CN113948663A - Quantum dot light-emitting diode and preparation method thereof - Google Patents
Quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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- CN113948663A CN113948663A CN202010680027.5A CN202010680027A CN113948663A CN 113948663 A CN113948663 A CN 113948663A CN 202010680027 A CN202010680027 A CN 202010680027A CN 113948663 A CN113948663 A CN 113948663A
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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]
- H10K50/18—Carrier blocking 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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Abstract
The application relates to the technical field of display, and provides a quantum dot light-emitting diode which comprises a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged between the cathode and the anode, a hole transport layer arranged between the anode and the quantum dot light-emitting layer, and a hole blocking layer arranged between the hole transport layer and the quantum dot light-emitting layer; wherein the material of the hole blocking layer is at least one selected from potassium chloride and sodium chloride. By adopting at least one of potassium chloride, sodium chloride and potassium bromide as the material of the hole barrier layer, the electron and hole injection balance of the quantum dot light-emitting diode is increased, the leakage current of the device is effectively reduced, the luminous efficiency of the quantum dot light-emitting diode is improved, and the service life of the quantum dot light-emitting diode is prolonged.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a quantum dot light-emitting diode and a preparation method thereof.
Background
Because Quantum Dots (QDs) have the advantages of narrow Light-Emitting line width, adjustable Light-Emitting wavelength, high Light-Emitting color saturation, wide Light-Emitting color gamut, and the like, and in addition, the Quantum dots (QLEDs) with Quantum dots as Light-Emitting centers have the advantages of long theoretical life of inorganic nanocrystals, good device stability, and the like, Quantum dots Light-Emitting Diodes (QLEDs) have great potential as next-generation display and solid-state illumination Light sources.
In order to promote the development of the QLED device, people continuously improve the performance of the QLED device by optimizing the device structure by changing the material of the charge transport layer. At present, the external quantum efficiency of a red light QLED device is up to more than 20%, and the device can be compared favorably with the performance of an Organic Light Emitting Diode (OLED), but quantum dots containing Cd are mostly adopted in QDs, and the use and development of Cd are limited by the heavy metal property of Cd. The performance of the green and environment-friendly InP quantum dot QLED device is far away from that of the quantum dot QLED containing Cd, and the commercialization requirement cannot be met. In the inverted QLED, solvents of a hole transport layer, such as chlorobenzene, dichlorobenzene, cyclohexylbenzene, toluene and the like, dissolve the QD layer, so that the luminous efficiency and the service life of the device are influenced; in addition, a large electron injection barrier exists in the QLED device, and more holes are injected than electrons, so that imbalance between hole injection and electron injection is caused, and the luminous efficiency and the service life of the device are further influenced.
Disclosure of Invention
The application aims to provide a quantum dot light-emitting diode and a preparation method thereof, and aims to solve the problems that the light-emitting efficiency and the service life of the conventional quantum dot light-emitting diode are to be improved.
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 quantum dot light emitting diode, including a cathode and an anode that are oppositely disposed, a quantum dot light emitting layer disposed between the cathode and the anode, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and a hole blocking layer disposed between the hole transport layer and the quantum dot light emitting layer; wherein, the material of the hole blocking layer is at least one selected from potassium chloride, sodium chloride and potassium bromide.
In a second aspect, the present application provides a method for preparing a quantum dot light emitting diode, comprising the following steps:
providing a halogen salt solution containing at least one of potassium chloride, sodium chloride and potassium bromide, and a cathode substrate;
preparing a quantum dot light-emitting layer on the surface of the cathode substrate;
depositing a solution of potassium chloride and/or sodium chloride on the surface of the quantum dot light-emitting layer, which is far away from the cathode substrate, and carrying out heat treatment to prepare a hole blocking layer;
depositing a hole transport material on the surface of the hole blocking layer, which is far away from the quantum dot light-emitting layer, so as to prepare a hole transport layer;
and preparing an anode on the surface of the hole transport layer, which is far away from the hole blocking layer.
The application provides a quantum dot emitting diode, through adopting at least one in potassium chloride, sodium chloride, the potassium bromide as the material of hole barrier layer, increase quantum dot emitting diode's electron and hole injection balance, effectively reduce the device and leak current, improve quantum dot emitting diode's luminous efficacy and life.
