CN113611806A - Light-emitting device, manufacturing method thereof and light-emitting device - Google Patents

Light-emitting device, manufacturing method thereof and light-emitting device Download PDF

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CN113611806A
CN113611806A CN202110473554.3A CN202110473554A CN113611806A CN 113611806 A CN113611806 A CN 113611806A CN 202110473554 A CN202110473554 A CN 202110473554A CN 113611806 A CN113611806 A CN 113611806A
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quantum dot
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light
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core
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CN113611806B (en
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张晓远
冯靖雯
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BOE Technology Group Co Ltd
Beijing BOE Technology Development Co Ltd
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BOE Technology Group Co Ltd
Beijing BOE Technology Development Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

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Abstract

The embodiment of the present disclosure provides a light emitting device, a method of manufacturing the same, and a light emitting apparatus, the light emitting device including: the first electrode and the second electrode are positioned on the substrate and are oppositely arranged; a quantum dot light emitting layer positioned between the first electrode and the second electrode; the quantum dot light-emitting layer comprises at least one quantum dot nanorod array layer, the quantum dot nanorod array layer comprises a plurality of quantum dot nanorods, each quantum dot nanorod comprises a quantum dot core and a rod-shaped shell layer coated outside the quantum dot core, each rod-shaped shell layer comprises a first end and a second end which are opposite, and the quantum dot core is located on one side, close to the first end, of a central point between the first end and the second end. The light-emitting device, the manufacturing method thereof and the light-emitting device provided by the embodiment of the disclosure can improve carrier injection balance in the device, and improve efficiency and service life of the device.

Description

Light-emitting device, manufacturing method thereof and light-emitting device
Technical Field
The present disclosure relates to the field of display technologies, and in particular, to a light emitting device, a method for manufacturing the same, and a light emitting apparatus.
Background
The colloidal quantum dots have great application potential in the aspect of high color quality display due to the excellent characteristics of high quantum efficiency, narrow excitation spectrum, unique size dependence excitation spectrum, good solution processing compatibility and the like. Quantum dot light-emitting diodes (QLEDs) are devices in which Quantum dots are used as light-emitting layers, are superior to organic light-emitting diodes, and are expected to become the core of the next generation of display technology. In recent years, with the continuous development of quantum dot electroluminescent technology, a small number of related display products are put on the market, but the distance from large-scale mass production is still long, mainly because the efficiency of the device is still low, and the service life needs to be improved continuously.
In the related art, the structure of the quantum dot light emitting diode mainly comprises an electrode, a hole and electron transport layer and a middle quantum dot light emitting layer, and the problem of unbalanced hole and electron injection exists, so that the efficiency of the device is not high, and the service life of the device is shortened.
Disclosure of Invention
The embodiment of the disclosure provides a light emitting device, a manufacturing method thereof and a light emitting device, which can improve carrier injection balance in the device, improve efficiency of the device and prolong service life of the device.
The technical scheme provided by the embodiment of the disclosure is as follows:
an aspect of an embodiment of the present disclosure provides a light emitting device, including:
a first electrode and a second electrode formed on the substrate and arranged oppositely;
a quantum dot light emitting layer positioned between the first electrode and the second electrode;
the quantum dot light-emitting layer comprises at least one quantum dot nanorod array layer, the quantum dot nanorod array layer comprises a plurality of quantum dot nanorods, each quantum dot nanorod comprises a quantum dot core and a rod-shaped shell layer coated outside the quantum dot core, each rod-shaped shell layer comprises a first end and a second end which are opposite, and the quantum dot core is located on one side, close to the first end, of a central point between the first end and the second end.
Illustratively, the light emitting device further includes: a hole transport layer between the first electrode and the quantum dot light emitting layer and an electron transport layer between the second electrode and the quantum dot light emitting layer; wherein the first end is proximate to the hole transport layer and the second end is proximate to the electron transport layer.
Illustratively, a plurality of the quantum dot nanorods are arranged in a perpendicular manner to the substrate.
Illustratively, the quantum dot core is a magnetic quantum dot core.
Illustratively, the surface of the magnetic quantum dot core comprises magnetic ions.
Illustratively, the magnetic ions include at least one of Co ions, Fe ions, and Ni ions.
Illustratively, the quantum dot nanorod further comprises a charged ligand at one end of the outer surface of the rod-shaped shell.
