CN111384301A - Perovskite quantum dot light-emitting diode and preparation method thereof - Google Patents
Perovskite quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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Abstract
The application provides a perovskite quantum dot light-emitting diode and a preparation method thereof. The preparation method of the perovskite quantum dot comprises the following steps: the method comprises the following steps that fog drops containing a charge transport substance and a solvent are deposited on a perovskite quantum dot light emitting layer, and the fog drops are gathered to form a liquid film layer; drying the liquid film layer to obtain a charge transport layer; the charge transport layer is an electron transport layer or a hole transport layer. This application is through the droplet that deposit contains the charge transport material on perovskite quantum dot luminescent layer to thereby prepare the charge transport layer through low temperature drying, reduction that can be very big is to the destruction of perovskite quantum dot luminescent layer.
Description
Technical Field
The application belongs to the field of semiconductor light-emitting devices, and particularly relates to a perovskite quantum dot light-emitting diode and a preparation method thereof.
Background
The perovskite quantum dot is a semiconductor material which can be processed by solution, has the characteristics of low cost, large light absorption coefficient, controllable emission wavelength, narrow half-peak width of the emission wavelength and the like, and has huge application prospect in the field of electroluminescence.
The perovskite quantum dot light-emitting diode comprises an anode, a hole transmission layer, a perovskite quantum dot light-emitting layer, an electron transmission layer and a cathode which are sequentially laminated. In the process of preparing a perovskite quantum dot light emitting diode, it is generally required to spin-coat a solution containing a hole transport material or a solution containing an electron transport material on a perovskite quantum dot light emitting layer, which easily damages the perovskite quantum dot light emitting layer.
Disclosure of Invention
In view of the above technical problems, the present application provides a method for manufacturing a perovskite quantum dot light emitting diode, so as to solve the problem that a perovskite quantum dot light emitting layer is easily damaged in the existing process of manufacturing a perovskite quantum dot light emitting diode.
According to an aspect of the present application, there is provided a method of manufacturing a perovskite quantum dot light emitting diode, comprising: the fog drops containing the charge transport material and the solvent are deposited on the perovskite quantum dot light emitting layer, and the fog drops are gathered to form a liquid film layer; drying the liquid film layer to obtain a charge transport layer; the charge transport layer is an electron transport layer or a hole transport layer.
According to different orders of preparing each functional layer of the perovskite quantum dot, the perovskite quantum dot light-emitting layer can be prepared in the prior art according to the order of an anode, a hole transmission layer, the perovskite quantum dot light-emitting layer, an electron transmission layer and a cathode, namely the electron transmission layer is prepared on the perovskite quantum dot light-emitting layer; the opposite is also possible, i.e. a hole transport layer is prepared on top of the perovskite quantum dot light emitting layer. In the present application, a charge transport material refers to a material having an electron transport property or a hole transport property, and it is understood that electron transport may be also referred to as "electron injection", "electron transport", and the like, and these terms are different from each other, but they refer to a transition layer for electron transport between a cathode and a perovskite quantum dot light emitting layer. Like electron transport, hole transport may also be referred to as "hole injection", "hole transport", and the like, although these terms are different, all refer to a transition layer for hole transport between the anode and the perovskite quantum dot light emitting layer.
Mist droplets in this application refer to small particles of liquid that can be suspended in air, and the size of the mist droplets is typically less than 100 microns. Due to the action of surface tension, fog drops deposited on the perovskite quantum dot light-emitting layer are slowly gathered together to form a liquid film layer. However, the perovskite quantum dot light-emitting layer is fluffy and is easy to wash away, and the ligand on the surface of the perovskite quantum dot is easy to fall off, so that when fog drops are deposited on the perovskite quantum dot light-emitting layer, the impact force of the fog drops with small sizes on the perovskite quantum dot light-emitting layer is extremely small. Therefore, compared with the process of spin coating or depositing large-particle liquid drops on the perovskite quantum dot light-emitting layer, the damage to the perovskite quantum dot light-emitting layer can be effectively reduced.
The mode of the fog drops deposited on the perovskite quantum dot light-emitting layer is preferably natural deposition, and external mechanical force can be applied to the fog drops in order to accelerate the deposition speed of the fog drops, for example, after the fog drops are atomized by a nozzle, the pressure generated by the nozzle is used for directly driving the fog drops to be deposited on the perovskite quantum dot light-emitting layer.
In the present application, perovskite quantum dots include, but are not limited to, CH3NH3PbX3、(CH3)3Bi2X9Or ABX3Wherein, A is Rb or Cs, B is Ge, Sn or Pb, and X is Cl, Br or I. For example, the perovskite quantum dot may be CH3NH3PbCl3、CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbBr2I、CH3NH3PbBr2Cl、(CH3)3Bi2Cl9、(CH3)3Bi2Br9、(CH3)3Bi2I9、CsPbI3、CsPbCl3、CsSnI3And the like.
