CN116981320A - Photoelectric device, preparation method thereof and display device - Google Patents
Photoelectric device, preparation method thereof and display device Download PDFInfo
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Abstract
The application discloses a photoelectric device, a preparation method thereof and a display device. The preparation method of the photoelectric device comprises the following steps: providing an anode; sequentially forming a hole function layer and a first light-emitting layer on the anode; a pretreatment electrode is arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply for electrifying treatment; removing the first light-emitting layer and the pretreatment electrode on the hole function layer; a second light emitting layer and a cathode are sequentially formed on the hole functional layer. Through electrical treatment, the hole function layer can reach the electrically stable structural state by electrical aging in advance, the service life of the photoelectric device is prolonged, and the forward aging process of the photoelectric device is shortened, so that the device reaches the maximum brightness in a short time, and the performance of the photoelectric device is improved. After the first luminescent layer is removed, the cathode and the new luminescent layer are reformed, so that structural damage to the first luminescent layer in the electrical treatment process is avoided, and the performance of the formed photoelectric device is influenced.
Description
Technical Field
The application relates to the technical field of display, in particular to a photoelectric device, a preparation method thereof and a display device.
Background
The photoelectric device is a device manufactured according to a photoelectric effect, and has wide application in the fields of new energy, sensing, communication, display, illumination and the like, such as a solar cell, a photoelectric detector and an organic electroluminescent device (OLED or quantum dot electroluminescent device (QLED).
The structure of the conventional photoelectric device mainly comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode. Under the action of the electric field, holes generated by the anode and electrons generated by the cathode of the photoelectric device move, are respectively injected into the hole transmission layer and the electron transmission layer and finally migrate to the light-emitting layer, and when the hole transmission layer and the electron transmission layer meet at the light-emitting layer, energy excitons are generated, so that light-emitting molecules are excited to finally generate visible light.
With the wide application of photoelectric devices, how to improve the performance and service life of the photoelectric devices is a technical problem to be solved.
Disclosure of Invention
In view of the above, the present application provides an optoelectronic device, a method for manufacturing the same, and a display device, which aim to improve performance and lifetime of the optoelectronic device.
The embodiment of the application is realized in such a way that a preparation method of a photoelectric device is provided, comprising the following steps: providing an anode; sequentially forming a hole function layer and a first light-emitting layer on the anode; a pretreatment electrode is arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply to carry out electrifying treatment; removing the first light-emitting layer and the pretreatment electrode on the hole function layer; and forming a second light-emitting layer and a cathode on the hole functional layer in sequence.
Alternatively, in some embodiments of the present application, the energizing process is constant current, and the current density of the energizing process at constant current is in the range of 1-100 mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Or the electrifying treatment is electrifying treatment under constant voltage, and the current density of the electrifying treatment under the constant voltage is less than or equal to 100mA/cm 2 。
Alternatively, in some embodiments of the application, the energizing process employs one or more of alternating current, cyclic voltammetry, or alternating current pulses.
Optionally, in some embodiments of the present application, the method for removing the first light emitting layer and the pre-treatment electrode on the hole function layer is a mechanical peeling method, a tape bonding method, or a chemical dissolution method.
Optionally, in some embodiments of the present application, the removing the first light emitting layer and the pretreatment electrode on the hole function layer is the chemical dissolution method, including: determining a kind of solvent based on a material of the first light emitting layer; dissolving and removing the first light-emitting layer by using the determined solvent; wherein the determining the kind of the solvent based on the material of the first light emitting layer includes: determining a solvent selection nonpolar solvent based on the fact that the material of the first luminescent layer is a quantum dot material, and the ligand of the quantum dot material is a long-chain ligand; or determining the solvent selection polar solvent based on the material of the first light-emitting layer being a quantum dot material, the ligand of the quantum dot material being a short chain ligand.
Optionally, in some embodiments of the present application, the material of the first light emitting layer is a quantum dot material, and the ligand of the quantum dot material is a long chain ligand; the hole function layer and the first light-emitting layer are sequentially formed on the anode, and the method comprises the following steps: arranging a halide solution on the first luminescent layer for ligand exchange, and replacing the long-chain ligand of the quantum dot material with a short-chain ligand; the removing the first light emitting layer and the pretreatment electrode on the hole function layer is the chemical dissolution method, comprising: the first light-emitting layer is dissolved and removed using a polar solvent.
Optionally, in some embodiments of the present application, a pretreatment electrode is disposed on the first light emitting layer, and the anode and the pretreatment electrode are respectively connected to a power source to perform an energizing process, including: a first electronic functional layer and the pretreatment electrode are arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply to carry out electrifying treatment; the removing the first light emitting layer and the pre-treatment electrode on the hole function layer includes: removing the first light-emitting layer, the first electron functional layer and the pre-treatment electrode on the hole functional layer; wherein the first electron functional layer comprises a first electron transport layer and/or a first electron injection layer.
Optionally, in some embodiments of the present application, before the forming the second light emitting layer and the cathode sequentially on the hole functional layer, the method further includes: detecting whether the first light-emitting layer is completely removed; and if the first light-emitting layer is not completely removed, repeating the removing step until the first light-emitting layer is completely removed.
Optionally, in some embodiments of the present application, the forming a second light emitting layer and a cathode sequentially on the hole functional layer includes: sequentially forming the second light-emitting layer, the second electron functional layer and the cathode on the hole functional layer; wherein the second electron functional layer comprises a second electron transport layer and/or a second electron injection layer.
Optionally, in some embodiments of the present application, the disposing a pretreatment electrode on the first light emitting layer includes: a metal electrode plate is used as the pretreatment electrode cover to be arranged on the first luminous layer; the removing the first light emitting layer and the pre-treatment electrode on the hole function layer includes: and removing the metal electrode plate from the first light-emitting layer, and removing the first light-emitting layer by a mechanical stripping method, an adhesive tape bonding method or a chemical dissolution method.
Optionally, in some embodiments of the present application, the disposing a metal electrode sheet as the pre-processing electrode cover on the first light emitting layer includes: a first electronic function layer is arranged on the metal electrode plate, and the metal electrode plate with the first electronic function layer is covered on the first luminous layer; wherein, the first electronic functional layer is close to one side of the first light-emitting layer and is contacted with the first light-emitting layer; said removing said metal electrode sheet from said first light emitting layer comprises: and removing the metal electrode plate and the first electronic function layer arranged on the metal electrode plate from the first light-emitting layer.