The application provides a preparation method of quantum dot emitting diode quantum dot luminescent layer deviates from the surface deposition of cathode substrate the halide salt solution that contains at least one in potassium chloride, sodium chloride, the potassium bromide prepares the hole barrier layer to increase quantum dot emitting diode's electron and hole injection balance, effectively reduce the device and leak current, improve quantum dot emitting diode's luminous efficacy and life.
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 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 disclosure;
fig. 2 is a schematic structural diagram of another quantum dot light emitting diode provided in an embodiment of the present application;
fig. 3 is a flowchart of a process for manufacturing a quantum dot light emitting diode according to an embodiment of the present disclosure.
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. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
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.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances, interfaces, messages, requests and terminals from one another and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a quantum dot light emitting diode, including a cathode and an anode that are oppositely disposed, a quantum dot light emitting layer disposed between the cathode and the anode, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and a hole blocking layer disposed between the hole transport layer and the quantum dot light emitting layer; wherein, the material of the hole blocking layer is at least one selected from potassium chloride, sodium chloride and potassium bromide.
The quantum dot light-emitting diode that this application embodiment provided, potassium chloride, sodium chloride, potassium bromide have good effect of blockking to the migration of hole, and simultaneously, the light transmissivity after the film-forming is better, consequently, this application embodiment is through adopting at least one in potassium chloride, sodium chloride, the potassium bromide as the material of hole barrier layer, increases quantum dot light-emitting diode's electron and hole injection balance, effectively reduces the device and leaks the current, improves quantum dot light-emitting diode's luminous efficacy and life.
The material of the hole blocking layer provided by the embodiment of the present application is selected from at least one of potassium chloride and sodium chloride, including four cases. In a first embodiment, the material of the hole blocking layer is selected from sodium chloride, i.e. the hole blocking layer is a sodium chloride layer; in a second embodiment, the material of the hole blocking layer is selected from potassium chloride, i.e. the hole blocking layer is a potassium chloride layer; in a third embodiment, the material of the hole blocking layer is selected from potassium bromide, i.e. the hole blocking layer is a potassium bromide layer; in a fourth embodiment, the material of the hole blocking layer is selected from a mixed material of at least two of potassium chloride, sodium chloride and potassium bromide, that is, the hole blocking layer is a mixed material layer of at least two of potassium chloride, sodium chloride and potassium bromide.
In some embodiments, the hole blocking layer has a thickness of 2nm to 7 nm. Under the condition, the hole barrier layer can increase the electron and hole injection balance of the quantum dot light-emitting diode, effectively reduce the leakage current of the device, improve the luminous efficiency of the quantum dot light-emitting diode and prolong the service life of the quantum dot light-emitting diode; and the light transmittance of the hole blocking layer is greater than or equal to 90%, so that the light transmittance of the quantum dot light-emitting diode can be met. In addition, due to the proper thickness, the increase of the starting voltage is avoided, and therefore the working energy consumption of the quantum dot light-emitting diode device is increased.
In some embodiments, the quantum dot light emitting diode further comprises an electronically functional layer disposed between the cathode and the quantum dot light emitting layer; in some embodiments, the quantum dot light emitting diode further comprises a hole injection layer disposed between the anode and the hole transport layer; in some embodiments, a quantum dot light emitting diode includes an electron functional layer disposed between a cathode and a quantum dot light emitting layer, and a hole injection layer disposed between an anode and a hole transport layer.
In the embodiment of the application, the quantum dot light emitting diode may further include a substrate, and the anode or the cathode is disposed on the substrate.
The quantum dot light-emitting diode provided by the embodiment of the application is divided into a positive type structure quantum dot light-emitting diode and an inversion type structure quantum dot light-emitting diode. Particularly, when the quantum dot light-emitting diode is an inverse-structure quantum dot light-emitting diode, in a device prepared by a solution method, because the solvents of potassium chloride, sodium chloride and potassium bromide are large-polarity solvents such as water, the solubility of the quantum dots of the quantum dot light-emitting layer is low, even the quantum dots are basically insoluble, and therefore, the interface performance of the quantum dot light-emitting layer cannot be influenced; when the hole transport layer is prepared, the influence of a hole transport material solvent on the quantum dot light-emitting layer can be avoided due to the blocking of the hole blocking layer.