The surface ligand of the perovskite quantum dot can be organic acid, organic amine, organic phosphine or mercaptan. For example, surface ligands include, but are not limited to, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, benzyl mercaptan, methyl amine, ethyl amine, propyl amine, butyl amine, pentyl amine, hexyl amine, octyl amine, dodecyl amine, hexadecyl amine, octadecyl amine, dimethyl amine, diethyl amine, dipropyl amine, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, benzoic acid, methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, pentyl phosphine, methyl phosphine oxide, ethyl phosphine oxide, propyl phosphine oxide, butyl phosphine oxide, diphenyl phosphine compound, or triphenyl phosphine compound. Preferably, the surface ligand of the perovskite quantum dot is oleylamine or oleic acid.
In one embodiment, the means for depositing the droplets comprises spraying. The means for obtaining the droplets comprises atomizing a liquid containing the charge transport material and the solution with a spray gun or a disc atomizer.
Different atomising means may be selected in this application to achieve a predetermined size of droplets. In a preferred embodiment, the size of the droplets is 0.1 to 50 μm, and more preferably, the size of the droplets is 1 to 10 μm. The inventor finds that when the size of the fog drops is larger than 50 micrometers, the impact effect on the perovskite quantum dot light-emitting layer is large when the fog drops are deposited, so that the perovskite quantum dots are washed away or ligands on the surface of the perovskite quantum dots are washed away; when the size of the droplets is less than 1 micron, especially less than 0.1 micron, the deposition rate of the droplets is slow, which is not favorable for preparing the charge transport layer with high efficiency. Therefore, the size of the mist droplets is preferably within the above range.
In one embodiment, the step of drying the liquid film layer is performed at 10-60 ℃, and in this application, since the boiling points of the different solvents are different, in order to enable the solvents to volatilize at the above temperature, the different solvents are selectively dried in different vacuum environments. When the liquid film layer is dried, when the drying temperature is high, for example, more than 70 ℃, especially more than 100 ℃, the surface ligand of the perovskite quantum dots in the perovskite quantum dot light emitting layer falls off, so that the light emitting efficiency of the perovskite quantum dots is seriously reduced, and the light emitting efficiency of the perovskite quantum dot light emitting diode is further reduced or even does not emit light. When the drying temperature is low, for example, less than 10 ℃, the vacuum degree required for solvent volatilization is high. Therefore, the step of drying the liquid film layer is preferably performed at 10 to 60 ℃.
In one embodiment, the charge transport material comprises at least one of small organic molecules, organic polymers, inorganic nanoparticles. For example, the charge transport material includes doped or undoped zinc oxide nanoparticles, doped or undoped magnesium oxide nanoparticles, doped or undoped tungsten oxide nanoparticles, doped or undoped nickel oxide nanoparticles, oxadiazoles, oxadiazole derivatives, oxazoles, oxazole derivatives, isoxazole derivatives, thiazole derivatives, 1,2, 3-triazole derivatives, 1,3, 5-triazine derivatives, quinoxaline derivatives, pyrrole oligomers, pyrrole polymers, vinylphenylene oligomers, vinylphenylene polymers, vinylcarbazole oligomers, vinylcarbazole polymers, fluorine oligomers, fluorine polymers, ethynylphenylene oligomers, ethynylphenylene polymers, Phenylene oligomers, phenylene polymers, thiophene oligomers, thiophene polymers, acetylene oligomers, acetylene polymers, tertiary arylamines, pyrrole oligomers, phthalocyanines, phthalocyanine derivatives, porphyrine and porphyrine derivatives. The inorganic nanoparticles are doped, for example, with non-metallic elements, or compounds of metals, so as to change the electrical properties of the inorganic nanoparticles, and the doped elements include, but are not limited to, magnesium, zinc, manganese, chromium, vanadium, halogens, lithium, and the like.
In one embodiment, the charge transport material is doped or undoped zinc oxide nanoparticles and the solvent is ethanol.
According to another aspect of the present application, there is provided a perovskite quantum dot light emitting diode comprising: the perovskite quantum dot light-emitting diode comprises an anode, a hole transport layer, a perovskite quantum dot light-emitting layer, an electron transport layer and a cathode which are sequentially stacked, and is prepared by any one of the preparation methods.
The application has the following beneficial effects:
(1) the fog drops containing the charge transport substances are deposited on the perovskite quantum dot light-emitting layer, so that the damage to the perovskite quantum dot light-emitting layer can be greatly reduced;
(2) the perovskite quantum dot light-emitting diode with excellent light-emitting property can be obtained by drying the liquid film layer at a lower temperature of 10-60 ℃.
