CN109285955B - Quantum dot light-emitting diode, manufacturing method thereof and display - Google Patents

Quantum dot light-emitting diode, manufacturing method thereof and display Download PDF

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CN109285955B
CN109285955B CN201710602180.4A CN201710602180A CN109285955B CN 109285955 B CN109285955 B CN 109285955B CN 201710602180 A CN201710602180 A CN 201710602180A CN 109285955 B CN109285955 B CN 109285955B
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layer
transparent conductive
quantum dot
conductive substrate
dot light
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CN109285955A (en
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张东华
向超宇
张滔
辛征航
李乐
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TCL Research America Inc
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TCL Research America Inc
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/841—Self-supporting sealing arrangements
    • 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 invention provides a quantum dot light-emitting diode, a manufacturing method thereof and a display. This quantum dot light emitting diode, including transparent conductive substrate, transparent conductive substrate has the front and the back, the blind hole has been seted up at transparent conductive substrate's the back, quantum dot light emitting diode is still located including the cover internal insulation layer on the blind hole lateral wall, locate in proper order hole injection layer, hole transport layer, quantum dot light emitting layer, electron transport layer and the back electrode layer in the blind hole. According to the invention, the hole injection layer, the hole transmission layer, the quantum dot light-emitting layer, the electron transmission layer and the back electrode layer are manufactured in the blind holes of the transparent conductive substrate, so that the quantum dot light-emitting layer can be isolated from being contacted with external water vapor, the light-emitting thin layer is prevented from being corroded and damaged, and the service life of a device is prolonged; the thickness of the front surface of the transparent conductive substrate is reduced, the path of light emitted by the quantum dot light emitting layer is shortened, and light emitting can be increased; the structure is simple and convenient to package, and is convenient for batch automatic production.

Description

Quantum dot light-emitting diode, manufacturing method thereof and display
Technical Field
The invention belongs to the field of light emitting diodes, and particularly relates to a quantum dot light emitting diode, a manufacturing method of the quantum dot light emitting diode and a display using the quantum dot light emitting diode.
Background
The liquid crystal is a substance which cannot emit light by itself, and can work by an additional light source, and the physical characteristic cannot be changed, so that the 'ultimate evolution' of the liquid crystal technology naturally needs to be started from a backlight system. The QLED is a short hand for 'Quantum Dot light Emitting Diode', the Chinese translation name is a Quantum Dot light Emitting Diode, and the display technology of the sub-screen can also be weighed. Current QLEDs typically have an anode layer, a hole injection layer, a quantum dot light emitting layer, an electron transport layer, and a cathode layer fabricated in sequence on a glass substrate. However, the quantum dot light emitting layer with the structure is easily corroded and damaged by external moisture.
Disclosure of Invention
The invention aims to provide a quantum dot light-emitting diode, which aims to solve the problem that a quantum dot light-emitting layer of the quantum dot light-emitting diode in the prior art is easily corroded and damaged by external moisture.
In order to achieve the purpose, the invention adopts the technical scheme that: the utility model provides a quantum dot emitting diode, includes transparent conductive substrate, transparent conductive substrate has the front and the back, the blind hole has been seted up at transparent conductive substrate's the back, quantum dot emitting diode is still including covering to be located internal insulation layer on the blind hole lateral wall, locate in proper order hole injection layer, hole transport layer, quantum dot luminescent layer, electron transport layer and back electrode layer in the blind hole.
Further, the display device further comprises an outer insulating layer covering the back electrode layer, and the outer insulating layer is spaced from the transparent conductive substrate.
Further, the edge of the inner insulating layer extends outwards to the back surface, the periphery of the back electrode layer covers the edge of the inner insulating layer, and the back electrode layer is spaced apart from the transparent conductive substrate.
Further, the surface of the inner insulating layer has a textured structure that is ion bombarded.
Furthermore, an included angle between the side wall of the blind hole and the bottom surface of the blind hole is larger than or equal to 90 degrees.
Furthermore, the transparent conductive substrate comprises a transparent substrate and a transparent conductive film arranged on the back of the transparent substrate, a groove is formed in the back of the transparent substrate, and the transparent conductive film covers the inner surface of the groove.
