CN114695708A - Light emitting device and method of manufacturing the same - Google Patents
Light emitting device and method of manufacturing the same Download PDFInfo
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- CN114695708A CN114695708A CN202011633001.1A CN202011633001A CN114695708A CN 114695708 A CN114695708 A CN 114695708A CN 202011633001 A CN202011633001 A CN 202011633001A CN 114695708 A CN114695708 A CN 114695708A
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- 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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- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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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
Abstract
The application belongs to the technical field of display equipment, and particularly relates to a preparation method of a light-emitting device, which comprises the following steps: obtaining a substrate deposited with a cathode; preparing an electron transport layer on the surface of the cathode, which is far away from the substrate, wherein the electron transport layer comprises a metal oxide transport material; and after the first ultraviolet irradiation treatment is carried out on the electron transport layer, a quantum dot light-emitting layer and an anode are sequentially prepared on the side surface of the electron transport layer departing from the cathode, so that the light-emitting device is obtained. According to the preparation method of the light-emitting device, after the metal oxide electron transmission layer is prepared on the surface of the cathode, the fusion of the metal oxide electron transmission material and the electrode is promoted through ultraviolet irradiation treatment, the potential barrier is reduced, and the electron injection efficiency is improved. Meanwhile, the bonding and crystal regrowth in the electron transport layer are promoted, so that the surface of the electron transport layer is smoother, the interface roughness is reduced, the interface gap is optimized, and the influence of charge accumulation on the service life of the device is avoided.
Description
Technical Field
The application belongs to the technical field of display equipment, and particularly relates to a light-emitting device and a preparation method thereof.
Background
Quantum dots are nanocrystalline particles with a radius less than or near the bohr exciton radius, typically having a size between one. The quantum dots have quantum confinement effect and can emit fluorescence after being excited. And the quantum dot has unique luminescence characteristics of wide excitation peak, narrow emission peak, adjustable luminescence spectrum and the like, so that the quantum dot material has wide application prospect in the field of photoelectric luminescence. Quantum dot light emitting diodes (QLEDs) are a new display technology that has rapidly emerged in recent years, and are devices using colloidal quantum dots as light emitting layers, and quantum dot light emitting layers are introduced between different conductive materials to obtain light of a desired wavelength. The quantum dot light emitting diode has the advantages of high color gamut, self-luminescence, low starting voltage, high response speed and the like.
At present, in order to balance carrier injection, an OLED device generally adopts a multi-layer device structure, and a quantum dot luminescent layer mostly adopts a quantum dot nanometer material with a core-shell structure. In the quantum dot light-emitting diode, the annealing temperature cannot be too high due to the organic surface ligand of quantum dot nano particles and the refined core-shell structure in the quantum dot light-emitting diode, so that the interface roughness of a formed quantum dot layer is higher. In addition, the annealing temperature of the quantum dot layer also limits the annealing temperature of the adjacent ETL, so that the electron transport material is difficult to reach a better crystallization temperature, the internal structure of the electron transport layer is discontinuous, the electron transport mobility is reduced, and the interface roughness is increased. However, the high interface roughness between the quantum dot light emitting layer and the electron transport layer affects the continuity of carrier injection into the quantum dot light emitting layer, the injection efficiency is low, and the carrier injection performance is reduced. In addition, charge accumulation centers are easily formed at the interface gaps, so that the aging of materials is accelerated, and the service life of the device is seriously influenced.
Disclosure of Invention
The application aims to provide a light-emitting device and a preparation method thereof, and aims to solve the problems that the interface fusion between an electron transport layer and an adjacent functional layer is poor, the electron injection efficiency is influenced, and the charge accumulation is easy to form to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for manufacturing a light emitting device, comprising the steps of:
obtaining a substrate deposited with a cathode;
preparing an electron transport layer on the surface of the cathode, which is far away from the substrate, wherein the electron transport layer comprises a metal oxide transport material;
and after the first ultraviolet irradiation treatment is carried out on the electron transport layer, a quantum dot light-emitting layer and an anode are sequentially prepared on the side surface of the electron transport layer departing from the cathode, so that the light-emitting device is obtained.
In a second aspect, the present application provides a light emitting device made by the above method.
According to the preparation method of the light-emitting device, after the metal oxide electronic transmission layer is prepared on the surface of the cathode, the electronic transmission layer is subjected to first ultraviolet irradiation treatment, and through the ultraviolet irradiation treatment, the metal oxide in the electronic transmission layer has a strong absorption effect on ultraviolet visible light, so that the internal temperature of the electronic transmission layer is increased, bonding electrons are activated, and the internal bonding and crystal regrowth in the electronic transmission layer are promoted. The defects of a metal oxide structure are reduced, and the surface roughness of a crystal material is reduced, so that the surface of an electron transport layer is smoother, the interface roughness is reduced, the bonding performance with an adjacent cathode is better, the interface gap is optimized, and the influence of charge accumulation on the service life of a device is avoided. Meanwhile, the ultraviolet irradiation treatment promotes the fusion of the metal oxide electron transport material and the electrode, reduces the potential barrier and improves the electron injection efficiency. In addition, the electronic transmission layer with a smoother surface is beneficial to the preparation of the subsequent quantum dot light-emitting layer on the surface, so that the interface bonding performance of the electronic transmission layer and the quantum dot layer is better, the transmission and injection efficiency of electrons is improved, and the influence of the accumulation of electric charges at the interface on the service life and the safety performance of the device is avoided.