Alternatively, in some embodiments of the present application, the first light emitting layer and the material of the first light emitting layer are each independently selected from an organic light emitting material, a quantum dot light emitting material, or a perovskite type semiconductor material; the organic luminescent material is at least one selected from a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe luminescent material emitting blue light, a TTPA luminescent material emitting green light, a TBRb luminescent material emitting orange light and a DBP luminescent material emitting red light; the quantum dot luminescent material is selected from at least one of single-structure quantum dots and core-shell structure quantum dots, the single-structure quantum dots are selected from at least one of II-VI compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound and II-IV-VI compound, the II-VI compound is selected from at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe, cdZnSTe, cdSeSTe and ZnSeSTe, the IV-VI compound is selected from at least one of PbS, pbSe, pbTe, pbSeS, pbSeTe, the III-V compound is selected from at least one of InP, inAs, gaP, gaAs, gaSb, gaAsP, inGaP, inGaAs, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the perovskite type semiconductor material is selected from doped or undoped inorganic perovskite type semiconductor or organic-inorganic hybrid perovskite type semiconductor; the structural general formula of the inorganic perovskite semiconductor is AMX 3 Wherein A is Cs + Ions, M is a divalent metal cation, including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2+ X is a halogen anion including but not limited to Cl-, br - 、I - The method comprises the steps of carrying out a first treatment on the surface of the The structural general formula of the organic-inorganic hybridization perovskite type semiconductor is BMX 3 Wherein B is an organic amine cation including, but not limited to CH 3 (CH 2 ) n-2 NH 3+ Or NH 3 (CH 2 ) n NH 3 2+ Wherein n is greater than or equal to 2; m is a divalent metal cation including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2 + 、Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the X is a halogen anion including but not limited to Cl - 、Br - I-; and/or the hole functional layer comprises a hole transport layer and/or a hole injection layer, wherein the material of the hole transport layer is selected from 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 (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped graphene, C60, niO, o 60 3 、WO 3 、V 2 O 5 P-type gallium nitride, crO 3 、CuO、MoS x 、MoSe x 、WSx、WSe x And one or more of CuS, cuSCN; the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiOx, moOx, WOx, crOx, cuO, anThe metal chalcogenide compound includes one or more of MoSx, moSex, WSx, WSex, cuS; and/or the materials of the anode, the pretreatment electrode and the cathode are respectively and independently selected from a metal electrode, a carbon electrode and a composite electrode formed by one or more of doped or undoped metal oxide electrodes; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 At least one of them.
Correspondingly, the embodiment of the application also provides a photoelectric device, which is prepared by the preparation method of the photoelectric device.
Correspondingly, the embodiment of the application also provides a display device which comprises the photoelectric device.
The optoelectronic device of the present application comprises: providing an anode; sequentially forming a hole function layer and a first light-emitting layer on the anode; a pretreatment electrode is arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply for electrifying treatment; removing the first light-emitting layer and the pretreatment electrode on the hole function layer; a second light emitting layer and a cathode are sequentially formed on the hole functional layer. Through electrical treatment, electrical and electrochemical reactions are generated between the hole functional layer and the light-emitting layer, so that the interface between the hole functional layer and the light-emitting layer is subjected to pre-passivation treatment, and the electrical performance of the finally formed photoelectric device can be more matched, thereby improving the performance of the photoelectric device. And the hole function layer can reach the electrically stable structural state by the advanced electrical aging, which is beneficial to prolonging the service life of the photoelectric device. In addition, the positive aging process of the photoelectric device is shortened due to the fact that the hole functional layer is subjected to electrical pretreatment, so that the device reaches maximum brightness in a short time, and the rapid response speed of the photoelectric device is improved. After the first luminescent layer is removed, the cathode and a new luminescent layer (second luminescent layer) are formed again, so that structural damage to the first luminescent layer in the electrical treatment process is avoided, the performance of the formed photoelectric device is influenced, the second luminescent layer formed after the electrical treatment is not subjected to electrical treatment, the structure and the performance of the second luminescent layer are not influenced by the electrical treatment, and the original luminescent performance of the second luminescent layer can be realized. Further, since the first light-emitting layer is removed after the energization pretreatment, the influence of the energization treatment on the first light-emitting layer can be eliminated during the energization treatment, the condition limitation of the energization treatment can be reduced, the matching property between the hole function layer and a photoelectric device formed later can be improved to the maximum extent, and the performance of the photoelectric device can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an embodiment of a method for fabricating an optoelectronic device according to the present application;
fig. 2 is a schematic flow chart of another embodiment of a method for manufacturing an optoelectronic device according to the present application;
fig. 3 a-3 c are schematic flow diagrams illustrating a method for manufacturing an optoelectronic device according to an embodiment of the present application;
FIG. 4a is a graph of current density versus voltage for a quantum dot light emitting diode;
fig. 4b is a graph of current density versus luminance for a qd led.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application based on the embodiments of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application. In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the most common photoelectric device structure at present, a certain interface effect exists between a hole functional layer (comprising a Hole Injection Layer (HIL) and a Hole Transport Layer (HTL)) and an emitting layer (EML), which is shown by high hole injection barrier, large contact potential leads to increased hole injection voltage and small current. In the process of driving the photoelectric device to emit light, the electrical aging process is accompanied with gradual increase of the conductivity of the hole functional layer, the resistance between the hole functional layer and the light emitting layer is reduced, the contact with the light emitting layer is improved, and the brightness of the photoelectric device is increased. As the electrical aging process proceeds, electrons are injected too much and accumulate at the HTL/EML interface, causing damage to the HTL interface, and simultaneously generating a large amount of heat may further damage the HTL, thereby affecting the performance and lifetime of the photovoltaic device. Similarly, a certain electrochemical reaction exists between the anode and the HIL, and the continuous irreversible electrochemical reaction causes the property of the HIL layer to be changed, even causes the structure of the HIL layer to be damaged, and influences the performance and the service life of the photoelectric device.
Based on the above, the application provides a preparation method of the photoelectric device, so as to improve the performance and service life of the photoelectric device.
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for manufacturing an optoelectronic device according to the present application, which specifically includes the following steps:
Step S10: an anode is provided.
In this step, the anode may be disposed on the substrate.
Step S20: a hole function layer and a first light emitting layer are sequentially formed on the anode.