Further, the thickness of the transparent conductive substrate is 1.5-2.5mm, and the depth of the blind hole is 1/3-2/3 of the thickness of the transparent conductive substrate.
Another object of the present invention is to provide a method for manufacturing the quantum dot light emitting diode, which comprises the following steps:
prefabrication: providing a transparent conductive substrate, wherein a blind hole is formed in the back surface of the transparent conductive substrate; cleaning the transparent conductive substrate;
masking: coating a film on the back surface of the transparent conductive substrate in the area outside the inner insulating layer;
manufacturing an inner insulating layer: depositing and manufacturing an inner insulating layer in a region which is not coated with a film on the back surface of the transparent conductive substrate by adopting a chemical vapor deposition method;
removing the mask: cleaning the film on the transparent conductive substrate with the inner insulating layer by using an organic solvent;
preparing an intermediate layer: sequentially manufacturing a hole injection layer, a hole transmission layer, a quantum dot light-emitting layer and an electron transmission layer in the blind holes of the transparent conductive substrate obtained in the mask removing step;
preparing a back electrode: covering a mask in the region outside the blind hole and outside the inner insulating layer on the back surface of the transparent conductive substrate after the step of manufacturing the middle layer, then manufacturing a back electrode layer, and removing the mask.
Further, before the step of manufacturing the intermediate layer, the method also comprises the step of ion bombardment: and bombarding the surface of the inner insulating layer by adopting plasma.
It is another object of the present invention to provide a display including a plurality of quantum dot light emitting diodes arranged in an array as described above.
The quantum dot light-emitting diode provided by the invention has the beneficial effects that: compared with the prior art, the hole injection layer, the hole transmission layer, the quantum dot light-emitting layer, the electron transmission layer and the back electrode layer are manufactured in the blind holes of the transparent conductive substrate, so that the quantum dot light-emitting layer can be isolated from being contacted with external moisture, the quantum dot light-emitting layer is prevented from being corroded and damaged, and the service life of a device is prolonged; the front side of the transparent conductive substrate is thinned, the path of light emitted by the quantum dot light emitting layer is shortened, light emitting can be increased, and meanwhile, the transparent conductive substrate is used, so that the absorption of light can be reduced, and the light emitting rate is further increased; in addition, the structure is simple and convenient to package, and is convenient for batch automatic production.
The display provided by the invention uses the quantum dot light emitting diode, and the plurality of quantum dot light emitting diode arrays are arranged, so that large-area display equipment can be conveniently manufactured.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a transparent conductive substrate of a quantum dot light emitting diode according to a second embodiment of the present invention;
fig. 3 is a schematic structural diagram of an insulating layer formed on a transparent conductive substrate of a quantum dot light-emitting diode according to a third embodiment of the present invention;
FIG. 4 is a schematic view illustrating an ion bombardment process of an insulating layer of the quantum dot light emitting diode shown in FIG. 3;
fig. 5 is a flowchart of a method for manufacturing a quantum dot light emitting diode according to an embodiment of the present invention.
Fig. 6 is a schematic front view of a transparent conductive substrate array of a display according to an embodiment of the present invention.
Wherein, in the drawings, the reference numerals are mainly as follows:
100-quantum dot light emitting diodes; 11-a transparent conductive substrate; 110-blind holes; 111-a transparent substrate; 112-a transparent conductive film; 12-an inner insulating layer; 13-a hole injection layer; 14-a hole transport layer; 15-a quantum dot light emitting layer; 16-an electron transport layer; 17-a back electrode layer; 18-an outer insulating layer; 19-film; 20-microcavity structure;
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description of the present invention, it is to be understood that the terms "center", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The first embodiment is as follows:
referring to fig. 1, a quantum dot light emitting diode 100 according to the present invention will now be described. The quantum dot light emitting diode 100 comprises a transparent conductive substrate 11, an inner insulating layer 12, a hole injection layer 13, a hole transport layer 14, a quantum dot light emitting layer 15, an electron transport layer 16 and a back electrode layer 17. The transparent conductive substrate 11 is provided with a front surface and a back surface, the back surface of the transparent conductive substrate 11 is provided with a blind hole 110, an inner insulating layer 12 is covered on the side wall of the blind hole 110, and a hole injection layer 13, a hole transport layer 14, a quantum dot light emitting layer 15, an electron transport layer 16 and a back electrode layer 17 are sequentially arranged in the blind hole 110, so that two ends of the hole injection layer 13, two ends of the hole transport layer 14, two ends of the quantum dot light emitting layer 15, two ends of the electron transport layer 16 and two ends of the back electrode layer 17 are separated from the transparent conductive substrate 11 through the inner insulating layer 12; the hole injection layer 13, the hole transport layer 14, the quantum dot light emitting layer 15 and the electron transport layer 16 are sequentially arranged in the blind hole 110, so that the blind hole can be isolated from external moisture, corrosion and damage are avoided, and the service life is prolonged; the thickness of the quantum dot light-emitting layer 15 corresponding to the corresponding position on the transparent conductive substrate 11 can be shortened, the light emitting path is shortened, and the light emitting rate is increased; in addition, the structure is convenient to package, such as directly packaging by adopting packaging glue.