According to the luminescent device provided by the second aspect of the application, because the first ultraviolet illumination treatment is carried out after the electron transport layer is prepared on the surface of the cathode, the fusion of the metal oxide electron transport material and the electrode is promoted, the potential barrier is reduced, and the electron injection efficiency is improved. Meanwhile, internal bonding and crystal regrowth in the electron transport layer are promoted, the internal physical structure defects and surface roughness of the electron transport layer are reduced, and the electron mobility in the electron transport layer is improved, so that the efficiency and stability of the photoelectric device are improved, and the service life of the device is prolonged.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, 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 application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for manufacturing a light-emitting device provided in an embodiment of the present application;
fig. 2 is a schematic structural diagram of a quantum dot light emitting diode provided in an embodiment of the present application;
FIG. 3 is a graph showing the efficiency of the quantum dot light emitting diode provided in example 1 and comparative example 1 of the present application;
FIG. 4 is a graph of current density versus voltage for quantum dot light emitting diodes provided in example 1 and comparative example 1 of the present application;
fig. 5 is a graph showing luminance curves of the quantum dot light emitting diodes provided in example 1 and comparative example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application. The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for manufacturing a light emitting device, including the following steps:
s10, obtaining a substrate deposited with a cathode;
s20, preparing an electron transmission layer on the surface of the cathode, which is far away from the substrate, wherein the electron transmission layer comprises a metal oxide transmission material;
and S30, after the first ultraviolet irradiation treatment is carried out on the electron transport layer, a quantum dot light emitting layer and an anode are sequentially prepared on the side surface of the electron transport layer, which is far away from the cathode, so that the light emitting device is obtained.
According to the preparation method of the light-emitting device, after the metal oxide electronic transmission layer is prepared on the surface of the cathode, the electronic transmission layer is subjected to first ultraviolet irradiation treatment, and through the ultraviolet irradiation treatment, the metal oxide in the electronic transmission layer has a strong absorption effect on ultraviolet visible light, so that the internal temperature of the electronic transmission layer is increased, bonding electrons are activated, and the internal bonding and crystal regrowth in the electronic transmission layer are promoted. The defects of a metal oxide structure are reduced, and the surface roughness of a crystal material is reduced, so that the surface of an electron transport layer is smoother, the interface roughness is reduced, the bonding performance with an adjacent cathode is better, the interface gap is optimized, and the influence of charge accumulation on the service life of a device is avoided. Meanwhile, the ultraviolet irradiation treatment promotes the fusion of the metal oxide electron transport material and the electrode, reduces the potential barrier and improves the electron injection efficiency. In addition, the electronic transmission layer with a smoother surface is beneficial to the preparation of the subsequent quantum dot light-emitting layer on the surface, so that the interface bonding performance of the electronic transmission layer and the quantum dot layer is better, the transmission and injection efficiency of electrons is improved, and the influence of the accumulation of electric charges at the interface on the service life and the safety performance of the device is avoided.
Specifically, in the above step S10, the substrate on which the cathode is deposited is obtained. In some embodiments, the cathode comprises at least one metal material or at least two alloy materials of Mg, Ag, Al, and Ca, and under the condition of ultraviolet irradiation, the cathode metal material has good fusion effect with the metal oxide electron transport material, so that the electron injection barrier can be reduced, and the efficiency of injecting electrons into the photoelectric device can be improved.
In some embodiments, the cathode has a thickness of 10 to 200 nm. The thickness of the cathode in the embodiment of the present application is preferably 200nm or less, and when the ultraviolet light wave is irradiated from the cathode side, it is preferably 100nm or less, so as to avoid attenuation of the cathode metal layer to the transition of the irradiated light.
Specifically, in step S20 described above, a metal oxide electron transport layer is prepared on the side surface of the cathode facing away from the substrate. In some embodiments, the metal oxide transport material is selected from: ZnO, TiO2、Fe2O3、SnO2、Ta2O3At least one of; the metal oxide materials have high electron mobility, have good fusion with a cathode after being excited by ultraviolet light, and are beneficial to reducing potential barriers and improving electron injection efficiency.
In some embodiments, the metal oxide transport material is selected from: metallic element-doped ZnO, TiO2、Fe2O3、SnO2、Ta2O3Wherein the metal element comprises at least one of aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium and cobalt. The metal oxide transmission material in the embodiment of the application is doped with metal elements such as aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, cobalt and the like, so that the electron transmission and migration efficiency of the material can be further improved.