In one embodiment, a positive type structure quantum dot light emitting diode includes an anode and a cathode disposed opposite to each other, a quantum dot light emitting layer disposed between the anode and the cathode, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and a hole blocking layer disposed between the hole transport layer and the quantum dot light emitting layer, and the anode is disposed on a substrate. Furthermore, an electronic function layer such as an electron transmission layer, an electron injection layer and the like can be arranged between the cathode and the quantum dot light-emitting layer; a hole injection layer may be disposed between the anode and the hole transport layer. In some embodiments of the positive-type quantum dot light emitting diode, the quantum dot light emitting diode comprises a substrate, an anode disposed on a surface of the substrate, a hole injection layer disposed on a surface of the anode, a hole transport layer disposed on a surface of the hole injection layer, a hole blocking layer disposed on a surface of the hole transport layer, a quantum dot light emitting layer disposed on a surface of the hole blocking layer, an electron transport layer disposed on a surface of the quantum dot light emitting layer, and a cathode disposed on a surface of the electron transport layer.
In one embodiment, an inverted structure quantum dot light emitting diode includes a stacked structure including an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and a hole blocking layer disposed between the hole transport layer and the quantum dot light emitting layer, and the cathode is disposed on a substrate. Furthermore, an electronic function layer such as an electron injection layer, an electron transmission layer and the like can be arranged between the cathode and the quantum dot light-emitting layer; a hole transport layer may be disposed between the anode and the quantum dot light emitting layer. In some embodiments of the quantum dot light emitting diode with the inverse structure, the quantum dot light emitting diode comprises a substrate, a cathode arranged on the surface of the substrate, an electron transport layer arranged on the surface of the cathode, a quantum dot light emitting layer arranged on the surface of the electron transport layer, a hole blocking layer arranged on the surface of the quantum dot light emitting layer, a hole transport layer arranged on the surface of the hole blocking layer, a hole injection layer arranged on the surface of the hole transport layer and an anode arranged on the surface of the hole injection layer.
In the above embodiments, the substrate may include a rigid substrate such as glass, metal foil, and the like, which are commonly used, or a flexible substrate such as Polyimide (PI), Polycarbonate (PC), Polystyrene (PS), Polyethylene (PE), polyvinyl chloride (PV), polyvinyl pyrrolidone (PVP), polyethylene terephthalate (PET), and the like, which mainly plays a role of support.
The anode can be made of common anode materials and thicknesses, and the embodiment of the application is not limited. For example, the anode material may be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO) conductive glass, or indium tin oxide, indium zinc oxide electrode, or may be other metal materials such as gold, silver, aluminum, and the like. In some embodiments, the cathode has a thickness of 20-80 nm.
In the embodiments of the present application, the cathode may be made of a common cathode material and thickness, and the embodiments of the present application are not limited. In some embodiments, the material of the cathode is selected from one or more of a conductive carbon material, a conductive metal oxide material, and a metallic material. Wherein the conductive carbon material includes, but is not limited to, one or more of doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, and porous carbon; the conductive metal oxide material includes, but is not limited to, one or more of ITO, FTO, ATO, and AZO; the metal material includes, but is not limited to, Al, Ag, Cu, Mo, Au, Ba, Ca, Mg, or alloys thereof. The metal material has a form including, but not limited to, one or more of a dense thin film, a nanowire, a nanosphere, a nanorod, a nanocone, and a hollow nanosphere. In which, materials such as nano-Ag wires or Cu wires are used, which have smaller resistance to enable carriers to be injected more smoothly. The thickness of the cathode is less than or equal to 100nm, and in some embodiments, the thickness of the cathode is 15-30 nm.