Compared with the prior art, the quantum dot light-emitting diode 100 provided by the invention has the advantages that the hole injection layer 13, the hole transmission layer 14, the quantum dot light-emitting layer 15, the electron transmission layer 16 and the back electrode layer 17 are manufactured in the blind hole 110 of the transparent conductive substrate 11, so that the quantum dot light-emitting layer 15 can be isolated from being contacted with external moisture, the quantum dot light-emitting layer 15 is prevented from being corroded and damaged, and the service life of a device is prolonged; the front thickness of the transparent conductive substrate 11 is reduced, the path of light emitted by the quantum dot light-emitting layer 15 is shortened, and light emission can be increased; in addition, the structure is simple and convenient to package, and is convenient for batch automatic production. And the transparent conductive substrate 11 can reduce the absorption of light, so that the light can be output better, and the light-emitting rate is further increased.
Further, referring to fig. 1, as an embodiment of the quantum dot light emitting diode 100 provided by the present invention, the quantum dot light emitting diode 100 further includes an outer insulating layer 18 covering the back electrode layer 17, and the outer insulating layer 18 is spaced apart from the transparent conductive substrate 11. The back electrode layer 17 is provided with an external insulating layer 18, which can protect the back electrode layer 17. While the outer insulating layer 18 is spaced apart from the transparent conductive substrate 11 so as to connect external electrodes.
Further, referring to fig. 1, as an embodiment of the quantum dot light emitting diode 100 provided by the present invention, an edge of the inner insulating layer 12 extends outward to a back surface, a periphery of the back electrode layer 17 covers the edge of the inner insulating layer 12, and the back electrode layer 17 is spaced apart from the transparent conductive substrate 11. Extending the edge of the inner insulating layer 12 outward onto the back surface may better space the back electrode layer 17 from the transparent conductive substrate 11; specifically, one end of the inner insulating layer 12 close to the back surface of the transparent conductive substrate 11 may extend outward to the blind hole 110 to a section of the back surface of the transparent conductive substrate 11. The periphery of the back electrode layer 17 is covered on the edge of the inner insulating layer 12, so that the back electrode layer 17 can be exposed in a larger area to be connected with an external electrode, and the packaging is convenient.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the external insulating layer 18 covers the back electrode layer 17 at a position corresponding to the blind hole 110. This structure facilitates the processing preparation to when preparation back electrode layer 17, the periphery of back electrode layer 17 extends outside blind hole 110, can make back electrode layer 17 go up the position that corresponds blind hole 110 and form the depressed trench, then can be at this depressed trench preparation outer insulating layer 18, processing preparation is convenient.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the thickness of the transparent conductive substrate 11 is 1.5-2.5mm, and the depth of the blind hole 110 is 1/3-2/3 of the thickness of the transparent conductive substrate 11. The thickness of the transparent conductive substrate 11 is 1.5-2.5mm, the thickness is small, light emission is facilitated, the depth of the blind hole 110 is set to be 1/3-2/3 of the thickness of the transparent conductive substrate 11, and the hole injection layer 13, the hole transport layer 14, the quantum dot light emitting layer 15, the electron transport layer 16 and the back electrode layer 17 can be conveniently and sequentially arranged in the blind hole 110.