In some embodiments, the particle size of the metal transmission material is less than or equal to 10nm, and the transmission material with small particle size is more favorable for forming a compact, uniform-thickness and flat-surface electron transmission layer; and the metal oxide material with small particle size has larger specific surface area, has better fusion effect with the metal electrode layer after being excited by ultraviolet light, is more favorable for reducing potential barrier and improving electron injection efficiency.
Specifically, in step S30, the electron transport layer is subjected to the first ultraviolet irradiation treatment. In some embodiments, the step of the first ultraviolet light irradiation treatment comprises: the wavelength of ultraviolet light is 250-420 nm, and the light wave density is 10-300 mJ/cm2Under the condition (1), the electron transport layer is irradiated for 10-60 min. The ultraviolet irradiation treatment condition of the embodiment of the application can better promote the internal bonding of the metal oxide transmission material in the electron transmission layer and the crystal regrowth, is favorable for promoting the interface fusion between the electron transmission layer and the metal cathode layer, enables the combination to be tighter, reduces interface gaps, optimizes interface roughness and enables electrons to be more favorable for being injected into the electron transmission layer from the cathode.
In some embodiments, the step of the first ultraviolet light irradiation treatment comprises: the wavelength is 320-420 nm, and the light wave density is 10-150 mJ/cm2The ultraviolet light waves are irradiated for 10-60 min from one side of the electron transport layer. When the ultraviolet light wave is from electron transport layer one side, metal oxide electron transport material can directly absorb UV light and carry out crystal regrowth and inside bonding, and the decay of light is less, therefore can adopt the longer wavelength relatively alright reach the treatment effect, and is little to the material influence.
In some embodiments, the step of the first ultraviolet light irradiation treatment comprises: the wavelength is 250-320 nm, and the light wave density is 100-300 mJ/cm2The ultraviolet light waves are irradiated for 10-60 min from one side of the cathode. When this application embodiment ultraviolet light wave was followed cathode layer one side, because free electron is many in the metal cathode layer, to the light loss big, light is great through cathode metal layer decay, need adopt shorter wavelength, the higher UV light of density to handle this moment just can reach better treatment effect.
In some embodiments, the conditions of the first ultraviolet light irradiation treatment further include: at H2O content less than 1ppm, temperature 80 toIs carried out in the environment of 120 ℃. Examples of the present application are as follows2The O content is less than 1ppm, and the ultraviolet irradiation treatment is carried out in the environment with the temperature of 80-120 ℃, so that the influence on the material performance in the irradiation treatment process due to overhigh water content in the environment is avoided. Meanwhile, the heating environment of 80-120 ℃ is favorable for further promoting the bonding of electrons exciting O and zinc ions and activating bonding electrons.
In some embodiments, the electron transport layer has a thickness of 10 to 200nm, which satisfies device and structural requirements. In some embodiments, when the thickness of the electron transport layer is less than 80nm, the ultraviolet light irradiation treatment is performed for a period of 15 minutes to 45 minutes. When the thickness of the electron transmission layer is lower than 80nm, the light wave energy of the material layer with low thickness is relatively easy to penetrate, the illumination time required for achieving the treatment effect is short, and the duration of ultraviolet irradiation treatment is appropriate from 15 minutes to 45 minutes. In other embodiments, when the thickness of the electron transport layer is greater than 80nm, the ultraviolet light irradiation treatment is performed for a period of 30 minutes to 90 minutes. When the thickness of the electronic transmission layer is higher than 80nm, the light wave energy of the material layer with thicker thickness is difficult to penetrate, the illumination time required for achieving the treatment effect is longer, and the duration of the ultraviolet irradiation treatment is suitable from 30 minutes to 90 minutes.
Specifically, in step S30, the step of preparing the quantum dot light emitting layer on the side surface of the electron transport layer facing away from the cathode includes: and after the quantum dot material is deposited on the side surface of the electron transport layer departing from the cathode, carrying out secondary ultraviolet irradiation treatment to form a quantum dot light-emitting layer. According to the embodiment of the application, the secondary ultraviolet irradiation treatment is carried out after the quantum dot material is deposited on the surface of the electron transport layer, through the ultraviolet irradiation treatment, electrons of O in the metal oxide transport material in the electron transport layer are excited to form a complex with active metal elements such as Zn in the quantum dot light emitting layer, an ETL-QD interface is optimized through formation of a coordination bond, interface defects are reduced, and injection of electrons from the electron transport layer to the inside of the quantum dot light emitting layer is facilitated. And because the electrons of the O are coordinated with the metal of the quantum dot material, the bonding defect inside the electron transport layer is increased, so that the electron mobility in the electron transport layer is improved. In addition, the formed complex has a strong absorption effect on UV, so that the temperature at the interface of the electron transmission layer and the quantum dot light-emitting layer is increased, bonding electrons are activated, crystal regrowth in the electron transmission layer is promoted, the defects of the internal physical structure and the surface roughness of the electron transmission layer are reduced, the QD-ETL interface is better in combination tightness, the electron accumulation centers in the electron transmission layer and the QD-ETL interface are reduced, the electron injection efficiency in the light-emitting layer is improved, the material aging is slowed down, and the service life of a device is prolonged.