Drawings
FIG. 1 is a graph showing electroluminescence spectra of perovskite quantum dot light emitting diodes in examples 1 to 4;
fig. 2 is an electroluminescence spectrum of the perovskite quantum dot light emitting diode in comparative example 1.
Detailed Description
The following describes technical solutions in the examples of the present application in detail with reference to the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the present application, and not all embodiments.
Example 1
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. And then, baking at 50 ℃ under a vacuum-pumping condition, and removing n-hexane to obtain a perovskite quantum dot light-emitting layer, wherein the perovskite quantum dot is CsPbCl3, and the surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (2) loading the ethanol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the ethanol solution onto the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 5 microns, and stopping spraying after the fog drops are deposited for 2 min. Vacuumizing, and removing ethanol at 60 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of example 1.
Example 2
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. Then baking at 50 ℃ under the condition of vacuum pumping, removing n-hexane, and obtaining a perovskite quantum dot luminescent layer, wherein the perovskite quantum dot is CsPbCl3The surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (3) loading the ethanol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the ethanol solution onto the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 20 microns, and stopping spraying after the fog drops are deposited for 2 min. Vacuumizing, and removing ethanol at 60 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of example 2.
Example 3
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: using deionized water and acetone to the ITO glass substrateCleaning, ultrasonic treating in isopropanol for about 15min, and then using N2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. Then baking at 50 ℃ under the condition of vacuum pumping, removing n-hexane, and obtaining a perovskite quantum dot luminescent layer, wherein the perovskite quantum dot is CsPbCl3The surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (2) loading the ethanol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the ethanol solution onto the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 1 micron, and stopping spraying after the fog drops are deposited for 2 min. Vacuumizing, and removing ethanol at 60 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of example 3.
Example 4
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. Then baking at 50 ℃ under the condition of vacuum pumping, removing n-hexane, and obtaining a perovskite quantum dot luminescent layer, wherein the perovskite quantum dot is CsPbCl3The surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (2) loading the ethanol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the ethanol solution onto the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 5 microns, and stopping spraying after the fog drops are deposited for 2 min. Vacuumizing, and removing ethanol at 30 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of example 4.
Comparative example 1
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparation of perovskite quantum dot light emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. Then baking at 50 ℃ under the condition of vacuum pumping, removing n-hexane, and obtaining a perovskite quantum dot luminescent layer, wherein the perovskite quantum dot is CsPbCl3The surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: an ethanol solution of ZnO nanoparticles (average size about 6nm) at a concentration of about 20mg/ml was spin coated on the perovskite quantum dot light emitting layer at a spin speed of 2000rpm for a spin time of 20 s. Vacuumizing, and removing ethanol at 60 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of comparative example 1.
Comparative example 2
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. Then baking at 50 ℃ under the condition of vacuum pumping, removing n-hexane, and obtaining a perovskite quantum dot luminescent layer, wherein the perovskite quantum dot is CsPbCl3The surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (2) loading the ethanol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the ethanol solution onto the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 5 microns, and stopping spraying after the fog drops are deposited for 2 min. Vacuumizing, and removing ethanol at 70 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of comparative example 2.
Comparative example 3
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: CsPbCl with a spin concentration of 10mg/ml on the hole transport layer3And (3) carrying out spin coating on the quantum dot in n-hexane solution at the rotation speed of 4000rpm for 20 s. Then baking at 50 ℃ under the condition of vacuum pumping, removing n-hexane, and obtaining a perovskite quantum dot luminescent layer, wherein the perovskite quantum dot is CsPbCl3The surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (3) putting the n-butyl alcohol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the solution on the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 1 micron, and stopping spraying after the fog drops are deposited for 2 min. Vacuumizing, and removing n-butyl alcohol at 100 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer having a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of comparative example 3.
Comparative example 4
The preparation method of the perovskite quantum dot light-emitting diode comprises the following steps:
preparing an anode: cleaning ITO glass substrate with deionized water and acetone, performing ultrasonic treatment in isopropanol for about 15min, and performing N treatment2And blowing the solvent clean by an air gun to obtain the ITO anode used subsequently.
Preparing a hole transport layer: and (3) spin-coating a PEDOT PSS aqueous solution on an ITO anode, then transferring the PEDOT PSS aqueous solution into an Ar gas glove box, and drying to obtain the PEDOT PSS layer. And then spin-coating a toluene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) with a concentration of about 1mg/ml on a PEDOT (PSS) layer, and drying to obtain a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) layer, thereby preparing the hole transport layer.