Illustratively, the quantum dot nanorod has a length of 20-80 nm and a diameter of 3-10 nm.
Illustratively, the material of the rod-shaped shell layer includes ZnS, CdS, ZnSe, ZnSeS, CdZnS, ZnO, ZnCdS, CdxZn1-xSeyS1-yWherein 0 is<x<1，0<y<1。
Illustratively, the host material of the quantum dot core comprises CdSe and the material of the rod-like shell layer comprises CdS.
Illustratively, the quantum dot light-emitting layer further comprises at least one quantum dot nanoparticle array layer, the quantum dot nanoparticle array comprises quantum dot nanoparticles, the quantum dot nanoparticles comprise quantum dot cores and spherical shell layers wrapping the quantum dot cores, and the quantum dot nanoparticle array layer is arranged on one side of the quantum dot nanorod array layer, which is close to the hole transport layer and/or the electron transport layer.
The embodiment of the present disclosure also provides a light emitting apparatus, which includes a plurality of light emitting devices arranged in an array.
The embodiment of the present disclosure also provides a method for manufacturing a light emitting device, for manufacturing the light emitting device provided by the embodiment of the present disclosure, the method including:
forming the first electrode on a substrate;
forming the quantum dot light-emitting layer on the first electrode, wherein the quantum dot light-emitting layer comprises at least one quantum dot nanorod array layer, the quantum dot nanorod array layer comprises a plurality of quantum dot nanorods, each quantum dot nanorod comprises a quantum dot core and a rod-shaped shell layer coated outside the quantum dot core, each rod-shaped shell layer comprises a first end and a second end which are opposite, and the quantum dot core is positioned on one side, close to the first end, of a central point between the first end and the second end;
forming the second electrode on the quantum dot light emitting layer.
Illustratively, the forming the quantum dot light emitting layer specifically includes:
preparing a quantum dot core;
introducing magnetic ions on the surface of the quantum dot core to form a magnetic quantum dot core, wherein the surface of the magnetic quantum dot core is provided with the magnetic ions;
wrapping a rod-shaped shell layer around the quantum dot core, wherein a ligand with charges is formed at one end of the surface of the rod-shaped shell layer, so as to obtain a quantum dot nanorod solution;
and forming the quantum dot nanorod array layer by film formation of the quantum dot nanorod solution, wherein in the film formation process of the quantum dot nanorod solution, the orientation of the quantum dot nanorods is controlled by applying an electric field and a magnetic field and controlling the direction of the electric field, the quantum dot cores are positioned at the positions close to the first ends of the rod-shaped shell layers by controlling the direction of the magnetic field, and the quantum dot nanorod array layer is obtained by annealing, drying and film formation.
Illustratively, the magnetic ion is introduced to the surface of the quantum dot core to obtain a magnetic quantum dot core, which specifically includes:
and the outermost surface of the quantum dot core is provided with anions and cations which are alternately arranged, the quantum dot core is dissolved in a nonpolar solvent and heated in an inert gas atmosphere, and a small amount of material with magnetic ions is added into the nonpolar solvent, so that the magnetic ions are combined with part of the anions to form the magnetic ions on the surface of the quantum dot core, and the magnetic quantum dot core is obtained.
The beneficial effects brought by the embodiment of the disclosure are as follows:
the luminescent device, the manufacturing method thereof and the luminescent device provided by the embodiment of the disclosure have the advantages that the quantum dot layer comprises at least one quantum dot nanorod array layer, the quantum dot nanorods are in a rod-shaped structure, and the quantum dot cores are not arranged at the centers of rod-shaped shell layers but are biased to one ends of the rod-shaped shell layers, so that the positions of the quantum dot cores can be adjusted by controlling the orientation of the quantum dot nanorods, the transmission distance between electrons and holes can be adjusted, the balance of carrier injection can be adjusted, and the efficiency and the service life of the device can be improved.
In addition, in some embodiments of the present disclosure, the quantum dot core of the quantum dot nanorod is a magnetic quantum dot core, and the quantum dot nanorod can be orderly arranged at a predetermined angle with the electron transport layer by magnetic field control, and the quantum dot core is close to one side of the hole transport layer, so that the hole transport distance is reduced, and the electron transport distance is increased to adjust carrier balance; in addition, the quantum dot nanorods are orderly arranged at a preset angle with the electron transport layer, so that the light extraction efficiency can be improved, and finally the efficiency of the device is improved.