In some embodiments, the quantum dot material is a core-shell structure, and the outer shell layer of the quantum dot material contains zinc element. Because the existing quantum dot synthesis mostly adopts II-VI group elements, Zn and VI group elements have better matching property in the aspects of lattice matching and band gap, and can cover the whole visible light wave band, and the shell layer of the quantum dot material containing the Zn element has suitable chemical activity, high flexibility and controllability, wide band gap, good exciton constraint property, high quantum efficiency and good water oxygen stability. In addition, the coordination effect of the zinc element and the electrons of O is better and more stable. By UV irradiation, electrons of O of the metal oxide transport material in the electron transport layer are excited, and a complex, i.e., a ZnO complex, is easily formed with Zn element in the QD. The formation of ZnO matched bonds is beneficial to electron injection, and the electron mobility in the electron transport layer is improved. Meanwhile, the ZnO complex has a strong absorption effect on ultraviolet wavelength, and is beneficial to activating bonding electrons, so that crystals in the ETL grow again, the defects of the internal physical structure and the surface roughness of the ETL are reduced, the electron injection is facilitated, the electron accumulation is reduced, the material aging is slowed down, and the service life of a device is prolonged.
In some embodiments, the outer shell layer of quantum dot material comprises: the shell material contains zinc element, the zinc element has high activity, and has better coordination effect with excited O electrons in the electron transport material.
In some embodiments, the thickness of the outer shell layer of the quantum dot material is 0.2-6.0 nm, and the thickness ensures the stability and the carrier injection effect of the inner layer material of the quantum dot, and simultaneously ensures the coordination effect of the zinc element in the outer shell layer and the O element in the metal oxide transmission material.
In some embodiments, the quantum dot light emitting layer has a thickness of 8 to 100nm, which satisfies device requirements and structural requirements.
In some embodiments, the step of second uv irradiation treatment comprises: the ultraviolet light wavelength is 300-420 nm, and the light wave density is 10-300 mJ/cm2Under the condition, the quantum dot material of the quantum dot light-emitting layer is irradiated for 10-60 min. In some embodiments, the conditions of the second ultraviolet light irradiation treatment include: at H2The O content is less than 1 ppm. According to the ultraviolet illumination condition of the quantum dot light emitting layer after the quantum dot material is deposited, on one hand, the ultraviolet illumination condition is beneficial to promoting electrons of O in the metal oxide transmission material in the electron transmission layer to be excited and forming a complex with active metal elements such as Zn in the quantum dot light emitting layer, an ETL-QD interface is optimized through formation of a coordination bond, interface defects are reduced, and injection of electrons from the ETL to the inside of the QD is facilitated. On the other hand, the characteristics of the quantum dot material with the core-shell structure are fully considered, and in order to avoid the destructive effect of ultraviolet energy on the quantum dot material, light with longer wavelength and lower light wave energy is adopted for processing.
In some embodiments, when the shell layer of the quantum dot material is ZnS, the wavelength of the ultraviolet irradiation treatment is 300-355 nm, and the optical density is 50-150 mJ/cm2. In the embodiment of the application, when the shell layer is ZnS, the ZnS bond energy is about 3.5eV, the ZnO bond energy is about 3.3eV, the wavelength is 300-355 nm, and the optical wave density is 50-150 mJ/cm2Under the condition, the transfer of bonding charges of electronic transmission materials such as ZnS and ZnO in the shell of the quantum dot material can be caused, so that the zinc element in the shell layer and the O element in the electronic transmission material have better coordination effect, and a complex of the electronic transmission material and the quantum dot material is formed.
In some embodiments, when ZnSe is used as the shell layer of the quantum dot material, the wavelength of the ultraviolet irradiation treatment is 320-375 nm, and the optical density is 30-120 mJ/cm2. In the embodiment of the application, when the outer shell layer is ZnSe, the ZnSe bond energy is about 2.9eV, and the ZnO bond energyAbout 3.3eV, a wavelength of 320-375 nm in ultraviolet irradiation treatment, and a light wave density of 30-120 mJ/cm2Under the condition, the transfer of bonding charges of electronic transmission materials such as ZnSe and ZnO in the shell of the quantum dot material can be caused, so that the zinc element in the shell layer and the O element in the electronic transmission material have better coordination effect, and a complex of the electronic transmission material and the quantum dot material is formed.