In this step, the hole-functional layer includes a hole-transporting layer and/or a hole-injecting layer. In other words, the hole-functional layer may include any one of a hole-transporting layer and a hole-injecting layer, or may include a two-layer structure of a hole-transporting layer and a hole-injecting layer. When the hole function layer is a two-layer structure including a hole transport layer and a hole injection layer, the hole injection layer is disposed near one side of the anode, and the hole transport layer is disposed near one side of the light emitting layer.
Step S30: and a pretreatment electrode is arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply to carry out electrifying treatment.
In this step, the anode and the pretreatment electrode are connected to the two poles of the power supply, and the power supply is turned on to form an electrical loop between the anode, the hole function layer, the first light emitting layer and the pretreatment electrode, thereby performing electrical treatment. The electrifying treatment can be performed in an environment isolated from water and oxygen, for example, inert gas can be used as protective gas in inert gas atmosphere, so that side reactions of each film layer and water and oxygen in the electrifying treatment are avoided, and the structure and performance of each film layer are influenced. Specifically, the inert gas may be argon, nitrogen, or the like. It is understood that if each formed film structure is insensitive to water and oxygen and does not undergo side reaction in the energized state, the energized treatment may not be limited to an environment isolated from water and oxygen.
Step S40: the first light emitting layer and the pre-treatment electrode on the hole function layer are removed.
In this step, the first light emitting layer and the pre-treatment electrode may be removed at the same time, or the removal may be performed in steps, that is, the pre-treatment electrode is removed first and then the first light emitting layer is removed. When the first light-emitting layer is removed step by step, the first light-emitting layer or the pretreatment electrode can be removed once, or the first light-emitting layer or the pretreatment electrode can be removed multiple times, and the removal mode is not limited.
Step S50: a second light emitting layer and a cathode are sequentially formed on the hole functional layer.
In this embodiment, through electrical treatment, an electrical and electrochemical reaction occurs between the hole functional layer and the light emitting layer, so that the interface between the hole functional layer and the light emitting layer is subjected to a passivation treatment in advance, which can be more matched with the electrical performance of the finally formed photoelectric device, thereby improving the performance of the photoelectric device. And the hole function layer can reach the electrically stable structural state by the advanced electrical aging, which is beneficial to prolonging the service life of the photoelectric device. In addition, the positive aging process of the photoelectric device is shortened due to the fact that the hole functional layer is subjected to electrical pretreatment, so that the device reaches maximum brightness in a short time, and the rapid response speed of the photoelectric device is improved. In addition, after the first luminescent layer is removed, the cathode and a new luminescent layer (a second luminescent layer) are formed again, so that structural damage to the first luminescent layer in the electrical treatment process is avoided, the performance of the formed photoelectric device is influenced, the second luminescent layer is not subjected to electrical treatment, the structure and the performance of the second luminescent layer are not influenced by the electrical treatment, and the original luminescent performance of the second luminescent layer can be realized. Further, since the first light-emitting layer is removed after the energization pretreatment, the influence of the energization treatment on the first light-emitting layer can be eliminated during the energization treatment, the condition limitation of the energization treatment can be reduced, the matching property between the hole function layer and a photoelectric device formed later can be improved to the maximum extent, and the performance of the photoelectric device can be improved.
In an embodiment, the energizing process in step S30 may be at constant current or constant voltage. In particular, under constant currentThe current density of the electrifying treatment is 1-100 mA/cm 2 . The constant voltage electrifying treatment corresponds to a threshold current, and the current density is not more than (less than or equal to) 100mA/cm 2 . The constant current and constant voltage electrifying treatment is two different treatment modes, namely unidirectional current. The structure damage of the hole function layer and the film layer of other electric treatment passing current caused by the overlarge current or current density is avoided in both treatment modes, and the effect of pretreatment is not obvious due to the overlarge current.
In another embodiment, the energizing process may employ one or more of alternating current, cyclic voltammetry, or alternating current pulses. Specifically, the frequency range of alternating current, cyclic volt-ampere or alternating current pulse is 20-60 Hz, and the current amplitude is less than or equal to 100mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The cyclic voltammetry scanning speed is 5 mV/s-1000 mV/s, and the reverse cut-off current is 100mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pulse frequency is 10-200 Hz, and the pulse current value is 100mA/cm 2 . Under the action of an electric field in the same direction, charged ion groups (charged after electrons are lost from molecules) or ions in each film layer under the electric pretreatment are driven by the electric field to move in a diffusion way along a specific direction; when the electric field changes alternately, the charged ion groups or ions are approximately balanced by the alternating acting force, so that irreversible metal ions in each film layer are prevented from being diffused, the conductivity of the electrode is deteriorated, and the energy level of each film layer in the photoelectric device changes to form a potential barrier. In addition, defects caused by diffusion of metal ions to other film layers are avoided, and adverse effects such as charge trapping, exciton quenching and the like are avoided, so that the performance and the service life of the photoelectric device are influenced. For example, in ions In the ITO anode are prevented from diffusing into the hole injection layer, even into the hole transport layer/light emitting layer, etc., and thus the anode conductivity is deteriorated, and the energy level is changed to form a potential barrier.
In an embodiment, the method of removing the first light emitting layer and the pre-treating electrode on the hole transport layer in step S40 may be a physical method or a chemical method. The physical method may be a mechanical peeling method or a tape sticking method. The chemical method includes a chemical dissolution method, and can be selected according to the material of the first light-emitting layer and the material property of the pre-treatment electrode, for example, the material can be removed by chemical reagent dissolution or reaction dissolution. It will be appreciated that the removal method employed should reduce or even avoid adversely affecting the hole function layer.
Further, in one embodiment, the step S40 is divided into two steps, specifically: the pretreatment electrode is removed first, and then the first light-emitting layer is removed. In a specific embodiment, the first light-emitting layer is removed by a mechanical lift-off method, which may specifically be: and (3) setting an adhesive tape on the first light-emitting layer, adhering the first light-emitting layer, and removing the first light-emitting layer on the hole function layer through the adhesive tape.