Further, as an embodiment of the quantum dot light emitting diode 100 provided by the present invention, SiOx, SiNx, TiO may be used as the inner insulating layer 122And the like. Specifically, the manufacturing method may use a chemical vapor deposition method. Preferably, the inter-insulating layer 12 is formed using a plasma chemical vapor deposition method.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the thickness range of the inner insulating layer 12 is 100-1000nm, so as to insulate and isolate the sidewall of the blind via 110.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the hole injection layer 13 may be manufactured by a method using a solution method, such as printing or spraying. In other embodiments, the hole injection layer 13 may also be formed by vacuum evaporation, sputtering, chemical vapor deposition, or other vacuum methods.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the electron transport layer 16 may be manufactured by a method using a solution method, such as printing or spraying. In other embodiments, the electron transport layer 16 can also be formed by vacuum evaporation, sputtering, chemical vapor deposition, and the like.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the hole transport layer 14 may be manufactured by a method using a solution method, such as printing or spraying. In other embodiments, the hole transport layer 14 can also be formed by vacuum evaporation, sputtering, chemical vapor deposition, and the like.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the quantum dot light emitting layer 15 may be manufactured by a printing and spraying method.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the back electrode layer 17 may be fabricated by using a chemical vapor deposition method, a magnetron sputtering method, a sol-gel method, or the like. Further, the back electrode layer 17 may be made of aluminum.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, in the present embodiment, an included angle α between a side wall of the blind via 110 and a bottom surface of the blind via 110 is equal to 90 degrees.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the transparent conductive substrate 11 includes a transparent substrate 111 and a transparent conductive film 112, the transparent conductive film 112 is disposed on the back of the transparent substrate 111; the back surface of the transparent substrate 111 is provided with a groove, and the inner surface of the groove is covered by the transparent conductive film 112 to form the blind hole 110.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the transparent substrate 111 may be transparent glass. Of course, in some embodiments, the transparent substrate 111 may also be a transparent plastic or the like.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the transparent conductive film 112 may be a thin film made of ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), or other materials.
Of course, in other embodiments, the transparent conductive substrate 11 may also be FTO; the FTO conductive glass is fluorine-doped SnO2 transparent conductive glass (SnO 2: F), which is abbreviated as FTO.
Example two:
referring to fig. 2 and fig. 1, the areas of the quantum dot light emitting diode 100 of the present embodiment and the quantum dot light emitting diode of the first embodiment are:
in this embodiment, the included angle α between the sidewall of the blind via 110 and the bottom surface of the blind via 110 is greater than 90 degrees, so that the sidewall of the blind via 110 is an inclined-plane structure, which facilitates the fabrication of the inner insulating layer 12 on the sidewall of the blind via 110.
Other structures of the quantum dot light emitting diode 100 of the present embodiment are the same as those of the quantum dot light emitting diode of the first embodiment, and are not described herein again.
Example three:
referring to fig. 3 and also to fig. 1, the areas of the quantum dot light emitting diode 100 of the present embodiment and the quantum dot light emitting diode of the second embodiment are:
in this embodiment, the transparent conductive substrate 11 includes a transparent substrate 111 and a transparent conductive film 112, and the transparent conductive film 112 is disposed on the back of the transparent substrate 111; the back surface of the transparent substrate 111 is provided with a groove, and the inner surface of the groove is covered by the transparent conductive film 112 to form the blind hole 110.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the transparent substrate 111 may be transparent glass. Of course, in some embodiments, the transparent substrate 111 may also be a transparent plastic or the like.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, the transparent conductive film 112 may be a thin film made of ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), or other materials.
Further, as a specific embodiment of the quantum dot light emitting diode 100 provided by the present invention, before the inner insulating layer 12 is fabricated, the film 19 may be coated on the region outside the inner insulating layer 12 on the back surface of the transparent conductive substrate 11 to cover the region, and then the inner insulating layer 12 is fabricated by using a plasma vapor deposition method, and then the film 19 is cleaned, so that the inner insulating layer 12 can be fabricated on the designated region on the back surface of the transparent conductive substrate 11 accurately.