In some embodiments, when the shell layer of the quantum dot material is ZnSeS, the wavelength of the ultraviolet irradiation treatment is 350-375 nm, and the light wave density is 30-150 mJ/cm2. When the outer shell layer is ZnSeS, the ZnSeS bond energy is about 2.7eV, the ZnO bond energy is about 3.3eV, the wavelength of ultraviolet irradiation treatment is 350-375 nm, and the optical wave density is 30-150 mJ/cm2Under the condition, the transfer of bonding charges of electronic transmission materials such as ZnSeS, ZnO and the like in the shell of the quantum dot material can be caused, so that the zinc element in the shell layer and the O element in the electronic transmission material have better coordination effect, and a complex of the electronic transmission material and the quantum dot material is formed.
In some embodiments, after the preparing the sub-dot light emitting layer, the method further comprises the following steps: and preparing a hole transport layer on the surface of the quantum dot light emitting layer deviating from the electron transport layer, and preparing an anode on the surface of the hole transport layer deviating from the quantum dot light emitting layer.
In some embodiments, the fabrication of the light emitting device of the embodiments of the present application includes the steps of:
s40, providing a substrate deposited with a cathode;
s50, preparing an electron transmission layer on the side surface of the cathode, which is far away from the substrate, wherein the electron transmission layer comprises a metal oxide transmission material;
s60, carrying out first ultraviolet irradiation treatment on the electron transport layer;
s70, preparing a quantum dot light-emitting layer on the side surface of the electron transport layer, which is far away from the cathode;
s80, carrying out secondary ultraviolet light treatment on the quantum dot light-emitting layer;
s90, preparing a hole transport layer on the surface of the quantum dot light emitting layer;
s100, evaporating an anode on the hole injection layer to obtain the light-emitting device.
Specifically, in step S40, in order to obtain a high-quality light emitting device, the substrate needs to undergo a pretreatment process including the steps of: cleaning the substrate with a cleaning agent to primarily remove stains on the surface, then sequentially and respectively ultrasonically cleaning the substrate in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally blowing the substrate with high-purity nitrogen for drying.
Specifically, in step S50, the step of preparing the electron transport layer includes: the electron transmission layer is made of a metal oxide transmission material, a prepared metal oxide transmission material solution with a certain concentration is deposited on a cathode to form a film through the processes of drop coating, spin coating, soaking, coating, printing, evaporation and the like, the thickness of the electron transmission layer is controlled by adjusting the concentration of the solution, the deposition speed (preferably, the rotating speed is 3000-5000 rpm) and the deposition time to be about 20-60 nm, then the film is annealed to form the film at the temperature of 150-200 ℃, and the solvent is sufficiently removed to obtain the electron transmission layer.
Specifically, in step S60, the step of performing the first ultraviolet irradiation treatment on the electron transport layer includes: at H2The O content is less than 1ppm, the ultraviolet light wavelength is 250-420 nm and the light wave density is 10-300 mJ/cm under the environment of 80-120 DEG C2The ultraviolet light vertically irradiates the electron transport layer for 10-60 min.
Specifically, in step S70, the step of preparing the quantum dot light emitting layer includes: and depositing a prepared luminescent material solution with a certain concentration on the electron transport layer to form a film through processes of drop coating, spin coating, soaking, coating, printing, evaporation and the like, controlling the thickness of the luminescent layer to be about 20-60 nm by adjusting the concentration, the deposition speed and the deposition time of the solution, and drying at a proper temperature.
Specifically, in step S80, the step of performing the second ultraviolet irradiation treatment on the quantum dot light-emitting layer includes: at H2The O content is less than 1ppm, the temperature is 80-120 ℃, the ultraviolet wavelength is 300-420 nm, and the light wave density is 10-300 mJ/cm2The ultraviolet light vertically irradiates the electron transport layer for 10-60 min.
Specifically, in step S90, the step of preparing the hole transport layer includes: depositing a prepared solution of the hole transport material on the surface of the quantum dot light-emitting layer to form a film through processes of dropping coating, spin coating, soaking, coating, printing, evaporation and the like; the film thickness is controlled by adjusting the concentration of the solution, the deposition rate and the deposition time, and then the thermal annealing treatment is performed at an appropriate temperature.
Specifically, in step S100, the substrate on which the functional layers are deposited is placed in an evaporation chamber to prepare an anode by deposition.
In a further embodiment, the obtained QLED device is subjected to a packaging process, and the packaging process may be performed by a common machine or by a manual method. Preferably, the oxygen content and the water content are both lower than 0.1ppm in the packaging treatment environment to ensure the stability of the device.
A second aspect of embodiments of the present application provides a light emitting device, which is manufactured by the above-described method.
According to the luminescent device provided by the second aspect of the application, because the first ultraviolet irradiation treatment is carried out after the electron transport layer is prepared on the surface of the cathode, the fusion of the metal oxide electron transport material and the electrode is promoted, the potential barrier is reduced, and the electron injection efficiency is improved. Meanwhile, internal bonding and crystal regrowth in the electron transport layer are promoted, the internal physical structure defects and surface roughness of the electron transport layer are reduced, and the electron mobility in the electron transport layer is improved, so that the efficiency and stability of the photoelectric device are improved, and the service life of the device is prolonged.