The quantum dots of the quantum dot light-emitting layer are direct band gap compound semiconductors with light-emitting capability, and conventional quantum dot materials can be selected according to conventional quantum dot types. For example, the quantum dots of the quantum dot light-emitting layer can be one of red quantum dots, green quantum dots, blue quantum dots and yellow quantum dots; the quantum dot material may or may not contain cadmium; the quantum dots can be oil soluble quantum dots including binaryPhase, ternary phase, quaternary phase quantum dots. The materials of the quantum dot light emitting layer provided by the embodiment of the application include, but are not limited to, one or more of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds or IV elementary substances. In some embodiments, the semiconductor materials used for the quantum dot light emitting layer include, but are not limited to, nanocrystals of II-VI semiconductors such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, and other binary, ternary, quaternary II-VI compounds; nanocrystals of group III-V semiconductors such as GaP, GaAs, InP, InAs and other binary, ternary, quaternary III-V compounds; and are not limited to group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, group IV simple substances, and the like. In some embodiments, the material of the quantum dot light emitting layer may also be a doped or undoped inorganic perovskite-type semiconductor, and/or an organic-inorganic hybrid perovskite-type semiconductor. Specifically, the structural general formula of the inorganic perovskite type semiconductor is AMX3Wherein A is Cs+Ion, M is a divalent metal cation, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+X is a halide anion, including but not limited to Cl-、Br-、I-(ii) a The structural general formula of the organic-inorganic hybrid perovskite type semiconductor is BMX3Wherein B is an organic amine cation including but not limited to CH3(CH2)n-2NH3+(n.gtoreq.2) or CH3(CH2)nNH3 2+(n.gtoreq.2). When n is 2, the inorganic metal halide octahedron MX6 4-The metal cations M are positioned in the center of a halogen octahedron through connection in a roof sharing mode, and the organic amine cations B are filled in gaps among the octahedrons to form an infinitely extending three-dimensional structure; inorganic metal halide octahedra MX linked in a coterminous manner when n > 26 4-Is formed by extending in two dimensionsThe laminated structure is characterized in that an organic amine cation bilayer (protonated monoamine) or an organic amine cation monolayer (protonated diamine) is inserted between layers, and the organic layer and the inorganic layer are overlapped to form a stable two-dimensional laminated structure; m is a divalent metal cation including, but not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+(ii) a X is a halide anion, including but not limited to Cl-、Br-、I-。
In some embodiments, the quantum dots are InP/ZnSe/ZnS core-shell structure quantum dots. In this case, the InP/ZnSe/ZnS core-shell structure quantum dots can reduce the migration of holes; in addition, the quantum dot light-emitting diode is provided with the hole blocking layer which is made of at least one of potassium chloride, sodium chloride and potassium bromide between the quantum dot light-emitting layer and the hole transmission layer, so that the injection balance of carriers can be further improved, the light-emitting efficiency and the service life of the device are improved, and the device is expected to replace the traditional cadmium selenide quantum dot light-emitting diode serving as a light-emitting material.
The hole injection layer may be made of a hole injection material conventional in the art, including, but not limited to, PEODT: PSS, CuPc, HATCN, WO3、MoO3、CrOx、NiO、CuO、V2O5、CuS、MoS2、MoSe2、WS2、WSe2But is not limited thereto. In some embodiments, the hole injection layer has a thickness of 5nm to 10 nm.
The materials of the hole transport layer can be made of hole transport materials conventional in the art, including but not limited to: poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N 'bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4', 4 ″ -tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazolyl) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, 15N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, stoneAt least one of graphene and C60. As another example, the hole transport layer is selected from inorganic materials with hole transport capability, including but not limited to NiOx、MoOx、WOx、CrOx、CuO、MoSx、MoSex、WSx、WSexAnd CuS. The thickness of the hole transport layer is 20nm-30 nm.
The material of the electron transport layer can adopt oxide semiconductor nano-particle materials with electron transport capability and band gap larger than that of the luminescent material, including but not limited to ZnO and TiO2、SnO2、Ta2O3、ZrO2One or more of NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO and InSnO.
As shown in fig. 2, the quantum dot light emitting diode includes a cathode and an anode disposed opposite to each other, a quantum dot light emitting layer disposed between the cathode and the anode, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and a hole blocking layer disposed between the hole transport layer and the quantum dot light emitting layer, an electron transport layer disposed between the cathode and the quantum dot light emitting layer, and a hole injection layer disposed between the anode and the hole transport layer; wherein, the cathode is an ITO cathode; the electron transmission layer is made of zinc oxide nanoparticles, and the thickness of the electron transmission layer is 30-70 nm; the quantum dot light-emitting layer is made of InP quantum dots, and the thickness of the quantum dot light-emitting layer is 10-30 nm; the hole blocking layer is made of sodium chloride and has the thickness of 2-7 nm; the hole transport layer is made of TFB and has a thickness of 20-30 nm; the hole injection layer is made of molybdenum oxide and has the thickness of 5-10 nm; the anode is made of gold or silver and has a thickness of 20-80 nm. In some embodiments, the quantum dot light emitting diode is an inverted quantum dot light emitting diode, i.e. the cathode is disposed on the substrate.
The quantum dot light-emitting diode provided by the embodiment of the application can be prepared by the following method.
