrate, a first electrode, a carrier film layer, a quantum dot layer and a second electrode which are stacked, wherein the quantum dot layer comprises a quantum dot and a second ligand connected to a surface of the quantum dot, the second ligand comprises: an inner group coordinated with the quantum dot and a second photosensitive group connected to the inner group, the second photosensitive group is a group reserved after a first photosensitive group in the quantum dot material is irradiated by ultraviolet light, and the first photosensitive group and the inner group are the first photosensitive group and the inner group in the quantum dot material according to claim 1 , respectively.
15 . The light-emitting device according to claim 14 , wherein a structure of the quantum dot material in the quantum dot layer is
16 . The light-emitting device according to claim 14 , wherein the first electrode is a cathode, the second electrode is an anode, the carrier film layer is an electron transport layer, and the light-emitting device further comprises a hole transport layer between the quantum dot layer and the second electrode; and the inner group is configured to adsorb the quantum dot material of the quantum dot layer on a surface of the electron transport layer.
17 . The light-emitting device according to claim 16 , further comprising a hole injection layer between the hole transport layer and the second electrode.
18 . The light-emitting device according to claim 14 , wherein the first electrode is an anode, the second electrode is a cathode, the carrier film layer is a hole transport layer, and the light-emitting device further comprises an electron transport layer between the quantum dot layer and the second electrode; and the inner group is configured to adsorb the quantum dot material of the quantum dot layer on a surface of the hole transport layer.
19 . The light-emitting device according to claim 18 , further comprising a hole injection layer between the hole transport layer and the first electrode.
20 . A display apparatus, comprising the light-emitting device according to claim 14 .

Description

The present application is a National Stage of International Application No. PCT/CN2020/139540, filed on Dec. 25, 2020, which is hereby incorporated by reference in its entirety. FIELD The present disclosure relates to the technical field of display, in particular to a quantum dot material, a light-emitting device and a manufacturing method therefor, and a display apparatus. BACKGROUND Quantum dots (QDs), also known as semiconductor nanocrystals and semiconductor nanoparticles, refer to nanosolid materials that have sizes in the order of nanometers in three dimensions of space or are composed of QDs as basic units, and are aggregates of atoms and molecules on a nanoscale. A light-emitting diode based on the quantum dots is called a quantum dot light-emitting diode (QLED), and is a novel light-emitting device. SUMMARY A quantum dot material provided by an embodiment of the present disclosure, includes: a quantum dot and at least one first ligand connected to a surface of the quantum dot, wherein the first ligand includes: an inner group connected to the quantum dot, a first photosensitive group connected to the inner group, and an outer group connected to the first photosensitive group; and the inner group is configured to adsorb the quantum dot material on a surface of a carrier film layer, the first photosensitive group is configured to break under irradiation of ultraviolet light, such that the outer group is separated from the inner group, and the outer group is configured to ionize in an aqueous solution to make the quantum dot material electropositive or electronegative. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, a structural formula of the inner group is R1-R2-R3, wherein, R1 includes —S, —NH, —P or —PO2, R2 is polyethylene oxide or polyethylene glycol, R3 is a group obtained after a high-effective and specific chemical reaction of a first group, and the first group includes an azide group, a mercapto group, an amino group, a carboxyl group, an alkyne group, an olefin group, a succinimidyl ester group, a maleimide group, an isothiocyanic acid group, a tetrafluorophenyl ester group, a sulfonated tetrafluorophenyl ester group, a diamide group, a hydroxylamine group or a carbodiimide group. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, a structural formula of the first photosensitive group is wherein, R3′ is a group obtained after a high-effective and specific chemical reaction between a second group and the first group, and the second group includes an alkyne group, an olefin group, a succinimidyl ester group, a maleimide group, an isothiocyanic acid group, a tetrafluorophenyl ester group, a sulfonated tetrafluorophenyl ester group, a diamide group, a hydroxylamine group or a carbodiimide group, an azide group, a mercapto group, an amino group or a carboxyl group; and R4 is a group obtained after a polymerization reaction initiated by alkane with halogen atoms as an initiator. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, in the alkane with the halogen atoms, carbon atoms connected to the halogen atoms are further at least connected to two methyl groups. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, the alkane with the halogen atoms includes bromopropane. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, the outer group includes polyacrylate or derivatives thereof, derivatives of polystyrene, or polyvinylpyridine. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, when the outer group includes the polyacrylate or the derivatives thereof, the outer group is wherein, n≥3, R5 is H or an alkane group, R6 is H, or R6 is or derivatives thereof, and X− is F−, Cl−, Br−, I−, ClO4−, SCN or HSO3−; when the outer group is the derivatives of the polystyrene, the outer group is wherein, n≥3, R5 is H or an alkane group, and R7 is Li, Na, K, Rb, or Cs; or when the outer group is the polyvinylpyridine, the outer group is wherein, R5 is H or an alkane group, and n≥3. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, the first ligand includes: X− is F−, Cl−, Br−, I−, ClO4−, SCN− or HSO3−, or R7 is Li, Na, K, Rb or Cs, or wherein, 2≤m≤20. Optionally, in the above quantum dot material provided by the embodiment of the present disclosure, the quantum dot includes at least one of CdS, CdSe, ZnSe, InP, PbS, CsPbCl3, CsPbBr3, CsPbI3, CdS/ZnS, CdSe/ZnS, CdSe/ZnSe, InP/ZnS, PbS/ZnS, CsPbCl3/ZnS, CsPbBr3/ZnS, CsPbI3/ZnS, or ZnTeSe/ZnSe. Accordingly, an embodiment of the present disclosure further provides a manufacturing method for a light-emitting device, including: forming a first electrode on a substrate; forming a carrier film layer on the first electrode, a surfa