In one embodiment, the light emitting device includes a stacked structure of an anode and a cathode disposed opposite each other, a light emitting layer disposed between the anode and the cathode, and the cathode disposed on a substrate. Further, a hole functional layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the light-emitting layer; an electron-transporting layer, an electron-injecting layer, a hole-blocking layer, and other electron-functional layers may also be provided between the cathode and the light-emitting layer, as shown in fig. 2. In some embodiments of the structural device, the light emitting device includes a substrate, a cathode disposed on a surface of the substrate, an electron transport layer disposed on a surface of the cathode, a light emitting layer disposed on a surface of the electron transport layer, a hole transport layer disposed on a surface of the light emitting layer, and an anode disposed on a surface of the hole transport layer.
In some embodiments, the substrate is not limited to be used, and a rigid substrate or a flexible substrate may be used. In some embodiments, the rigid substrate includes, but is not limited to, one or more of glass, metal foil. In some embodiments, the flexible substrate includes, but is not limited to, one or more of polyethylene terephthalate (PET), polyethylene terephthalate (PEN), Polyetheretherketone (PEEK), Polystyrene (PS), Polyethersulfone (PES), Polycarbonate (PC), Polyarylate (PAT), Polyarylate (PAR), Polyimide (PI), polyvinyl chloride (PV), Polyethylene (PE), polyvinylpyrrolidone (PVP), textile fibers.
In some embodiments, the anode material is selected without limitation and may be selected from doped metal oxides including, but not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO). Or a composite electrode with metal sandwiched between doped or undoped transparent metal oxides, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2、TiO2/Al/TiO2One or more of (a).
In some embodiments, the hole injection layer includes, but is not limited to, one or more of an organic hole injection material, a doped or undoped transition metal oxide, a doped or undoped metal chalcogenide compound. In some embodiments, the organic hole injection material includes, but is not limited to, one or more of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT: PSS), copper phthalocyanine (CuPc), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN). In some embodiments, the transition goldThe metal oxide includes but is not limited to MoO3、VO2、WO3、CrO3And CuO. In some embodiments, the metal chalcogenide compounds include, but are not limited to, MoS2、MoSe2、WS2、WSe2And CuS.
In some embodiments, the hole transport layer may be selected from an organic material having a hole transport ability and/or an inorganic material having a hole transport ability. In some embodiments, the organic material having hole transport capability includes, but is not limited to, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK), poly (N, N ' bis (4-butylphenyl) -N, N ' -bis (phenyl) benzidine) (poly-TPD), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4,4,4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 4,4' -bis (9-Carbazole) Biphenyl (CBP), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB). In some embodiments, inorganic materials with hole transport capability include, but are not limited to, doped graphene, undoped graphene, C60, doped or undoped MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2And CuS.
In some embodiments, the light emitting layer includes a quantum dot material, the quantum dot material is a quantum dot material with a core-shell structure, and an outer shell layer of the quantum dot material contains zinc element. In some embodiments, the outer shell layer of quantum dot material comprises: at least one or at least two of ZnS, ZnSe, ZnTe, CdZnS and ZnCdSe. In some embodiments, the particle size range of the quantum dot material is 2-10 nm, the particle size is too small, the film forming property of the quantum dot material is poor, the energy resonance transfer effect among quantum dot particles is significant, the application of the material is not facilitated, the particle size is too large, the quantum effect of the quantum dot material is weakened, and the photoelectric property of the material is reduced.
In some embodiments, the material of the electron transport layer is the metal oxide transport material described above.
In some embodiments, the cathode material may be one or more of various conductive carbon materials, conductive metal oxide materials, metal materials. In some embodiments, the conductive carbon material includes, but is not limited to, doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, porous carbon, or mixtures thereof. In some embodiments, the conductive metal oxide material includes, but is not limited to, ITO, FTO, ATO, AZO, or mixtures thereof. In some embodiments, the metallic material includes, but is not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein the metal material is in a form including but not limited to a compact film, a nanowire, a nanosphere, a nanorod, a nanocone, a hollow nanosphere, or a mixture thereof; preferably, the cathode is Ag or Al.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art and to make the progress of the light emitting device and the manufacturing method thereof obvious, the above technical solution is illustrated by a plurality of examples below.
Example 1
A light emitting diode comprising the following fabrication steps:
(1) providing a substrate with an Al cathode deposited thereon, and performing cleaning pretreatment on the substrate.
(2) Forming an electron transport layer on the Al cathode of the step (1): in a glove box (the water oxygen content is less than 0.1ppm), ZnO solution (the concentration is 45mg/mL, the solvent is ethanol) is coated on an ITO cathode in a spinning way, the spinning is carried out at 3000rpm for 30s, and then the annealing treatment is carried out at 80 ℃ for 30min, thus forming the electron transmission layer.