As shown in fig. 3, a second aspect of the embodiments of the present application provides a method for manufacturing a quantum dot light emitting diode, including the following steps:
s01, providing a halogen salt solution containing at least one of potassium chloride, sodium chloride and potassium bromide and a cathode substrate;
s02, preparing a quantum dot light-emitting layer on the surface of a cathode substrate;
s03, depositing a halogen salt solution on the surface of the quantum dot light emitting layer, which is far away from the cathode substrate, and carrying out heat treatment to prepare a hole blocking layer;
s04, depositing a hole transport material on the surface of the hole blocking layer, which is far away from the quantum dot light emitting layer, and preparing a hole transport layer;
and S05, preparing an anode on the surface of the hole transport layer, which is far away from the hole blocking layer.
According to the preparation method of the quantum dot light-emitting diode, the halogen salt solution is deposited on the surface, away from the cathode substrate, of the quantum dot light-emitting layer, the hole blocking layer is prepared, so that the injection balance of electrons and holes of the quantum dot light-emitting diode is increased, the leakage current of the device is effectively reduced, the light-emitting efficiency of the quantum dot light-emitting diode is improved, and the service life of the quantum dot light-emitting diode is prolonged.
In the above step S01, the cathode substrate is a substrate provided with a cathode, and the cathode is typically a patterned cathode. The halogen salt solution is a solution containing a solute of at least one of potassium chloride, sodium chloride and potassium bromide. The halogen salt solution is prepared by dissolving at least one of potassium chloride, sodium chloride and potassium bromide in a solvent. In the resulting solution, the solute may be one such as potassium chloride or sodium chloride or potassium bromide; two of them, i.e., any two of potassium chloride, sodium chloride and potassium bromide, may be used in combination. In some embodiments, the solvent in the halide salt solution is selected from one of glycerol and water. Under the condition, the solvent cannot damage the quantum dots in the quantum dot light-emitting layer, has good dissolving performance on potassium chloride, sodium chloride and potassium bromide, is easy to remove in the heat treatment process and is not easy to remain, and therefore the influence on the performance of the device can be avoided.
In some embodiments, the concentration of solute, i.e., halide salt, in the halide salt solution is 0.5-5 mg/ml. Correspondingly, when the halogen salt solution is a potassium chloride solution, the concentration of the potassium chloride is 0.5-5 mg/ml; when the halogen salt solution is a sodium chloride solution, the concentration of the sodium chloride is 0.5-5 mg/ml; when the halogen salt solution is a potassium bromide solution, the concentration of the potassium bromide is 0.5-5 mg/ml; when the solute of the halogen salt solution contains at least two of sodium chloride, potassium chloride and potassium bromide, the total concentration of the at least two of the potassium chloride, the potassium chloride and the potassium bromide is 0.5-5 mg/ml. In this case, the hole blocking layer prepared by the solution processing method has a suitable thickness in the range of 2 to 7 nm.
In step S02, the quantum dot light-emitting layer is formed on the surface of the cathode substrate, that is, the quantum dot light-emitting layer is formed on the cathode surface of the cathode substrate. The method for preparing the quantum dot light-emitting layer on the surface of the cathode substrate can be realized by adopting a conventional method. In some embodiments, the quantum dot light emitting layer is prepared using a solution processing method. In some embodiments, the quantum dots are dissolved in toluene or n-hexane to provide a quantum dot solution or quantum dot ink. In some embodiments, a quantum dot light-emitting layer is prepared on the surface of the cathode substrate by a spin coating method, wherein the concentration of the quantum dot solution is 20-30mg/ml, and the spin coating speed is 2000-4000 rpm; in some embodiments, the quantum dot light emitting layer is prepared on the surface of the cathode substrate by a printing method, wherein the concentration of the quantum dot ink is 3-10 mg/ml. In some embodiments, the quantum dot material is InP/ZnSe/ZnS core-shell structure quantum dots, and the thickness of the quantum dot light emitting layer is 10-30 nm.
In some embodiments, before preparing the quantum dot light emitting layer, an electron transport layer is prepared on the surface of the cathode substrate. Namely, an electron transport layer is prepared on the surface of the cathode substrate, and then a quantum dot light-emitting layer is prepared on the surface of the electron transport layer, which is far away from the cathode substrate. The materials of the electron transport layer are as described above and will not be described herein for brevity.