In another embodiment, the first light emitting layer may be removed by a chemical dissolution method. Specifically, the solvent used may be selected according to the material of the first light emitting layer and the material of the hole functional layer, for example, the solvent used may include, but is not limited to, one or more of non-polar solvents such as alkane, chloroform, toluene, etc., or the solvent used may include, but is not limited to, one or more of polar solvents such as ethanol, methanol, isopropanol, etc. It will be appreciated that the solvent used needs to be such that: the material of the first luminescent layer has better solubility in the solvent, and the material of the hole functional layer is insoluble or indissoluble in the solution, so that etching and structural damage to the hole functional layer and the interface thereof can be avoided while the first luminescent layer is removed by solvent dissolution. The solvent dissolution and removal mode includes one or more of spin coating, spraying, atomization cleaning, soaking inversion and the like. For example, the first light emitting layer may be removed by spin coating or spray coating a nonpolar solvent toluene on the first light emitting layer to dissolve the first light emitting layer.
In a specific embodiment, the material of the first light emitting layer is a quantum dot material, and the ligand of the quantum dot layer is a long-chain ligand, and the first light emitting layer can be removed by dissolving in a nonpolar solvent. In another embodiment, the ligands of the quantum dot material are short chain ligands, and the first light emitting layer may be removed by dissolution in a polar solvent. Further, when the ligand of the quantum dot material is a long-chain ligand, the ligand can be replaced by a short-chain ligand by a ligand exchange mode. For example, in forming the first light emissionAfter the layer, the surface of the layer is treated by halide solution to exchange ligands, so that the ligands of the quantum dots in the first luminescent layer are replaced by short-chain ligands. After the electrical pretreatment, the first light-emitting layer may be dissolved and removed by using a polar solvent. Solutes in halide solutions include, but are not limited to, mgCl 2 、KCl、NaCl、MgBr 2 One or more of KBr, solvents including, but not limited to, one or more of ethanol, methanol, isopropanol. Polar solvents include, but are not limited to, one or more of ethanol, methanol, isopropanol. In this embodiment, the first light-emitting layer performs ligand exchange, so that the first light-emitting layer can be dissolved in a polar solvent, and the first light-emitting layer is removed by dissolving the first light-emitting layer in the polar solvent, and meanwhile, etching and structural damage to the hole function layer and the interface thereof due to the use of a nonpolar solvent can be avoided.
In a specific embodiment, in step S30, a pre-processing electrode is disposed on the first light-emitting layer, which may specifically be: the metal electrode sheet is arranged on the first light-emitting layer as a pretreatment electrode cover. Correspondingly, in step S40, the metal electrode sheet is directly removed from the first light-emitting layer, and then the first light-emitting layer is removed, so that the pretreatment electrode is conveniently and rapidly removed.
In an embodiment, referring to fig. 2, fig. 2 is a schematic flow chart of another embodiment of a method for manufacturing an optoelectronic device according to the present application. Prior to step S50, further comprising: it is detected whether the first light emitting layer is completely removed. In particular, the corresponding detection mode may be determined according to the properties of the material of the first luminescent layer. For example, the material of the first light emitting layer has fluorescent or phosphorescent properties, and can be irradiated by an Ultraviolet (UV) lamp, and if no light or only weak light is emitted on the hole function layer, the first light emitting layer is determined to be completely removed. If the hole function layer has obvious luminescence, determining that the first luminescent layer is not completely removed, repeating step S40, removing the first luminescent layer again, detecting whether the first luminescent layer is completely removed again, and continuously repeating the two steps until the detection confirms that the first luminescent layer is completely removed, and then proceeding to step S50. Alternatively, it is also possible to judge whether the removal of the light-emitting layer substance is complete by absorption spectroscopy. Specifically, by performing spectral absorption measurement on the substrate from which the first light-emitting layer is removed, comparing the absorption spectra of the light-emitting material solid-state film, if there is no absorption peak corresponding to the light-emitting material solid-state film, the removal is considered to be complete.
In one embodiment, step S30 is specifically: and a pretreatment electrode and a first electronic functional layer are arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply to carry out electrifying treatment. By adding the electronic functional layer in the electrifying pretreatment, the structure of the photoelectric device which is formed in practice can be better simulated more closely to the photoelectric device which is formed in practice, so that the matching performance of the hole functional layer with the photoelectric device after the electric treatment is improved, and the performance of the photoelectric device is improved. Further, the first electron functional layer is also removed when the first light emitting layer and the preconditioning electrode on the hole functional layer are removed in step S40. In step S50, a second light emitting layer, a second electron functional layer, and a cathode are sequentially formed on the hole functional layer.
In another embodiment, step S20 is to sequentially form a hole function layer and a first light emitting layer on the anode. In step S50, a second light emitting layer and a cathode are sequentially formed on the hole function layer, including: and forming a second light-emitting layer, a second electron functional layer and a cathode on the hole functional layer in sequence.
The first electron functional layer may include a first electron transport layer and/or a first electron injection layer. The second electron functional layer may include a second electron transport layer and/or a second electron injection layer. In other words, the first electron functional layer may include any one of the first electron transport layer or the first electron injection layer, or may include both of the first electron transport layer and the first electron injection layer. The second electron functional layer may include any one of the second electron transport layer or the second electron injection layer, or may include both of the second electron transport layer and the second electron injection layer. It will be appreciated that the first electronic functional layer or the second electronic functional layer may also comprise other layers, such as barrier layers, interface layers, etc.
In one embodiment, step S30 is specifically: and disposing a first electronic function layer on the metal pretreatment electrode, and covering the pretreatment electrode on which the first electronic function layer is formed on the first light-emitting layer, wherein the first electronic function layer is close to one side of the first light-emitting layer and is in contact with the first light-emitting layer. Correspondingly, the step S40 specifically includes: and removing the first light-emitting layer, the first electron functional layer and the pretreatment electrode on the hole functional layer. In this embodiment, the first electronic functional layer is disposed on the pre-processing electrode and integrally covers the first light-emitting layer for conducting pretreatment, and then the pre-processing electrode and the first electronic functional layer can be directly removed in step S40, so that the pre-processing electrode and the first electronic functional layer can be rapidly removed, and the operation is convenient and fast.