Drawings
Fig. 1 shows a schematic structural view of a quantum dot core of a quantum dot nanorod of a light emitting device in one embodiment provided by the present disclosure;
fig. 2 shows a schematic view of a quantum dot nanorod structure of a light emitting device in one embodiment provided by the present disclosure;
fig. 3 shows a schematic structural diagram of a light emitting device in an embodiment provided by the present disclosure;
fig. 4 shows a schematic structural diagram of a light emitting device in another embodiment provided by the present disclosure;
fig. 5 shows a schematic structural diagram of a light emitting device in another embodiment provided by the present disclosure;
fig. 6 shows a schematic structural diagram of a light-emitting device in another embodiment provided by the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be described clearly and completely with reference to the drawings of the embodiments of the present disclosure. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
Unless otherwise defined, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in this disclosure is not intended to indicate any order, quantity, or importance, but rather is used to distinguish one element from another. Also, the use of the terms "a," "an," or "the" and similar referents do not denote a limitation of quantity, but rather denote the presence of at least one. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships may also be changed accordingly.
Before detailed description of the light emitting device, the method for manufacturing the same, and the light emitting apparatus provided in the embodiments of the present disclosure, it is necessary to describe the following related art:
in the related art, a quantum dot light emitting device (QLED) mainly includes an anode, a cathode, a hole transport layer, an electron transport layer, and a quantum dot light emitting layer, where carrier mobility of the electron transport layer is different from that of the hole transport layer in the device, resulting in imbalance of carrier injection in the device, where electrons are often many and holes are few. The unbalance of carrier can cause the efficiency of device not high on the one hand, and on the other hand, to take electron to be many son and the hole is few son as an example, unnecessary electron can make the quantum dot electrified, makes the quantum dot take place to quench or makes the carrier form auger recombination, reduces the device life-span, consequently, improves the electron and hole injection's balance, and is very important to improving device efficiency and life-span.
In order to improve electron hole injection balance, embodiments of the present disclosure provide a light emitting device, a method of manufacturing the same, and a light emitting apparatus, which can improve carrier injection balance to improve device efficiency and lifetime.
As shown in fig. 1-6, in some embodiments, the present disclosure provides a light emitting device comprising:
a first electrode 200 and a second electrode 300 disposed on the substrate 100 in an opposing arrangement;
a quantum dot light emitting layer 400 positioned between the first electrode 200 and the second electrode 300;
the quantum dot light emitting layer 400 includes at least one quantum dot nanorod array layer 410, the quantum dot nanorod array layer 410 includes a plurality of quantum dot nanorods, each quantum dot nanorod includes a quantum dot core 411 and a rod-shaped shell layer 415 coated outside the quantum dot core 411, the rod-shaped shell layer 415 includes a first end and a second end opposite to each other, and the quantum dot core 411 is located at a side of a central point between the first end and the second end, the side being close to the first end.
In the above scheme, the quantum dot layer of the light emitting device includes at least one quantum dot nanorod array layer 410, the quantum dot nanorods are in a rod-like structure, and the quantum dot cores 411 are not located at the center of the rod-like shell 415 but biased to one end of the rod-like shell 415, so that the positions of the quantum dot cores 411 can be adjusted by controlling the orientation of the quantum dot nanorods to adjust the transmission distance of electrons and holes, thereby adjusting the balance of carrier injection, and improving the efficiency and the lifetime of the device.
In some embodiments of the present disclosure, the light emitting device further includes a hole transport layer 210 between the first electrode 200 and the quantum dot light emitting layer 400, and an electron transport layer 310 between the second electrode 300 and the quantum dot light emitting layer 400. The electron transport layer 310 may be made of an inorganic semiconductor material, for example, one or more of ZnO (zinc oxide) and ZnMgO (magnesium zinc oxide), which has high carrier mobility; the hole transport layer 210 may be made of an organic material, such as one or more of TFB, PVK, etc., which has a low carrier mobility and thus causes carrier injection imbalance.