In some embodiments, the material of the electron transport layer is zinc oxide nanoparticles. In some embodiments, the electron transport layer is prepared by depositing zinc oxide nanoparticles on the surface of the cathode substrate using solution processing. In some embodiments, the zinc oxide nanoparticle solution or the zinc oxide nanoparticle ink is prepared by dissolving zinc oxide nanoparticles in ethanol or n-butanol. In some embodiments, the electron transport layer is prepared on the surface of the cathode substrate by a spin coating method, wherein the concentration of the zinc oxide nanoparticle solution is 20-30mg/ml, and the spin coating speed is 2000-4000 rpm; in some embodiments, the electron transport layer is prepared on the surface of the cathode substrate by a printing method, wherein the concentration of the zinc oxide nanoparticle ink is 3-10 mg/ml. In some embodiments, after depositing zinc oxide nanoparticles on the surface of the cathode substrate by a solution processing method, the surface of the cathode substrate is heated at 80-120 ℃ for 20-40 minutes. In some embodiments, the electron transport layer has a thickness of 30-70 nm.
In step S03, the solution of potassium chloride and/or sodium chloride is deposited on the surface of the quantum dot light-emitting layer away from the cathode substrate, and may be spin-coated, blade-coated, printed, inkjet printed, or the like. And after the step of depositing the halogen salt solution on the surface of the quantum dot light-emitting layer departing from the cathode substrate, carrying out heat treatment to remove the solvent in the halogen salt solution and prepare the compact hole blocking layer. In some embodiments, the heat treatment temperature is 80-120 ℃ and the time is 5-30 minutes.
In step S04, depositing a hole transport material on the surface of the hole blocking layer away from the quantum dot light emitting layer can be achieved in a conventional manner. In some embodiments, the step of depositing the hole transport material on the surface of the hole blocking layer facing away from the quantum dot light emitting layer is performed using a solution processing method. In the embodiment, the hole blocking layer is prepared by depositing the halogen salt solution on the surface of the quantum dot light-emitting layer, which is away from the cathode substrate, so that the quantum dots in the quantum dot light-emitting layer can be effectively prevented from being dissolved by the hole transport material, and the performance of the quantum dot light-emitting diode is further improved.
In step S05, an anode is formed on the surface of the hole transport layer facing away from the hole blocking layer, and this can be achieved in a conventional manner. In some embodiments, before preparing the anode on the surface of the hole transport layer facing away from the hole blocking layer, preparing an electron injection layer on the surface of the hole transport layer facing away from the hole blocking layer is further included.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a quantum dot light-emitting diode comprises the following steps:
an ITO cathode on a transparent substrate;
dissolving ZnO nanoparticles in ethanol or n-butanol to prepare a ZnO nanoparticle solution with the concentration of 20mg/ml, spin-coating the ZnO nanoparticle solution on ITO, and heating at 80 ℃ for 30 minutes to prepare an electron transport layer;
dissolving InP/ZnSe/ZnS core-shell structure quantum dots in toluene or n-hexane to prepare a quantum dot solution with the concentration of 20mg/ml, and spin-coating the quantum dot solution on an electron transmission layer to prepare a quantum dot light-emitting layer;
dissolving sodium chloride (NaCl) in glycerol to prepare a sodium chloride solution, spin-coating the sodium chloride solution with the concentration of 1.0mg/ml on the quantum dot light-emitting layer, and performing heat treatment at 100 ℃ for 5min to prepare a hole blocking layer;
spin-coating TFB with concentration of 8mg/ml on the hole blocking layer, and performing heat treatment at 150 ℃ for 20min to prepare a hole transport layer;
evaporating a hole injection layer MoO on the surface of the hole transport layerxThe thickness of the hole injection layer is 10 nm;
and an Au anode is evaporated on the surface of the hole injection layer, and the thickness is 30 nm.
Example 2
A preparation method of a quantum dot light-emitting diode comprises the following steps:
an ITO cathode on a transparent substrate;
dissolving ZnO nanoparticles in ethanol or n-butanol to prepare ZnO nanoparticle ink with the concentration of 10mg/ml, printing the ZnO nanoparticle ink on ITO, and heating at 100 ℃ for 30 minutes to prepare an electron transmission layer;
dissolving InP/ZnSe/ZnS core-shell structure quantum dots in toluene or n-hexane to prepare quantum dot ink with the concentration of 10mg/ml, and printing the quantum dot ink on the electron transmission layer to prepare a quantum dot light-emitting layer;
dissolving potassium chloride (KCl) in glycerol to prepare a potassium chloride solution, spin-coating the potassium chloride solution with the concentration of 1.5mg/ml on the quantum dot light-emitting layer, and performing heat treatment at 90 ℃ for 5min to prepare a hole blocking layer;
spin-coating TFB with concentration of 8mg/ml on the hole blocking layer, and performing heat treatment at 150 ℃ for 20min to prepare a hole transport layer;
evaporating a hole injection layer MoO on the surface of the hole transport layerxThe thickness of the hole injection layer is 8 nm;
and depositing an Ag anode on the surface of the hole injection layer in a thickness of 70 nm.