In one embodiment, referring to fig. 3a to 3c, fig. 3a to 3c are schematic flow diagrams of a preparation method of an optoelectronic device according to an embodiment of the present application. Referring to fig. 3a, a hole injection layer 13, a hole transport layer 14, and a first light emitting layer 21 are sequentially formed on an ITO substrate (including a substrate 11 and an ITO electrode layer 12), a pre-treatment electrode 22 having a first electron transport layer 23 formed thereon is covered on the first light emitting layer 21, and a power supply is connected to the ITO electrode layer 12 through the pre-treatment electrode 22 to perform power-on pre-treatment. Then, referring to fig. 3b, after the pre-treatment electrode 22 and the first electron transport layer 23 thereon are removed, the first light emitting layer 21 is stuck by the adhesive tape 24 to perform removal peeling, and judgment is made by UV lamp irradiation until it is judged that the removal of the first light emitting layer 21 is complete. Subsequently, in conjunction with fig. 3c, a second light emitting layer 15, a second electron transport layer 16, and a cathode 17 are sequentially formed on the hole transport layer 14, forming the optoelectronic device 100.
In the above embodiments, the materials of the first light emitting layer and the first light emitting layer are independently selected from an organic light emitting material, a quantum dot light emitting material, or a perovskite semiconductor material, respectively; the organic luminescent material is at least one selected from a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe luminescent material emitting blue light, a TTPA luminescent material emitting green light, a TBRb luminescent material emitting orange light and a DBP luminescent material emitting red light; the quantum dot luminescent material is at least one of quantum dots with single structure and quantum dots with core-shell structure,the single structure quantum dot is selected from at least one of II-VI compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound and II-IV-VI compound, the II-VI compound is selected from at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe, cdZnSTe, cdSeSTe and ZnSeSTe, the IV-VI compound is selected from at least one of PbS, pbSe, pbTe, pbSeS, pbSeTe, the III-V compound is selected from at least one of InP, inAs, gaP, gaAs, gaSb, gaAsP, inGaP, inGaAs, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, the I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the perovskite type semiconductor material is selected from doped or undoped inorganic perovskite type semiconductor or organic-inorganic hybrid perovskite type semiconductor; the structural general formula of the inorganic perovskite semiconductor is AMX 3 Wherein A is Cs + Ions, M is a divalent metal cation, including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2+ X is a halogen anion including but not limited to Cl-, br-, I - The method comprises the steps of carrying out a first treatment on the surface of the The structural general formula of the organic-inorganic hybridization perovskite type semiconductor is BMX 3 Wherein B is an organic amine cation including, but not limited to CH 3 (CH 2 ) n-2 NH 3+ (n.gtoreq.2) or NH 3 (CH 2 ) n NH 3 2+ (n is more than or equal to 2); m is a divalent metal cation including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the X is a halogen anion including, but not limited to, cl-, br-, I-. The thickness of the first light emitting layer may be, for example, 10 to 200nm, such as 10nm, 50nm, 100nm, 150nm, 200nm, or the like. The thickness of the second light emitting layer may be, for example, 10 to 200nm, such as 10nm, 50nm, 100nm, 150nm, 200nm, etc.
In a specific embodiment, the materials of the first light emitting layer and the second light emitting layer are different, and in the above embodiment provided by the present application, the hole functional layer can reach an electrical stable state in advance and the interface between the hole functional layer and the anode and between the hole functional layer and the light emitting layer can be passivated through the power-on pretreatment, so that the performance and the service life of the photoelectric device are improved. In another embodiment, the materials of the first light emitting layer and the second light emitting layer are the same, so that the similarity between the structure subjected to power pretreatment and the actually formed photoelectric device is higher, the actually formed photoelectric device is better simulated, the hole functional layer subjected to power treatment can be more matched with the actually formed photoelectric device, and the performance and the service life of the photoelectric device are better improved.
In the above embodiments, the material of the hole injection layer may be selected from materials having hole injection ability, including, but not limited to, one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazabenzophenanthrene (HATCN), copper phthalocyanine (CuPc), transition metal oxide, transition metal chalcogenide. Wherein the transition metal oxide comprises one or more of NiOx, moOx, WOx, crOx, cuO. The metal chalcogenide compound includes one or more of MoSx, moSex, WSx, WSex, cuS. Wherein the value of x in each compound can be determined based on the valence of the atom in the compound. The hole injection layer thickness may be, for example, 10nm to 100nm, such as 10nm, 30nm, 50nm, 80nm, 100nm, etc.
In the above embodiment, the material of the hole transport layer may be selected from organic materials having hole transport ability, including but not limited to poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK),One or more of 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 "-tris (carbazol-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazol) 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), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), spiro-NPB, spiro-TPD, doped graphene, undoped graphene, and C60. The material of the hole transport layer may also be selected from inorganic materials with hole transport capability, including but not limited to doped or undoped NiO, moO 3 、WO 3 、V 2 O 5 P-type gallium nitride, crO 3 、CuO、MoS x 、MoSe x 、WSx、WSe x And one or more of CuS, cuSCN. The hole transport layer thickness may be, for example, 10nm to 100nm, such as 10nm, 30nm, 50nm, 80nm, 100nm, etc.
In the above-described embodiments, the materials of the first electron transport layer and the second electron transport layer may be materials known in the art for electron transport layers. For example, the materials of the first electron transport layer and the second electron transport layer may each be independently selected from, but not limited to, one or more of an inorganic nanocrystalline material, a doped inorganic nanocrystalline material, an organic material. The inorganic nanocrystalline material may include: the inorganic nanocrystalline material may include: one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide, and the doped inorganic nanocrystalline material comprises one or more of zinc oxide dopant, titanium dioxide dopant and tin dioxide dopant, wherein the doped inorganic nanocrystalline material is an inorganic material doped with other elements, and the doped elements are selected from Mg, ca, li, ga, al, co, mn and the like; the organic material may include one or both of polymethyl methacrylate and polyvinyl butyral. The first electron transport layer thickness may be, for example, 20nm to 100nm, such as 20nm, 40nm, 60nm, 80nm, 100nm, etc. The second electron transport layer may have a thickness of, for example, 20nm to 100nm Such as 20nm, 40nm, 60nm, 80nm, 100nm, etc. In one embodiment, the materials of the first electron transport layer and the second electron transport layer are respectively and independently selected from ZnO and TiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 One or more of NiO, tiLiO, znAlO, znO, znSnO, znLiO, inSnO.