In the example that the electron is a majority and the hole is a minority before the quantum dot nanorod array layer 410, in one embodiment, as shown in fig. 2 and 3, the first end of each quantum dot nanorod in the quantum dot nanorod array layer 410 is close to the hole transport layer 210, and the second end is close to the electron transport layer 310. Thus, the quantum dot core 411 is close to the hole transport layer 210 side, so that the hole transport distance can be reduced, and the electron transport distance can be increased, thereby adjusting the carrier injection balance.
It is understood that, in other embodiments, for example, before the quantum dot nanorod array layer 410, the electron in the device is minority and the hole is majority, the first end of each quantum dot nanorod in the quantum dot nanorod array layer 410 is close to the electron transport layer 310, and the second end is close to the hole transport layer 210. Thus, the quantum dot core 411 is close to the electron transport layer 310 side, so that the electron transport distance can be reduced, and the hole transport distance can be increased, thereby adjusting the carrier injection balance.
It should be understood that in practical applications, the quantum dot core 411 position of the quantum dot nanorod should be set according to the carrier injection balance requirement of the device.
Furthermore, in some embodiments of the present disclosure, each of the quantum dot nanorods is orderly arranged at a predetermined angle to the substrate 100. It should be noted that the term "ordered arrangement" refers to the ordered orientation of each quantum dot nanorod, for example, the orientation of each quantum dot nanorod is consistent. The predetermined angle is an angle between the length direction of the quantum dot nanorod and the substrate 100, and a value range of the predetermined angle can be determined according to a distance between the quantum dot core 411 and the electron transport layer 310 and a distance between the quantum dot core 411 and the hole transport layer 210 in practical application.
For example, as an exemplary embodiment, as shown in fig. 2, a plurality of the quantum dot nanorods are disposed in a perpendicular manner to the substrate 100. That is, the predetermined angle is substantially 90 °. It should be noted that, here, the quantum dot nanorods are perpendicular to the substrate 100, the predetermined angle is not limited to 90 °, and the angle is in the range of 80-100 °.
By adopting the scheme, the quantum dot nanorods are perpendicular to the substrate 100, namely perpendicular to other functional layers, such as the electron transport layer 310 and the hole transport layer 210, so that the structure is more favorable for improving light extraction, and the efficiency of the device is improved. It is of course understood that the orientation of the quantum dot nanorods may not be limited to the above manner in practical applications.
Further, as an exemplary embodiment, the quantum dot core 411 is a magnetic quantum dot core 411.
In some embodiments of the present disclosure, the surface of the magnetic quantum dot core 411 includes magnetic ions. The magnetic ions include, but are not limited to, one or more of Co (cobalt) ions, Fe (iron) ions, Ni (nickel) ions, and the like. The quantum dot nanorod further includes a charged ligand (not shown) at one end of the outer surface of the rod-shaped shell 415. The charged ligand material may include one or several of sodium polystyrene sulfonate, sodium aminobenzenesulfonate, sodium sulfamate, sodium amino carboxylate, etc.
With the above scheme, since the ligand at one end of the rod-shaped shell 415 has charged ions, in the process of forming the quantum dot nanorod layer, the quantum dot nanorods are orderly arranged in a direction forming a predetermined angle with the substrate 100 by using electric field regulation, that is, the orientation of the quantum dot nanorods can be controlled by electric field regulation; meanwhile, because the surface of the quantum dot core 411 also has magnetic ions, the quantum dot core 411 of the quantum dot nanorod can be close to the first end of the rod-shaped shell 415 by controlling the direction of the magnetic field.
In addition, as some exemplary embodiments, the quantum dot nanorod has a length of 20-80 nm and a diameter of 3-10 nm. It is of course understood that the length and diameter of the quantum dot nanorods are not limited to the above examples.
In addition, the material of the quantum dot core 411 may be selected from CdS, CdSe, CdSeS, CdTe, CdSeS, ZnSe, ZnCdSe, InP, CuInS, PbS, CsPbCl3，CsPbBr3，CsPbI3One or more of the following; the rod-shaped shell 415 can be made of ZnS, CdS, ZnSe, ZnSeS, CdZnS, ZnO, ZnCdS, CdxZn1-xSeyS1-yWherein 0 is<x<1，0<y<1。
In an exemplary embodiment, the host material of the quantum dot core 411 may be CdSe, and the material of the rod-shaped shell 415 may be CdS.