(3) At H2Irradiating the electron transport layer perpendicularly from the electron transport layer side at an O content of less than 1ppm and a temperature of 100 deg.C under UV wavelength of 400nm and intensity of 100mJ/cm2UV time 30 min.
(4) Forming a light emitting layer on the electron transport layer: taking a CdSe/ZnS quantum dot solution (with the concentration of 30mg/mL and the solvent of n-octane), and spin-coating the CdSe/ZnS quantum dot solution on the electron transport layer in a glove box (with the water oxygen content of less than 0.1ppm) at the rotating speed of 3000rpm to form a light-emitting layer.
(5) At H2O content less than 1ppm, and UV wavelength of 320nm and intensity of 150mJ/cm at 100 deg.C2The light emitting layer was irradiated vertically for 10 min.
(6) Forming a hole transport layer on the light emitting layer: under an electric field, spin-coating a TFB solution (with the concentration of 8mg/mL and the solvent of chlorobenzene) on a light-emitting layer, carrying out spin-coating at 3000rpm for 30s, and then carrying out annealing treatment at 80 ℃ for 30min to form a hole transport layer; wherein the action direction of the electric field is perpendicular to the anode and faces the hole transport layer, and the electric field intensity is 104V/cm。
(7) Forming a hole injection layer on the hole transport layer: spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on the hole transport layer under an electric field, spin-coating at 5000rpm for 40s, and then annealing at 150 ℃ for 15min to form a hole injection layer; wherein the action direction of the electric field is perpendicular to the anode and faces the hole injection layer, and the electric field intensity is 104V/cm。
(8) An ITO anode is formed on the hole injection layer.
Example 2
A light emitting diode, which was manufactured by the steps different from those of example 1: in the step (3), vertical UV irradiation is performed from the cathode side, the UV wavelength is 300nm, and the intensity is 200mJ/cm2UV time 30 min.
Example 3
A light emitting diode, which is manufactured by the steps different from those of example 1: TiO is adopted in the step (2)2The solution is spin coated on the luminescent layer.
Example 4
A light emitting diode, which is manufactured by the steps different from those of example 1: ZnMgO is adopted in the step (2).
Example 5
A light emitting diode, which was manufactured by the steps different from those of example 1: CdZnSe/ZnSe is adopted in the step (4). In the step (5), the ultraviolet illumination conditions are as follows: the UV wavelength is 340nm, and the intensity is 100mJ/cm2The light emitting layer was irradiated vertically for 10 min.
Example 6
A light emitting diode, which was manufactured by the steps different from those of example 1: CdZnSe/ZnSeS is adopted in the step (4). In the step (5), the ultraviolet illumination conditions are as follows: UV wavelength of 370nm and intensity of 120mJ/cm are adopted2The light emitting layer was irradiated vertically for 10 min.
Comparative example 1
A light emitting diode, which was manufactured by the steps different from those of example 1: the UV treatment of steps (3) and (5) is not performed.
Comparative example 2
A light emitting diode, which was manufactured by the steps different from those of example 1: without UV treatment in step (5).
Comparative example 3
A light emitting diode, which was manufactured by the steps different from those of example 1: the UV treatment of the step (3) is not carried out.
Further, in order to verify the advancement of the embodiments of the present application, the following performance tests were performed on the embodiments 1 to 6 and the comparative examples 1 to 3, wherein the test indexes and the test methods are as follows, and the test results are shown in the following table 1 and the accompanying drawings 3 to 5:
(1) construction of Current Density-Voltage (J-V) curves
And testing by adopting an efficiency testing system built by LabView control QE PRO spectrometer, Keithley2400 and Keithley6485 under the environment of room temperature and 30-60% of air humidity, and measuring parameters such as voltage and current to construct a J-V curve.
(2) External Quantum Efficiency (EQE):
the ratio of the number of electrons-holes injected into the quantum dots to the number of emitted photons, the unit is%, is an important parameter for measuring the quality of the electroluminescent device, and can be obtained by measuring with an EQE optical measuring instrument. The specific calculation formula is as follows:
where η e is the optical outcoupling efficiency, η r is the ratio of the number of recombination carriers to the number of injection carriers, χ is the ratio of the number of excitons that generate photons to the total number of excitons, KR is the radiative process rate, and KNR is the non-radiative process rate. And (3) testing conditions are as follows: the method is carried out at room temperature, and the air humidity is 30-60%.
(3) Construction of a Brightness-Voltage (L-V) Curve
The luminance (L) is the ratio (cd/m2) of the area of the luminous flux of the light emitting surface in a given direction to the luminous flux perpendicular to the given direction. And controlling the calibrated linear silicon light pipe system PDB-C613 by adopting LabView to measure, calculating the brightness of the device by combining a spectrum and a visual function, and constructing an L-V curve according to the change of the brightness along with the voltage.