In the above-described embodiments, the materials of the first electron injection layer and the second electron injection layer may be materials known in the art for the electron injection layers. For example, the materials of the first electron injection layer and the second electron injection layer may each be independently selected from, but not limited to, liF, mgP, mgF 2 、Al 2 O 3 、Ga 2 O 3 、LiF/Yb、ZnO、Cs 2 CO 3 、RbBr、Rb 2 CO 3 At least one of them. The thickness of the first electron injection layer may be, for example, 10nm to 100nm, such as 10nm, 20nm, 40nm, 60nm, 80nm, 100nm, etc. The thickness of the second electron injection layer may be, for example, 10nm to 100nm, such as 10nm, 20nm, 40nm, 60nm, 80nm, 100nm, etc.
In the above embodiments, the materials of the anode are materials known in the art for the anode, and the materials of the pre-treatment electrode and the cathode are materials known in the art for the cathode. The materials of the anode, the pre-treatment electrode and the cathode may be, for example, one or more of a metal, a carbon material and a metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be doped or undoped metal oxide including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode of doped or undoped transparent metal oxide with metal sandwiched therebetween, the composite electrode including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 One or more of the following. Wherein AZO/Ag/AZO represents an AZO layer,An electrode with a three-layer composite structure consisting of an Ag layer and an AZO layer. The anode thickness may be, for example, 10nm to 1000nm, such as 10nm, 200nm, 400nm, 600nm, 800nm, 1000nm, etc. The thickness of the cathode may be, for example, 10nm to 1000nm, such as 10nm, 200nm, 400nm, 600nm, 800nm, 1000nm, etc. In an embodiment, the thickness of the pre-treatment electrode may be, for example, 10nm to 1000nm, such as 10nm, 200nm, 400nm, 600nm, 800nm, 1000nm, etc. In another embodiment, the thickness of the pre-treatment electrode is 50 μm to 200 μm, such as 50 μm, 100 μm, 200 μm, etc.
Specifically, the materials of the pretreatment electrode and the cathode may be the same or different. In one embodiment, the pretreatment electrode and the cathode are made of the same material and are all Al electrodes. In another embodiment, the material of the pre-treatment electrode and the material of the cathode are different, the material of the pre-treatment electrode is an Al electrode, and the cathode is a composite electrode AZO/Al/AZO. When the materials of the pretreatment electrode and the cathode are different, the structure of the photoelectric device can be simulated to a certain extent through the multi-film structure subjected to the electrified pretreatment, so that the performance of the hole functional layer is more stable, the interface is more matched with the finally formed photoelectric device to a certain extent, and the performance and the service life of the photoelectric device can be improved. The pretreated electrode and the cathode are made of the same material, the pretreated multi-film structure is more similar to the structure of the finally formed photoelectric device, namely, the electrified pretreated multi-film structure can better simulate the structure of the photoelectric device, so that the electrified pretreated hole functional layer can be more matched with the finally formed photoelectric device, the electric stability is better, the interface is more adaptively matched with the luminous film in advance, and excessive electrons in the initial stage can be resisted in the luminous process of the formed photoelectric device without damaging the structure.
In the above-described embodiment, the kind of the substrate is not limited, and a conventionally used substrate may be used, for example, a rigid substrate, a glass material, or the like; the substrate may be polyimide or the like.
It is understood that the method for manufacturing the optoelectronic device may further include an encapsulation step, and the encapsulation material may be an acrylic resin or an epoxy resin, or the like. The encapsulation can be machine encapsulation or manual encapsulation, ultraviolet curing encapsulation can be adopted, and the concentration of oxygen and water in the environment where the encapsulation step is carried out is lower than a specific value, such as lower than 0.1ppm, so as to ensure the stability of the photoelectric device.
It will be appreciated that the materials, thicknesses, etc. of the various layers of the optoelectronic device may be adjusted according to the lighting requirements of the optoelectronic device.
Specifically, in the above steps, the method of forming the anode, the hole-functional layer, the first light-emitting layer, the second light-emitting layer, the electron-functional layer, and the cathode may be implemented by conventional techniques in the art, including but not limited to a solution method and a deposition method, wherein the solution method includes, but is not limited to, spin coating, inkjet printing, doctor blading, dip-lift, dipping, spray coating, roll coating, or casting; deposition methods include chemical methods including, but not limited to, chemical vapor deposition methods, continuous ion layer adsorption and reaction methods, anodic oxidation methods, electrolytic deposition methods, or co-precipitation methods, and physical methods. Physical methods include, but are not limited to, thermal vapor deposition, electron beam vapor deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, or pulsed laser deposition. When the solution method is adopted to prepare each layer of structure, a drying treatment procedure is required to be added. The drying treatment may be an annealing treatment. Wherein "annealing process" includes all treatment processes that enable the wet film to obtain higher energy, thereby converting from a wet film state to a dry state, for example "annealing process" may refer only to a heat treatment process, i.e., heating the wet film to a specific temperature and then holding for a specific time to allow the solvent in the wet film to sufficiently volatilize; as another example, the "annealing process" may further include a heat treatment process and a cooling process performed sequentially, i.e., heating the wet film to a specific temperature, then maintaining the wet film for a specific time to volatilize the solvent in the first wet film sufficiently, and then cooling at a suitable rate to eliminate residual stress and reduce the risk of layer deformation and cracking of the dried hole transport film.
The embodiment of the application also provides a display device which comprises the photoelectric device prepared by the preparation method of the photoelectric device. The display device may be any electronic product with a display function, including but not limited to a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle-mounted display, a television set or an electronic book reader, wherein the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, etc.
The technical solutions and effects of the present application will be described in detail by way of specific examples, comparative examples and experimental examples, which are only some examples of the present application, and are not intended to limit the present application in any way.
Example 1
A preparation process of a front bottom emission light emitting diode comprises the following steps:
step 1, firstly, ultrasonic cleaning is carried out on the ITO-plated substrate by using acetone and ethanol for 10-20 min (preferably 15 min), then deionized water is used for cleaning, and then drying is carried out, then drying is carried out on the ITO-plated substrate on a heating plate with the temperature of 100-200 ℃ (preferably 150 ℃) for 5-10 min (preferably 10 min), and then ultraviolet light irradiation (UV) is carried out for 15-30 min (preferably 20 min) so as to increase the work function of the ITO.
Step 2, placing the cleaned substrate into a glove box, and performing a Hole Injection Layer (HIL) PEDOT by adopting a spin coating method: PSS (mass fraction 2.8%) film was prepared, spin coated at 3000rpm for 30s, followed by heating on a hot plate at 150℃for 20min.
Step 3, spin-coating TFB (6.5 mg/mL), rotating speed 3000, time 30s, then heating at 120℃for 20min.