Further, in some exemplary embodiments of the present disclosure, as shown in fig. 3, the quantum dot light emitting layer 400 may include only one or at least two of the quantum dot nanorod array layers 410; in other exemplary embodiments of the present disclosure, as shown in fig. 4 to 6, the quantum dot light emitting layer 400 may further include at least one quantum dot nanoparticle array layer 420, where the quantum dot nanoparticle array layer 420 includes a plurality of quantum dot nanoparticles, and the quantum dot nanoparticles include a quantum dot core 421 and a spherical shell layer 422 wrapped outside the quantum dot core 421.
Taking fig. 4 as an example, the quantum dot nanorod array layer 420 is disposed on a side of the quantum dot nanorod array layer 410 close to the hole transport layer 210.
Taking fig. 5 as an example, the quantum dot nanorod array layer 420 is disposed on a side of the quantum dot nanorod array layer 410 close to the electron transport layer 310.
Taking fig. 6 as an example, the quantum dot nanorod array layer 420 has at least two layers, which are respectively disposed on the side of the quantum dot nanorod array layer 410 close to the electron transport layer 310 and the side of the quantum dot nanorod array layer 410 close to the hole transport layer 210.
The quantum dot core in the quantum dot nanoparticle may have magnetic ions (as shown in fig. 4 to 6) or may not have magnetic ions (not shown).
It should be further noted that, in some embodiments of the present disclosure, as shown in fig. 3, the light emitting device structure includes: the first electrode 200, the second electrode 300, the electron transport layer 310, the hole transport layer 210, and the quantum dot light emitting layer 400 may further include other functional layers to modify according to actual needs, for example, an electron injection layer, an electron blocking layer, a hole blocking layer, or a hole injection layer (not shown in the figure) may also be added to the light emitting device according to actual needs.
In addition, it should be noted that the light emitting device may be a positive light emitting device, i.e., the bottom electrode is an anode and the top electrode is a cathode; it may also be an inverted light emitting device, i.e. the bottom electrode is the cathode and the top electrode is the anode. Accordingly, the light emitting device may be a top light emitting device or a bottom light emitting device.
In addition, the embodiment of the disclosure also provides a light-emitting device, which comprises a plurality of light-emitting devices arranged in an array. Obviously, the light emitting device provided by the embodiment of the present disclosure can also bring the beneficial effects brought by the light emitting device provided by the embodiment of the present disclosure, and details are not repeated herein.
In addition, the embodiment of the present disclosure also provides a method for manufacturing a light emitting device, for manufacturing the light emitting device provided by the embodiment of the present disclosure, the method including:
forming a first electrode 200 on a substrate 100;
forming a quantum dot light emitting layer 400 on the first electrode 200, wherein the quantum dot light emitting layer 400 comprises at least one quantum dot nanorod array layer 410, the quantum dot nanorod array layer 410 comprises a plurality of quantum dot nanorods, the quantum dot nanorods comprise a quantum dot core 411 and a rod-shaped shell layer 415 coated outside the quantum dot core 411, the rod-shaped shell layer 415 comprises a first end and a second end which are opposite, and the quantum dot core 411 is located on one side of a central point between the first end and the second end, which is close to the first end;
a second electrode 300 is formed on the quantum dot light emitting layer 400.
According to the manufacturing method of the light-emitting device provided by the embodiment of the disclosure, the quantum dot layer comprises at least one quantum dot nanorod array layer 410, the quantum dot nanorods are in a rod-shaped structure, and the quantum dot cores 411 are not in the center of the rod-shaped shell layer 415 but are biased to one end of the rod-shaped shell layer 415, so that by controlling the orientation of the quantum dot nanorods, the positions of the quantum dot cores 411 can be adjusted to adjust the transmission distance of electrons and holes, thereby adjusting the balance of carrier injection, and improving the efficiency and the service life of the device.
As an exemplary embodiment, in the method, the forming the quantum dot light emitting layer 400 specifically includes the following steps:
step S01, preparing a quantum dot core 411;
the quantum dot core 411 may be made of CdS, CdSe, CdSeS, CdTe, CdSeS, ZnSe, ZnCdSe, InP, CuInS, PbS, CsPbCl3，CsPbBr3，CsPbI3And the like.