Preparing a perovskite quantum dot light-emitting layer: and spin-coating CsPbCl3 quantum dots in n-hexane solution with the concentration of 10mg/ml on the hole transport layer at the rotation speed of 4000rpm for 20 s. And then, baking at 50 ℃ under a vacuum-pumping condition, and removing n-hexane to obtain a perovskite quantum dot light-emitting layer, wherein the perovskite quantum dot is CsPbCl3, and the surface ligand of the perovskite quantum dot is oleic acid.
Preparing an electron transport layer: and (2) loading the ethanol solution of ZnO nano particles (the average size is about 6nm) with the concentration of about 20mg/ml into an atomizer, spraying the ethanol solution onto the perovskite quantum dot light-emitting layer when the spraying rate is stable, wherein the spraying rate is about 30ml/h, the average size of fog drops is about 60 microns, and stopping spraying after the fog drops are deposited for 1 min. Vacuumizing, and removing ethanol at 60 ℃ to obtain the electron transport layer.
Preparing a cathode: an Al layer with a thickness of about 100 nm was vapor-deposited on the electron transport layer to obtain a cathode, thereby obtaining the perovskite quantum dot light emitting diode of comparative example 4.
The perovskite quantum dot light emitting diodes of examples 1 to 4 and comparative examples 1 to 4 were tested for their electroluminescent properties using a PR-670 photometer manufactured by PHOTO RESEARCH corporation, usa.
The perovskite quantum dot light emitting diodes in examples 1 to 4 all have fluorescence emission spectra as shown in fig. 1, namely, a distinct emission peak at 516nm, which is consistent with the emission peak position and the emission peak shape of the CsPbCl3 quantum dots used in examples 1 to 4 in the solution.
The perovskite quantum dot light-emitting diode in the comparative example 1 has a fluorescence emission spectrum as shown in FIG. 2, namely, a distinct emission peak at 436nm is consistent with the emission peak of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine). The results indicate that in comparative example 1, when the electron transport layer was prepared on the perovskite quantum dot light emitting layer using the spin coating method, the perovskite quantum dot light emitting layer was directly washed away, so that the perovskite quantum dot light emitting diode exhibited the emission spectrum of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) originally used as the hole transport layer.
Unlike examples 1 to 4 and comparative example 1, in comparative example 2 and comparative example 3, the perovskite quantum dot light emitting diode does not substantially emit light. The result shows that the luminous efficiency of the perovskite quantum dots in the perovskite quantum dot luminous layer is seriously reduced due to the action of relatively high temperature, so that basically no light is emitted.
Whereas in comparative example 4, the light emitting efficiency of the perovskite quantum dot light emitting diode was significantly decreased. The result shows that when the perovskite quantum dot light-emitting layer is impacted by fog drops with larger sizes, the surface ligand of the perovskite quantum dot can fall off, so that the light-emitting efficiency of the perovskite quantum dot is seriously reduced, and the electroluminescent efficiency of the perovskite quantum dot light-emitting diode is reduced.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.
Claims (10)
1. A preparation method of a perovskite quantum dot light-emitting diode is characterized by comprising the following steps:
the method comprises the following steps that fog drops containing a charge transport substance and a solvent are deposited on a perovskite quantum dot light emitting layer, and the fog drops are gathered to form a liquid film layer;
drying the liquid film layer to obtain a charge transport layer; the charge transport layer is an electron transport layer or a hole transport layer.
2. The production method according to claim 1, wherein the perovskite quantum dot comprises CH3NH3PbX3、(CH3)3Bi2X9Or ABX3Wherein, A is Rb or Cs, B is Ge, Sn or Pb, and X is Cl, Br or I.
3. The preparation method according to claim 1, wherein the surface ligand of the perovskite quantum dot is an organic acid, an organic amine, an organic phosphine, or a thiol.
4. The method of claim 1, wherein the droplet deposition comprises spray coating.
5. The method according to claim 1, wherein the size of the mist droplets is 0.1 to 50 μm.
6. The method according to claim 5, wherein the size of the mist droplets is 1 to 10 μm.
7. The method according to claim 1, wherein the step of drying the liquid film layer is performed at 10 to 60 ℃.
8. The method according to claim 1, wherein the charge transport material comprises at least one of organic small molecules, organic polymers, and inorganic nanoparticles.
9. The production method according to claim 8, wherein the charge transporting substance is doped or undoped zinc oxide nanoparticles, and the solvent is ethanol.
10. A perovskite quantum dot light emitting diode comprising: an anode, a hole transport layer, a perovskite quantum dot light emitting layer, an electron transport layer and a cathode which are sequentially layered, wherein the perovskite quantum dot light emitting diode is prepared by the preparation method as claimed in any one of claims 1 to 9.
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