And 4, spin-coating ZnCdSe/ZnCdSe/ZnS/ZnCdS/ZnS Quantum Dots (QD) (10 mg/mL), rotating at 1500, for 30s, and heating on a heating plate at 100 ℃ for 5min to form a quantum dot luminescent layer.
And 5, directly covering the Al metal electrode on the light-emitting layer, wherein the thickness of the Al metal electrode is 100 mu m. And the anode ITO and the Al metal electrode are communicated with a power supply to carry out electrifying treatment, wherein the constant current is 0.5mA, and the electrifying time is 30min.
And 6, after the electrifying treatment is finished, removing the metal Al cathode, peeling the luminescent layer by using an adhesive tape, and judging whether the luminescent layer is completely removed by using UV lamp irradiation. And (3) repeating the step, namely stripping the adhesive tape and judging by irradiating with a UV lamp until the luminescent layer is completely removed, and performing the step 7.
And 7, preparing the same quantum dot luminescent layer according to the method of the step 4.
And 8, spin-coating ZnO (30 mg/mL ethanol colloid) on the quantum dot luminescent layer prepared in the step 7, rotating at 4000rpm for 30s, and then heating on a heating plate at 80 ℃ for 10min to form an Electron Transport Layer (ETL).
Step 9, evaporating by heat, the vacuum degree is not higher than 3x10 -4 Pa, evaporating Al at a speed of 1 angstrom/second for 100 seconds to form a cathode with a thickness of 100nm, and obtaining the positive quantum dot light emitting diode, wherein the structure of the device is shown in figure 3c.
Example 2
The present embodiment provides a method for manufacturing a quantum dot electroluminescent diode, which is different from embodiment 1 only in that: and 6, after the electrifying treatment is finished, removing the metal Al cathode, dripping n-octane solvent on the luminescent layer subjected to the electrical treatment, standing for 60 seconds, removing the solution by adopting a spin coating method, and judging whether the luminescent layer is completely removed by using a UV lamp. If the light-emitting layer is not completely removed, repeating the step, namely repeating the process of dissolving the light-emitting layer by n-octane and the irradiation judgment of the UV lamp until the light-emitting layer is completely removed, and performing the step 7.
Example 3
The present embodiment provides a method for manufacturing a quantum dot electroluminescent diode, which is different from embodiment 1 only in that: and 4, spin-coating ZnCdSe/ZnCdSe/ZnS/ZnCdS/ZnS Quantum Dots (QD) (10 mg/mL), rotating at 1500, for 30s, and heating on a heating plate at 100 ℃ for 5min to form a quantum dot luminescent layer. Dropwise adding 0.5M KCl ethanol solution on the quantum dot luminescent layer, standing for 3min for ligand exchange, removing redundant solvent by adopting a spin coating method, and heating on a heating plate at 100 ℃ for 5min. And 6, after the electrifying treatment is finished, removing the metal Al cathode, dripping ethanol on the luminescent layer subjected to the electrical treatment, standing for 60 seconds, removing the solution by adopting a spin coating method, and judging whether the luminescent layer is completely removed by adopting a UV lamp. If the light-emitting layer is not completely removed, repeating the step, namely repeating the process of dissolving the light-emitting layer by ethanol and the irradiation judgment by a UV lamp until the light-emitting layer is completely removed, and performing the step 7.
Example 4
The present embodiment provides a method for manufacturing a quantum dot electroluminescent diode, which is different from embodiment 3 only in that: and 5, covering an Al metal electrode which is provided with an electron transport layer in advance on the light-emitting layer, directly contacting the electron transport layer with the light-emitting layer, and communicating a power supply through the anode ITO and the cathode to carry out electrifying treatment, wherein the constant current is 0.5mA, and the electrifying time is 30min. Wherein an ethanol colloid of ZnO (30 mg/mL) was spin-coated on an Al metal electrode of 100 μm by spin-coating at 3000rpm for 30s, followed by drying at 80℃for 10min to form an electron transport layer.
Example 5
The present embodiment provides a method for manufacturing a quantum dot electroluminescent diode, which is different from embodiment 4 only in that: and 5, directly covering an Al metal electrode on the light-emitting layer, and communicating a power supply through the anode ITO and the cathode to perform electrifying treatment, wherein the alternating current is 0.5mA in amplitude, 2Hz in frequency and 30min in electrifying time.
Comparative example:
a preparation process of a positive top emission structure:
the present embodiment provides a method for manufacturing a quantum dot electroluminescent diode, which is different from embodiment 1 only in that: step 5-step 7 are not performed, i.e. no electrical pretreatment is performed.
Examples 1-5 and comparative examples were quantum dot light emitting diodes, JVL data of devices were tested to determine device electrical properties, as shown in fig. 4a and 4b, and fig. 4a and 4b are current density-voltage and current density-luminance graphs, respectively. Wherein the current density-voltage curve represents the conductivity of the device and the operating voltage characteristics of the device; the current density-luminance curve represents the operating efficiency of the device. And testing the maximum luminance L (cd/m) of the Quantum dot light emitting diodes of examples 1 to 5 and comparative examples 2 ) T95 (h) and T95_1K (h), the test results are shown in Table 1 below. Wherein the method comprises the steps of，L(cd/m 2 ) For maximum brightness under 1mA current drive, T95 (h) is the time required for the quantum dot light emitting diode to decay from 100% to 95% at maximum brightness. T95_1k (h) is the time required for the quantum dot light emitting diode to decay from 100% to 95% in brightness at 1000 nits.
Table 1:
| L(cd/m 2 ) | T95(h) | T95_1K(h) | |
| comparative example | 1818 | 3.16 | 8.74 |
| Example 1 | 2425 | 3.28 | 14.78 |
| Example 2 | 2558 | 3.68 | 18.14 |
| Example 3 | 2953 | 3.81 | 24.03 |
| Example 4 | 3194 | 3.96 | 28.48 |
| Example 5 | 3593 | 3.65 | 32.11 |
As can be seen from table 1, the maximum brightness and lifetime of the qd leds of examples 1 to 5 are significantly improved compared to the comparative examples. The preparation method of the photoelectric device can improve the performance and service life of the photoelectric device.
In each of examples 1 to 3, the light-emitting layer was removed by a different method by the power-on treatment, and then other layers were formed, and the device performance and lifetime were significantly improved and prolonged.