Further, referring to fig. 4, as an embodiment of the quantum dot light emitting diode 100 provided by the present invention, the surface of the inner insulating layer 12 has a textured structure 121 formed by ion bombardment. The textured structure 121 is formed by bombarding the surface of the inner insulating layer 12 with ions, so that the light trapping effect can be achieved, the internal propagation times of light emitted by the quantum dot light emitting layer 15 in the device are reduced (the internal propagation times are more and are easy to absorb), and the purpose of improving the light emitting rate of the device is achieved. And the ion bombardment can remove weak bonds on the surface of the inner insulating layer 12, reduce surface defects, obtain a more complete interface, improve the working current stability of the device and enhance the working stability of the device.
Specifically, the textured structure 121 may be formed by performing ion bombardment on the surface of the inner insulating layer 12 with plasma immediately after the inner insulating layer 12 is deposited.
Other structures of the quantum dot light emitting diode 100 of the present embodiment are the same as those of the quantum dot light emitting diode of the second embodiment, and are not described herein again.
Referring to fig. 1 to 5, the present invention further provides a method for fabricating a quantum dot light emitting diode, which can be used for fabricating the quantum dot light emitting diode 100. The manufacturing method of the quantum dot light-emitting diode comprises the following steps:
prefabrication S1: providing a transparent conductive substrate 11, wherein a blind hole 110 is formed in the back surface of the transparent conductive substrate 11; and cleaning the transparent conductive substrate 11;
mask S2: coating a film 19 on the back surface of the transparent conductive substrate 11 in the area except for the area for manufacturing the inner insulating layer 12;
manufacturing an inner insulating layer S3: depositing and manufacturing an inner insulating layer 12 in an area, which is not coated with a film, on the back surface of the transparent conductive substrate 11 by adopting a chemical vapor deposition method;
unmasking S5: cleaning the film 19 on the transparent conductive substrate 11 on which the inner insulating layer 12 is formed, by using an organic solvent;
preparing an intermediate layer S6: sequentially manufacturing a hole injection layer 13, a hole transport layer 14, a quantum dot light-emitting layer 15 and an electron transport layer 16 in the blind hole 110 of the transparent conductive substrate 11 obtained in the step of removing the mask S5;
back electrode manufacturing S7: covering a mask on the back surface of the transparent conductive substrate 11 after the step of manufacturing the intermediate layer S6 in the region outside the blind hole 110 and outside the internal insulation layer 12, then manufacturing the back electrode layer 17, and removing the mask.
The quantum dot light emitting diode 100 can be manufactured by the method. Through the prefabrication step, the transparent conductive substrate 11 can be ensured to be clean and clean, so that the inner insulating layer 12 can be better attached to the transparent conductive substrate 11. By the masking step, the internal insulating layer 12 can be formed on a predetermined region of the transparent conductive substrate 11.
In the above-mentioned prefabricating step, when the transparent conductive substrate 11 is cleaned, the transparent conductive substrate 11 may be placed in a container filled with a detergent solution, and the surface is brushed clean with a brush; then placing the mixture into isopropanol, and cleaning the mixture for about 20min by using ultrasonic oscillation; then, rinsing the surface of the transparent conductive substrate 11 with ultrapure water, putting the transparent conductive substrate into an ultrapure water beaker, and carrying out ultrasonic oscillation for about 10 min; and after cleaning, drying the transparent conductive substrate 11 by using a nitrogen gun.
In the step of manufacturing the inner insulating layer 12, the inner insulating layer 12 may be manufactured by a plasma vapor deposition method, and the specific plasma vapor deposition process parameters may be: the frequency of the radio frequency source is 13.56MHz, the deposition temperature is 200 ℃, the radio frequency power is 150W, the working gas pressure is 133Pa, and the gas source is Silane (SiH)4) And ammonia (NH)3) (ii) a The flow ratio of silane to ammonia was 10 sccm: 90 sccm; the protective gas is argon (Ar), the flow rate is 100sccm, and the deposition time is 5 min.