Example 3
A preparation method of a quantum dot light-emitting diode comprises the following steps:
an ITO cathode on a transparent substrate;
dissolving ZnO nanoparticles in ethanol or n-butanol to prepare ZnO nanoparticle ink with the concentration of 10mg/ml, printing the ZnO nanoparticle ink on ITO, and heating at 100 ℃ for 30 minutes to prepare an electron transmission layer;
dissolving InP/ZnSe/ZnS core-shell structure quantum dots in toluene or n-hexane to prepare quantum dot ink with the concentration of 10mg/ml, and printing the quantum dot ink on the electron transmission layer to prepare a quantum dot light-emitting layer;
dissolving potassium bromide (KBr) in glycerol to prepare a potassium bromide solution, spin-coating the potassium bromide solution with the concentration of 1.5mg/ml on the quantum dot light-emitting layer, and carrying out heat treatment at 90 ℃ for 5min to prepare a hole blocking layer;
spin-coating TFB with concentration of 8mg/ml on the hole blocking layer, and performing heat treatment at 150 ℃ for 20min to prepare a hole transport layer;
evaporating a hole injection layer MoO on the surface of the hole transport layerxThe thickness of the hole injection layer is 8 nm;
and depositing an Ag anode on the surface of the hole injection layer in a thickness of 70 nm.
Example 4
A preparation method of a quantum dot light-emitting diode comprises the following steps:
an ITO cathode on a transparent substrate;
dissolving ZnO nanoparticles in ethanol or n-butanol to prepare a ZnO nanoparticle solution with the concentration of 30mg/ml, spin-coating the ZnO nanoparticle solution on ITO, and heating at 90 ℃ for 30 minutes to prepare an electron transport layer;
dissolving InP/ZnSe/ZnS core-shell structure quantum dots in toluene or n-hexane to prepare a quantum dot solution with the concentration of 30mg/ml, and spin-coating the quantum dot solution on an electron transmission layer to prepare a quantum dot light-emitting layer;
dissolving at least two of sodium chloride (NaCl), potassium chloride (KCl) and potassium bromide (KBr) in glycerol to prepare solutions of at least two of sodium chloride, potassium chloride and potassium bromide (KBr), spin-coating the solutions of at least two of sodium chloride, potassium chloride and potassium bromide with the concentration of 2.0mg/ml on the quantum dot light-emitting layer, and performing heat treatment at 120 ℃ for 5min to prepare a hole blocking layer;
spin-coating TFB with concentration of 8mg/ml on the hole blocking layer, and performing heat treatment at 150 ℃ for 20min to prepare a hole transport layer;
evaporating a hole injection layer MoO on the surface of the hole transport layerxThe thickness of the hole injection layer is 5 nm;
and an Au anode is evaporated on the surface of the hole injection layer, and the thickness is 50 nm.
Comparative example 1
A method for preparing a quantum dot light emitting diode is different from the method of the embodiments 1 to 3 in that: the hole blocking layer was prepared directly on the quantum dot light emitting layer without the step of preparing the hole blocking layer (for example, in example 1, "sodium chloride (NaCl) was dissolved in glycerin to prepare a sodium chloride solution, a sodium chloride solution was spin-coated on the quantum dot light emitting layer at a concentration of 1.5mg/ml, and a heat treatment was performed at 90 ℃ for 5min to prepare the hole blocking layer", in example 2, "potassium chloride (KCl) was dissolved in glycerin to prepare a potassium chloride solution, a potassium chloride solution was spin-coated on the quantum dot light emitting layer at a concentration of 1.5mg/ml, and a heat treatment was performed at 90 ℃ for 5min to prepare the hole blocking layer", in example 3, "potassium bromide (KBr) was dissolved in glycerin to prepare a potassium bromide solution, a potassium bromide solution was spin-coated on the quantum dot light emitting layer at a concentration of 1.5mg/ml, and a heat treatment was performed at 90 ℃ for 5 min).