Taking the quantum dot core 411 material as an example, the specific synthesis method in one example of the quantum dot core 411 is as follows: 3g of TOPO (trioctylphosphine oxide), 0.28g of ODPA (4,4' -oxydiphthalic anhydride) and 0.06g of CdO (cadmium oxide) were added to the flask and heated to 150 ℃; then, vacuumizing the flask, and filling inert gas; continuously heating the flask to 300 ℃ to completely dissolve the CdO, and enabling the solution to become clear and transparent; under these conditions 1.5g of trioctylphosphine are added; thereafter, the temperature was raised to 370 ℃ and a solution of trioctylphosphine in which Se (selenium) was dissolved (for example, the solution of trioctylphosphine in which Se (selenium) was dissolved can be obtained by dissolving 58mg of Se in 360mg of TOP) was rapidly added, and the reaction was stopped after about 3 minutes; and extracting and washing the nanocrystals with methanol and toluene, repeating for three times to finally obtain the CdSe quantum dot core 411, wherein the outermost surface of the CdSe quantum dot core 411 is provided with anions Se 412 and cations Cd 413 which are alternately arranged.
Step S02, introducing magnetic ions on the surface of the quantum dot core 411 to form a magnetic quantum dot core 411, where the surface of the magnetic quantum dot core 411 has magnetic ions, and fig. 1 is a schematic structural diagram of the magnetic quantum dot core 411 in an embodiment;
specifically, step S02 may include the following steps: the outermost surface of the quantum dot core 411 has anions and cations alternately arranged, the quantum dot core 411 is dissolved in a nonpolar solvent and heated under an inert gas atmosphere, a small amount of a material having magnetic ions is added to the nonpolar solvent, so that the magnetic ions are combined with a part of the anions by replacing a part of the cations through an ion exchange reaction to form magnetic ions on the surface of the quantum dot core 411, resulting in the magnetic quantum dot core 411.
For example, taking the CdSe quantum dot core 411 prepared by the above steps as an example, the anion Se 412 and the cation Cd 413 are alternately arranged on the outermost layer of the CdSe quantum dot core 411, and the amount of the magnetic ion cobalt is controlled so that the cobalt ion is combined with only the anion Se 412 on the outermost layer of the quantum dot core 411 to form a single layer of cobalt ion 414. One specific embodiment may be as follows: and dissolving the CdSe quantum dot core 411 in trioctylphosphine, heating to 130 ℃ in an inert gas atmosphere, adding a small amount of cobalt oleate into the solution, stirring for reacting for 30 minutes, and stopping to obtain the CdSe quantum dot core 411 solution with Co ions.
Step S03, wrapping a rod-shaped shell 415 around the quantum dot core 411, and forming a charged ligand at one end of the surface of the rod-shaped shell 415 to obtain a quantum dot nanorod solution, which is shown in fig. 3 as a schematic structural diagram of a quantum dot nanorod;
wherein the material of the rod-shaped shell 415 can be selected from ZnS, CdS, ZnSe, ZnSeS, CdZnS, ZnO, ZnCdS, CdxZn1-xSeyS1-yWherein 0 is<x<1，0<y<1；
The material of the charged ligand can be one or more selected from sodium polystyrene sulfonate, sodium aminobenzenesulfonate, sodium sulfamate, sodium aminocarboxylate and the like.
Taking the rod-shaped shell 415 as an example of CdS, a specific synthesis method can be as follows: firstly, 120mg of sulfur is dissolved in 1.5g of TOP (trioctylphosphine), 0.2ml of CdSe quantum dot solution is heated to 300 ℃, trioctylphosphine and sulfur are rapidly added, sodium aminobenzenesulfonate and oleic acid are added into the solution after the reaction is carried out for 10 minutes at 350 ℃, the reaction is continued for 15 minutes at 350 ℃, and then the quantum dot nanorod solution is obtained.
Step S04, forming the quantum dot nanorod array layer 410 by the quantum dot nanorod solution, wherein in the quantum dot nanorod solution film forming process, the quantum dot nanorods are orderly arranged by applying an electric field and a magnetic field and controlling the direction of the electric field, the quantum dot cores 411 are located at a position close to the first end of the rod-shaped shell layer 415 by controlling the direction of the magnetic field, and annealing, drying and film forming are performed to obtain the quantum dot nanorod array layer 410.