Further, as a specific implementation manner of the manufacturing method of the quantum dot light emitting diode provided by the present invention, before the step of preparing the intermediate layer S6, the method further includes a step of ion bombardment S4: the surface of the inner insulating layer 12 is bombarded with plasma. Through ion bombardment on the surface of the inner insulating layer 12, the textured structure 121 can be formed on the surface of the inner insulating layer 12, a light trapping effect can be achieved, the number of times of light emitted by the quantum dot light emitting layer 15 in the device is reduced (the number of times of light emitted in the device is increased, and the light is easy to absorb), and the purpose of improving the light emitting rate of the device is achieved. And the ion bombardment can remove weak bonds on the surface of the inner insulating layer 12, reduce surface defects, obtain a more complete interface, improve the working current stability of the device and enhance the working stability of the device.
Specifically, after the inner insulating layer 12 is fabricated, the sample may be transferred to the IBE vacuum chamber by a robot in the transfer chamber until the vacuum reaches 3 × 10-4pa, setting parameters, setting the radio frequency power to 180W,the voltage of Grid61 is-525V, the voltage of Grid62 is 100V, the gas is argon (Ar), the flow rate is 18sccm, the inclination angle of the substrate is 65 degrees, the time is 30s, and the click starts after the check is correct. To ion bombard the surface of the inner insulating layer 12.
Further, as a specific implementation manner of the manufacturing method of the quantum dot light emitting diode provided by the present invention, after the step of manufacturing the back electrode S7, the method further includes a packaging step: and covering the back surface of the transparent conductive substrate 11 with packaging adhesive.
The invention also discloses two examples of manufacturing the quantum dot light-emitting diode 100 by adopting the manufacturing method of the quantum dot light-emitting diode, which are as follows:
example one:
a transparent conductive substrate 11 as shown in FIG. 1 is used, the transparent conductive substrate 11 can be ITO glass, that is, transparent glass is used as a substrate, a transparent conductive film on the transparent glass is made of ITO, the transparent conductive substrate 11 (the length, width and thickness of the transparent conductive substrate 11 are 2cm multiplied by 2mm, the side wall inclination angle α of the blind hole 110 is 90 degrees, the length, width and thickness of the blind hole 110 is 1.5cm multiplied by 1mm), the transparent conductive substrate 11 is placed in a container filled with a detergent solution, the surface is cleaned by a brush, then the transparent conductive substrate 11 is placed in isopropanol and cleaned by ultrasonic oscillation for about 20min, then the surface of the transparent conductive substrate 11 is washed by ultrapure water, then the transparent conductive substrate 11 is placed in an ultrapure water beaker and subjected to ultrasonic oscillation for about 10min, and the transparent conductive substrate 11 is dried by a nitrogen gun.
Depositing the inner insulating layer 12 by Plasma Enhanced Chemical Vapor Deposition (PECVD), coating a film 19 on the transparent conductive substrate 11 as shown in FIG. 3, and depositing the inner insulating layer 12 in the area without the film 19; specifically, the inner insulating layer 12 is deposited by using SiNx material and Plasma Enhanced Chemical Vapor Deposition (PECVD), and then the film 19 is cleaned with an organic solvent. PECVD deposition process parameters: the frequency of the radio frequency source is 13.56MHz, the deposition temperature is 200 ℃, the radio frequency power is 150W, the working gas pressure is 133Pa, and the gas source is Silane (SiH)4) And ammonia (NH)3) (ii) a The flow ratio of silane to ammonia was 10 sccm: 90 sccm; the protective gas is argon (Ar), the flow rate is 100sccm, and the deposition time is 5 min.
Finished internal insulationAfter layer 12, the sample can be transferred to the IBE vacuum chamber by a robot in the transfer chamber until a vacuum of 3 × 10 is achieved-4pa, setting parameters, setting the radio frequency power to be 180W, setting the Grid61 voltage to be 525V, setting the Grid62 voltage to be 100V, setting the gas to be argon (Ar), setting the flow to be 18sccm, setting the substrate inclination angle to be 65 degrees, setting the time to be 30s, and clicking to start after checking is correct. To ion bombard the surface of the inner insulating layer 12.
After the surface of the inner insulating layer 12 is bombarded by Ar ions, a hole injection layer 13(HIL), a hole transport layer 14(HTL), a quantum dot light emitting layer 15(QD) and an electron transport layer 16(ETL) are sequentially printed in the blind hole 110 by a printing method.