Comparative example 2
The difference between the preparation method of the quantum dot light-emitting diode and the embodiment 1 is that: the method does not comprise the step of preparing the hole blocking layer, namely dissolving sodium chloride (NaCl) in glycerol to prepare a sodium chloride solution, spin-coating the sodium chloride solution with the concentration of 1.5mg/ml on the quantum dot light-emitting layer, and carrying out heat treatment at 90 ℃ for 5min to prepare the hole blocking layer, and directly preparing the hole transmission layer on the quantum dot light-emitting layer; and the material of the quantum dot light-emitting layer is cadmium selenide quantum dots.
The quantum dot light emitting diodes provided in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance tests, and the test indexes and test methods were as follows:
(1) external Quantum Efficiency (EQE): measured using an EQE optical test instrument.
The test results are shown in table 1 below.
TABLE 1
As can be seen from table 1, the quantum dot light emitting diode provided in example 1 of the present application has improved external quantum efficiency after the hole blocking layer selected from potassium chloride, sodium chloride, and potassium bromide is provided.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed.
Claims (10)
1. The quantum dot light-emitting diode is characterized by comprising a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged between the cathode and the anode, a hole transport layer arranged between the anode and the quantum dot light-emitting layer, and a hole blocking layer arranged between the hole transport layer and the quantum dot light-emitting layer; wherein, the material of the hole blocking layer is at least one selected from potassium chloride, sodium chloride and potassium bromide.
2. The quantum dot light-emitting diode of claim 1, wherein the hole blocking layer has a thickness of 2nm to 7 nm.
3. The qd-led of claim 1 or 2, wherein the InP/ZnSe/ZnS core-shell structure qd.
4. The qd-led of claim 1 or claim 2, further comprising an electronically functional layer disposed between the cathode and the qd-light emitting layer; and/or
Further comprising a hole injection layer disposed between the anode and the hole transport layer.
5. The quantum dot light-emitting diode of claim 1, wherein the quantum dot light-emitting diode further comprises an electron transport layer disposed between the cathode and the quantum dot light-emitting layer, and a hole injection layer disposed between the anode and the hole transport layer; wherein,
the cathode is an ITO cathode; the electron transmission layer is made of zinc oxide nanoparticles, and the thickness of the electron transmission layer is 30-70 nm; the quantum dot light-emitting layer is made of InP quantum dots, and the thickness of the quantum dot light-emitting layer is 10-30 nm; the hole blocking layer is made of sodium chloride and has the thickness of 2-7 nm; the hole transport layer is made of TFB and has a thickness of 20-30 nm; the hole injection layer is made of molybdenum oxide and has the thickness of 5-10 nm; the anode is made of gold or silver and has a thickness of 20-80 nm.
6. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing a halogen salt solution containing at least one of potassium chloride, sodium chloride and potassium bromide, and a cathode substrate;
preparing a quantum dot light-emitting layer on the surface of the cathode substrate;
depositing the halogen salt solution on the surface of the quantum dot light-emitting layer, which is far away from the cathode substrate, and carrying out heat treatment to prepare a hole blocking layer;
depositing a hole transport material on the surface of the hole blocking layer, which is far away from the quantum dot light-emitting layer, so as to prepare a hole transport layer;
and preparing an anode on the surface of the hole transport layer, which is far away from the hole blocking layer.
7. The method for preparing a quantum dot light-emitting diode according to claim 6, wherein the concentration of the halogen salt in the halogen salt solution is 0.5-5 mg/ml.
8. The method for preparing a quantum dot light-emitting diode according to claim 6, wherein the temperature of the heat treatment is 80 to 120 ℃ and the time is 5 to 30 minutes.
9. The method of any one of claims 6 to 8, wherein the solvent in the halide salt solution is selected from the group consisting of glycerol and water.
10. The method of any one of claims 6 to 8, wherein the step of depositing the hole transport material on the surface of the hole blocking layer facing away from the quantum dot light emitting layer is performed by a solution processing method.
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| CN1838846A (en) * | 2004-12-31 | 2006-09-27 | 三星Sdi株式会社 | Organic electroluminescent device |
| CN101038953A (en) * | 2007-02-02 | 2007-09-19 | 东南大学 | Improved organic light-emitting device |
| CN101894918A (en) * | 2009-05-18 | 2010-11-24 | 精工爱普生株式会社 | The manufacture method of light-emitting device, light-emitting device, display unit and electronic equipment |
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| CN106848076A (en) * | 2017-01-06 | 2017-06-13 | 西安交通大学 | A kind of organo-mineral complexing perovskite LED device and preparation method thereof |
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