Taking the preparation of the upright light emitting device as an example, the manufacturing method of the light emitting device provided by the embodiment of the present disclosure may specifically include the following steps:
the method comprises the following steps of (1) ultrasonically cleaning a substrate 100 (such as an ITO conductive substrate) by using water, ethanol and acetone for 10 minutes in sequence, and then drying for later use;
forming a first electrode 200 on a substrate 100;
depositing hole transport layer 210(HT) ink in the pixels of substrate 100 and drying to form a film, forming hole transport layer 210;
under the conditions of an electric field and a magnetic field, printing the quantum dot nanorod solution, adjusting the electric field to enable quantum dot nanorods to be orderly arranged in a pixel in a direction forming a preset angle with the substrate 100, meanwhile, controlling the direction of the magnetic field to enable one end, where a quantum dot core 411 of each quantum dot nanorod is located, to be close to the hole transport layer 210 for arrangement, annealing, drying and forming a film, and forming a quantum dot nanorod array layer 410;
after the quantum rod is formed into a film, printing the electron transport layer 310, annealing and drying the film to form the electron transport layer 310;
the device is transferred to a vacuum evaporator to evaporate the second electrode 300, and the device is packaged.
When the light emitting device in the embodiment shown in fig. 4 to 6 is manufactured by the above method, the forming the quantum dot light emitting layer 400 in the method specifically further includes:
forming the quantum dot nanorod array layer 420 before forming the quantum dot nanorod array layer 410;
and/or, after forming the quantum dot nanorod array layer 410, forming the quantum dot nanoparticle array layer 420.
The quantum dot nanoparticle array layer 420 includes a quantum dot core 421 and a spherical shell 422 wrapping the quantum dot core 421, and the manufacturing method of the quantum dot core 421 may be the same as the preparation method of the quantum dot core 411 in the quantum dot nanorod, and details are not repeated here.
The following points need to be explained:
(1) the drawings of the embodiments of the disclosure only relate to the structures related to the embodiments of the disclosure, and other structures can refer to the common design.
(2) For purposes of clarity, the thickness of layers or regions in the figures used to describe embodiments of the present disclosure are exaggerated or reduced, i.e., the figures are not drawn on a true scale. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" or "under" another element, it can be "directly on" or "under" the other element or intervening elements may be present.
(3) Without conflict, embodiments of the present disclosure and features of the embodiments may be combined with each other to arrive at new embodiments.
The above is only a specific embodiment of the present disclosure, but the scope of the present disclosure is not limited thereto, and the scope of the present disclosure should be determined by the scope of the claims.

Claims (15)

1. A light emitting device, comprising:
a first electrode and a second electrode disposed opposite to each other on the substrate;
a quantum dot light emitting layer positioned between the first electrode and the second electrode;
the quantum dot light-emitting layer comprises at least one quantum dot nanorod array layer, the quantum dot nanorod array layer comprises a plurality of quantum dot nanorods, each quantum dot nanorod comprises a quantum dot core and a rod-shaped shell layer coated outside the quantum dot core, each rod-shaped shell layer comprises a first end and a second end which are opposite, and the quantum dot core is located on one side, close to the first end, of a central point between the first end and the second end.
2. The light-emitting device according to claim 1,
the light emitting device further includes: a hole transport layer between the first electrode and the quantum dot light emitting layer and an electron transport layer between the second electrode and the quantum dot light emitting layer; wherein the content of the first and second substances,
the first end is adjacent to the hole transport layer and the second end is adjacent to the electron transport layer.
3. The light-emitting device according to claim 1,
the quantum dot nanorods are arranged in a manner of being perpendicular to the substrate.
4. The light-emitting device according to claim 1,
the quantum dot core is a magnetic quantum dot core.
5. The light-emitting device according to claim 4,
the surface of the magnetic quantum dot core includes magnetic ions.
6. The light-emitting device according to claim 5,
the magnetic ions include at least one of Co ions, Fe ions, and Ni ions.
7. The light-emitting device according to claim 1,
the quantum dot nanorod further comprises a charged ligand positioned at one end of the outer surface of the rod-shaped shell layer.
8. The light-emitting device according to claim 1,
the quantum dot nanorod is 20-80 nm in length and 3-10 nm in diameter.