And evaporating metal aluminum on the back surface of the transparent conductive substrate 11 to be 100nm thick to form a back electrode layer 17, wherein the back electrode layer 17 covers the inner insulating layer 12 as shown in FIG. 1, and the back electrode layer 17 is separated from the transparent conductive substrate 11 through the inner insulating layer 12 to avoid short circuit. Then, the back electrode layer 17 is covered with a mask to form an outer insulating layer 18.
Example two:
a transparent conductive substrate 11 as shown in FIG. 2 is used, the transparent conductive substrate 11 can be ITO glass, that is, transparent glass is used as a substrate, a transparent conductive film on the transparent glass is made of ITO, the transparent conductive substrate 11 (the length, width and thickness of the transparent conductive substrate 11 are 2cm multiplied by 2mm, the side wall inclination angle α of the blind hole 110 is 120 degrees, the length, width and thickness of the blind hole 110 is 1.5cm multiplied by 1mm), the transparent conductive substrate 11 is placed in a container filled with a detergent solution, the surface is cleaned by a brush, then the transparent conductive substrate 11 is placed in isopropanol and cleaned by ultrasonic oscillation for about 20min, then the surface of the transparent conductive substrate 11 is washed by ultrapure water, then the transparent conductive substrate 11 is placed in an ultrapure water beaker and subjected to ultrasonic oscillation for about 10min, and the transparent conductive substrate 11 is dried by a nitrogen gun.
Depositing the inner insulating layer 12 by Plasma Enhanced Chemical Vapor Deposition (PECVD), coating a film 19 on the transparent conductive substrate 11 as shown in FIG. 3, and depositing the inner insulating layer 12 in the area without the film 19; specifically, the inner insulating layer 12 is deposited by using SiNx material and Plasma Enhanced Chemical Vapor Deposition (PECVD), and then the film 19 is cleaned with an organic solvent. PECVD deposition process parameters: radio frequency source frequencyThe deposition rate is 13.56MHz, the deposition temperature is 200 ℃, the radio frequency power is 150W, the working gas pressure is 133Pa, and the gas source is Silane (SiH)4) And ammonia (NH)3) (ii) a The flow ratio of silane to ammonia was 10 sccm: 90 sccm; the protective gas is argon (Ar), the flow rate is 100sccm, and the deposition time is 5 min.
After the inner insulating layer 12 is manufactured, the sample can be transferred to the IBE vacuum chamber by a manipulator in the transfer chamber until the vacuum reaches 3 × 10-4pa, setting parameters, setting the radio frequency power to be 180W, setting the Grid61 voltage to be 525V, setting the Grid62 voltage to be 100V, setting the gas to be argon (Ar), setting the flow to be 18sccm, setting the substrate inclination angle to be 65 degrees, setting the time to be 30s, and clicking to start after checking is correct. To ion bombard the surface of the inner insulating layer 12.
After the surface of the inner insulating layer 12 is bombarded by Ar ions, a hole injection layer 13(HIL), a hole transport layer 14(HTL), a quantum dot light emitting layer 15(QD) and an electron transport layer 16(ETL) are sequentially printed in the blind hole 110 by a printing method.
And evaporating metal aluminum on the back surface of the transparent conductive substrate 11 to be 100nm thick to form a back electrode layer 17, wherein the back electrode layer 17 covers the inner insulating layer 12 as shown in FIG. 1, and the back electrode layer 17 is separated from the transparent conductive substrate 11 through the inner insulating layer 12 to avoid short circuit. Then, the back electrode layer 17 is covered with a mask to form an outer insulating layer 18.
Referring to fig. 6 and fig. 1, the present invention further provides a display device, which includes the above-mentioned qd-led 100 arranged in an array. The display uses the quantum dot light emitting diode 100 and is provided with the plurality of quantum dot light emitting diodes 100 in an array mode, large-area display equipment can be manufactured conveniently, and meanwhile the display is long in service life and high in light emitting rate. And a micro-cavity structure 20 can be formed between two adjacent quantum dot light-emitting diodes 100, so that the light-emitting rate is further improved.