(4) Life test
In the following examples, the lifetime test was carried out by a constant current method at a constant 50mA/cm2Under the drive of current, a silicon optical system is adopted to test the brightness change of the device, the time LT95 of the brightness of the device from the highest point to the highest brightness of 95% is recorded, and then the service life of the device 1000nit LT95S is extrapolated by an empirical formula:
1000nit LT95＝(LMax/1000)1.7×LT95；
the method is convenient for comparing the service lives of devices with different brightness levels, and has wide application in practical photoelectric devices.
TABLE 1
As can be seen from the test results in Table 1 of examples 1 to 6 and comparative examples 1 to 3, and the efficiency curves (voltage on the abscissa and external quantum efficiency on the ordinate) of FIG. 3, the current density-voltage curves (voltage on the abscissa and current density on the ordinate) of FIG. 4, and the luminance curves (time on the abscissa and luminance on the ordinate) of FIG. 5 of examples 1 to 6 of the present application, the devices treated with UV have better luminous efficiency and longer luminous life than the devices of comparative examples 1 to 3, in addition to the efficiency curves (voltage on the abscissa and external quantum efficiency on the abscissa) of example 1(S2) and comparative example 1 (S1).
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for manufacturing a light emitting device, comprising the steps of:
obtaining a substrate deposited with a cathode;
preparing an electron transport layer on the surface of the cathode, which is far away from the substrate, wherein the electron transport layer comprises a metal oxide transport material;
and after the first ultraviolet irradiation treatment is carried out on the electron transport layer, a quantum dot light-emitting layer and an anode are sequentially prepared on the side surface of the electron transport layer departing from the cathode, so that the light-emitting device is obtained.
2. The method for manufacturing a light-emitting device according to claim 1, wherein the first ultraviolet light irradiation treatment step includes: the wavelength of ultraviolet light is 250-420 nm, and the light wave density is 10-300 mJ/cm2Under the condition (1), irradiating the electron transport layer for 10-60 min.
3. The method for manufacturing a light-emitting device according to claim 2, wherein the first ultraviolet irradiation treatment step includes: the wavelength is 320-420 nm, and the light wave density is 10-150 mJ/cm2Irradiating the ultraviolet light waves from one side of the electron transport layer for 10-60 min;
alternatively, the first ultraviolet irradiation treatment step includes: the wavelength is 250-320 nm, and the light wave density is 100-300 mJ/cm2The ultraviolet light waves are irradiated for 10-60 min from one side of the cathode.
4. A method for manufacturing a light-emitting device according to claim 3, wherein the conditions of the first ultraviolet light irradiation treatment further include: at H2The O content is less than 1ppm, and the reaction is carried out at the temperature of 80-120 ℃.
5. The method according to any one of claims 1 to 4The method for producing a light-emitting device of (1), wherein the metal oxide transport material is selected from the group consisting of: ZnO, TiO2、Fe2O3、SnO2、Ta2O3At least one of (a);
and/or, the metal oxide transport material is selected from: ZnO, TiO doped with metal element2、Fe2O3、SnO2、Ta2O3Wherein the metal element comprises at least one of aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, and cobalt;
and/or the particle size of the metal transmission material is less than or equal to 10 nm.
6. The method for manufacturing a light-emitting device according to claim 5, wherein the cathode comprises at least one metal material or an alloy material of at least two of Mg, Ag, Al, Ca;
and/or the thickness of the cathode is 10-200 nm.
7. The method of claim 6, wherein the step of forming a quantum dot light emitting layer on a side surface of the electron transport layer facing away from the cathode comprises: after quantum dot materials are deposited on the side surface, away from the cathode, of the electron transport layer, secondary ultraviolet irradiation treatment is carried out, and a quantum dot light emitting layer is formed;
and/or, after the quantum dot light-emitting layer is prepared, the method also comprises the following steps: and preparing a hole transport layer on the surface of the quantum dot light-emitting layer, which is far away from the electron transport layer, and preparing the anode on the surface of the hole transport layer, which is far away from the quantum dot light-emitting layer.
8. The method for manufacturing a light-emitting device according to claim 7, wherein the quantum dot material has a core-shell structure, and an outer shell layer of the quantum dot material contains zinc;
and/or the shell layer of the quantum dot material comprises: at least one or two of ZnS, ZnSe, ZnTe, CdZnS and ZnCdSe;
and/or the thickness of the shell layer of the quantum dot material is 0.2-6.0 nm.
9. The method for manufacturing a light-emitting device according to claim 8, wherein the second ultraviolet light irradiation treatment step includes: the ultraviolet light wavelength is 300-420 nm, and the light wave density is 10-300 mJ/cm2Under the condition (1), carrying out irradiation treatment on the quantum dot light-emitting layer for 10-60 min;
and/or the conditions of the second ultraviolet irradiation treatment comprise: at H2The O content is less than 1 ppm.
10. A light-emitting device produced by the method according to any one of claims 1 to 9.
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