9. The light-emitting device according to claim 1,
the rod-shaped shell layer is made of ZnS, CdS, ZnSe, ZnSeS, CdZnS, ZnO, ZnCdS, CdxZn1-xSeyS1-yWherein 0 is<x<1，0<y<1。
10. The light-emitting device according to claim 8, wherein the light-emitting device comprises a light-emitting element
The main body material of the quantum dot core comprises CdSe, and the material of the rod-shaped shell layer comprises CdS.
11. The light-emitting device according to claim 1,
the quantum dot light-emitting layer further comprises at least one quantum dot nanoparticle array layer, the quantum dot nanoparticle array comprises quantum dot nanoparticles, the quantum dot nanoparticles comprise quantum dot cores and spherical shell layers wrapping the quantum dot cores, and the quantum dot nanoparticle array layer is arranged on one side, close to the hole transmission layer and/or the electron transmission layer, of the quantum dot nanorod array layer.
12. A light-emitting apparatus comprising a plurality of light-emitting devices according to any one of claims 1 to 11 arranged in an array.
13. A method for manufacturing a light emitting device, characterized by being used for manufacturing the light emitting device according to any one of claims 1 to 11, the method comprising:
forming the first electrode on a substrate;
forming the quantum dot light-emitting layer on the first electrode, wherein the quantum dot light-emitting layer comprises at least one quantum dot nanorod array layer, the quantum dot nanorod array layer comprises a plurality of quantum dot nanorods, each quantum dot nanorod comprises a quantum dot core and a rod-shaped shell layer coated outside the quantum dot core, each rod-shaped shell layer comprises a first end and a second end which are opposite, and the quantum dot core is positioned on one side, close to the first end, of a central point between the first end and the second end;
forming the second electrode on the quantum dot light emitting layer.
14. The method according to claim 13, wherein the forming the quantum dot light emitting layer specifically comprises:
preparing a quantum dot core;
introducing magnetic ions on the surface of the quantum dot core to form a magnetic quantum dot core, wherein the surface of the magnetic quantum dot core is provided with the magnetic ions;
wrapping a rod-shaped shell layer around the quantum dot core, wherein a ligand with charges is formed at one end of the surface of the rod-shaped shell layer, so as to obtain a quantum dot nanorod solution;
and forming the quantum dot nanorod array layer by film formation of the quantum dot nanorod solution, wherein in the film formation process of the quantum dot nanorod solution, the orientation of the quantum dot nanorods is controlled by applying an electric field and a magnetic field and controlling the direction of the electric field, the quantum dot cores are positioned at the positions close to the first ends of the rod-shaped shell layers by controlling the direction of the magnetic field, and the quantum dot nanorod array layer is obtained by annealing, drying and film formation.
15. The method according to claim 14, wherein magnetic ions are introduced to the surface of the quantum dot core to obtain a magnetic quantum dot core, and specifically comprises:
and the outermost surface of the quantum dot core is provided with anions and cations which are alternately arranged, the quantum dot core is dissolved in a nonpolar solvent and heated in an inert gas atmosphere, and a small amount of material with magnetic ions is added into the nonpolar solvent, so that the magnetic ions are combined with part of the anions to form the magnetic ions on the surface of the quantum dot core, and the magnetic quantum dot core is obtained.
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CN106356465A (en) * 2016-10-27 2017-01-25 Tcl集团股份有限公司 Efficient QLED (Quantum Dot Light Emitting Diode) device based on nano-rod and display device
CN108539031A (en) * 2018-04-12 2018-09-14 京东方科技集团股份有限公司 Quantum dot film build method, display panel and preparation method thereof, display device
CN112652649A (en) * 2020-12-21 2021-04-13 深圳扑浪创新科技有限公司 Quantum dot display device and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140145144A1 (en) * 2012-11-23 2014-05-29 Lg Display Co., Ltd. Quantum rod and method of fabricating the same
CN106356465A (en) * 2016-10-27 2017-01-25 Tcl集团股份有限公司 Efficient QLED (Quantum Dot Light Emitting Diode) device based on nano-rod and display device
CN108539031A (en) * 2018-04-12 2018-09-14 京东方科技集团股份有限公司 Quantum dot film build method, display panel and preparation method thereof, display device
CN112652649A (en) * 2020-12-21 2021-04-13 深圳扑浪创新科技有限公司 Quantum dot display device and preparation method and application thereof

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