Further, as a specific embodiment of the display provided by the present invention, the transparent conductive substrate 11 of the plurality of quantum dot light emitting diodes 100 is integrally formed. The structure can be convenient for integrating a plurality of quantum dot light-emitting diodes 100 on the same transparent conductive substrate 11 to form a panel structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. Quantum dot light emitting diode, including transparent electrically conductive base plate, transparent electrically conductive base plate has front and back, its characterized in that: the back surface of the transparent conductive substrate is provided with a blind hole, and the quantum dot light-emitting diode further comprises an inner insulating layer, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a back electrode layer, wherein the inner insulating layer is arranged on the side wall of the blind hole in a covering manner, and the hole injection layer, the hole transport layer, the quantum dot light-emitting layer, the electron transport layer; the surface of the inner insulating layer has a textured structure bombarded by ions.
2. The quantum dot light-emitting diode of claim 1, wherein: the display device further comprises an outer insulating layer which covers the back electrode layer, and the outer insulating layer is spaced from the transparent conductive substrate.
3. The quantum dot light-emitting diode of claim 1, wherein: the edge of the inner insulating layer extends outwards to the back surface, the periphery of the back electrode layer covers the edge of the inner insulating layer, and the back electrode layer is spaced from the transparent conductive substrate.
4. The qd-led of any one of claims 1-3, wherein: and an included angle between the side wall of the blind hole and the bottom surface of the blind hole is more than or equal to 90 degrees.
5. The qd-led of any one of claims 1-3, wherein: the transparent conductive substrate comprises a transparent substrate and a transparent conductive film arranged on the back of the transparent substrate, a groove is formed in the back of the transparent substrate, and the transparent conductive film covers the inner surface of the groove.
6. The qd-led of any one of claims 1-3, wherein: the thickness of the transparent conductive substrate is 1.5-2.5mm, and the depth of the blind hole is 1/3-2/3 of the thickness of the transparent conductive substrate.
7. The method of claim 1, wherein: the method comprises the following steps:
prefabrication: providing a transparent conductive substrate, wherein a blind hole is formed in the back surface of the transparent conductive substrate; cleaning the transparent conductive substrate;
masking: coating a film on the back surface of the transparent conductive substrate in the area outside the inner insulating layer;
manufacturing an inner insulating layer: depositing and manufacturing an inner insulating layer in a region which is not coated with a film on the back surface of the transparent conductive substrate by adopting a chemical vapor deposition method;
removing the mask: cleaning the film on the transparent conductive substrate with the inner insulating layer by using an organic solvent;
preparing an intermediate layer: sequentially manufacturing a hole injection layer, a hole transmission layer, a quantum dot light-emitting layer and an electron transmission layer in the blind holes of the transparent conductive substrate obtained in the mask removing step;
preparing a back electrode: covering a mask on the back surface of the transparent conductive substrate after the step of manufacturing the middle layer in the areas outside the blind holes and the inner insulating layer, then manufacturing a back electrode layer, and removing the mask;
before the step of preparing the intermediate layer, the method also comprises the step of ion bombardment: and bombarding the surface of the inner insulating layer by adopting plasma.
8. A display comprising a plurality of quantum dot light emitting diodes according to any of claims 1 to 6 arranged in an array.
CN201710602180.4A 2017-07-21 2017-07-21 Quantum dot light-emitting diode, manufacturing method thereof and display Active CN109285955B (en)

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CN104218050A (en) * 2013-06-04 2014-12-17 三星显示有限公司 Organic light-emitting display apparatus and method for manufacturing the same
CN104425766A (en) * 2013-08-30 2015-03-18 株式会社日本显示器 Electroluminescence device and manufacturing method thereof
CN108539028A (en) * 2017-03-01 2018-09-14 Tcl集团股份有限公司 A kind of light emitting diode with quantum dots device and preparation method thereof

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US7915068B2 (en) * 2008-03-14 2011-03-29 Atomic Energy Council—Institute of Nuclear Energy Research Method for making solar cells with sensitized quantum dots in the form of nanometer metal particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104218050A (en) * 2013-06-04 2014-12-17 三星显示有限公司 Organic light-emitting display apparatus and method for manufacturing the same
CN104425766A (en) * 2013-08-30 2015-03-18 株式会社日本显示器 Electroluminescence device and manufacturing method thereof
CN108539028A (en) * 2017-03-01 2018-09-14 Tcl集团股份有限公司 A kind of light emitting diode with quantum dots device and preparation method thereof

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