As can be seen from examples 3 and 4, by adding an electron transport layer in the pretreated analog device, the structure of the actually formed photoelectric device can be better simulated, so that the matching performance of the hole functional layer (hole transport layer) with the photoelectric device after electric treatment is improved, and the performance and the service life of the photoelectric device are improved.
As can be seen from examples 4 and 5, the alternating current treatment can prevent irreversible metal ion diffusion of the anode ITO and improve the performance and lifetime of the device, compared with the constant current treatment in example 4.
The above description is made in detail on the preparation method of the photoelectric device, the photoelectric device and the display device provided by the embodiment of the present application, and specific examples are applied to the description of the principle and the implementation of the present application, where the description of the above examples is only used to help understand the method and the core idea of the present application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (14)
1. A method of fabricating an optoelectronic device, comprising:
providing an anode;
sequentially forming a hole function layer and a first light-emitting layer on the anode;
a pretreatment electrode is arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply to carry out electrifying treatment;
removing the first light-emitting layer and the pretreatment electrode on the hole function layer;
and forming a second light-emitting layer and a cathode on the hole functional layer in sequence.
2. The method according to claim 1, wherein the energizing treatment is a constant current, and the current density of the energizing treatment under the constant current is in the range of 1 to 100mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Or alternatively
The electrifying treatment is carried out under a constant voltage, and the current density of the electrifying treatment under the constant voltage is less than or equal to 100mA/cm 2 。
3. The method of claim 1, wherein the energizing is performed with one or more of alternating current, cyclic voltammetry, or alternating current pulses.
4. The method according to claim 1, wherein the method of removing the first light-emitting layer and the pre-treatment electrode on the hole function layer is a mechanical peeling method, a tape sticking method, or a chemical dissolution method.
5. The method according to claim 4, wherein the removing the first light-emitting layer and the pretreatment electrode on the hole function layer is by the chemical dissolution method, comprising:
determining a kind of solvent based on a material of the first light emitting layer;
dissolving and removing the first light-emitting layer by using the determined solvent;
wherein the determining the kind of the solvent based on the material of the first light emitting layer includes:
determining a solvent selection nonpolar solvent based on the fact that the material of the first luminescent layer is a quantum dot material, and the ligand of the quantum dot material is a long-chain ligand; or alternatively
And determining a solvent selection polar solvent based on the fact that the material of the first luminescent layer is a quantum dot material and the ligand of the quantum dot material is a short-chain ligand.
6. The method of claim 5, wherein the material of the first luminescent layer is a quantum dot material, and the ligand of the quantum dot material is a long-chain ligand;
the hole function layer and the first light-emitting layer are sequentially formed on the anode, and the method comprises the following steps: arranging a halide solution on the first luminescent layer for ligand exchange, and replacing the long-chain ligand of the quantum dot material with a short-chain ligand;
The removing the first light emitting layer and the pretreatment electrode on the hole function layer is the chemical dissolution method, comprising:
the first light-emitting layer is dissolved and removed using a polar solvent.
7. The method according to claim 1, wherein the step of providing a pretreatment electrode on the first light-emitting layer, and connecting the anode and the pretreatment electrode to power supplies, respectively, and performing the energization process comprises:
a first electronic functional layer and the pretreatment electrode are arranged on the first luminous layer, and the anode and the pretreatment electrode are respectively communicated with a power supply to carry out electrifying treatment;
the removing the first light emitting layer and the pre-treatment electrode on the hole function layer includes:
removing the first light-emitting layer, the first electron functional layer and the pre-treatment electrode on the hole functional layer; wherein the first electron functional layer comprises a first electron transport layer and/or a first electron injection layer.
8. The method of claim 1, wherein before sequentially forming the second light-emitting layer and the cathode on the hole-functional layer, further comprising:
detecting whether the first light-emitting layer is completely removed;
And if the first light-emitting layer is not completely removed, repeating the removing step until the first light-emitting layer is completely removed.
9. The method of claim 1, wherein forming a second light emitting layer and a cathode sequentially on the hole function layer comprises:
sequentially forming the second light-emitting layer, the second electron functional layer and the cathode on the hole functional layer; wherein the second electron functional layer comprises a second electron transport layer and/or a second electron injection layer.
10. The method of manufacturing according to claim 1, wherein the disposing a pre-treatment electrode on the first light-emitting layer comprises:
a metal electrode plate is used as the pretreatment electrode cover to be arranged on the first luminous layer;
the removing the first light emitting layer and the pre-treatment electrode on the hole function layer includes:
and removing the metal electrode plate from the first light-emitting layer, and removing the first light-emitting layer by a mechanical stripping method, an adhesive tape bonding method or a chemical dissolution method.
11. The method of manufacturing according to claim 10, wherein the disposing the metal electrode sheet as the pre-treatment electrode cap on the first light emitting layer comprises:
A first electronic function layer is arranged on the metal electrode plate, and the metal electrode plate with the first electronic function layer is covered on the first luminous layer; wherein, the first electronic functional layer is close to one side of the first light-emitting layer and is contacted with the first light-emitting layer;
said removing said metal electrode sheet from said first light emitting layer comprises:
and removing the metal electrode plate and the first electronic function layer arranged on the metal electrode plate from the first light-emitting layer.
12. The method according to claim 1, wherein the materials of the first light-emitting layer and the first light-emitting layer are each independently selected from an organic light-emitting material, a quantum dot light-emitting material, or a perovskite-type semiconductor material; the organic luminescent material is at least one selected from a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe luminescent material emitting blue light, a TTPA luminescent material emitting green light, a TBRb luminescent material emitting orange light and a DBP luminescent material emitting red light; the quantum dot luminescent material is selected from at least one of single-structure quantum dots and core-shell structure quantum dots, the single-structure quantum dots are selected from at least one of II-VI compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound and II-IV-VI compound, the II-VI compound is selected from at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe, cdZnSTe, cdSeSTe and ZnSeSTe, the IV-VI compound is selected from at least one of PbS, pbSe, pbTe, pbSeS, pbSeTe, the III-V compound is selected from at least one of InP, inAs, gaP, gaAs, gaSb, gaAsP, inGaP, inGaAs, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the perovskite type semiconductor material is selected from doped or undoped inorganic perovskite type semiconductor or organic-inorganic hybrid perovskite type semiconductor; the structural general formula of the inorganic perovskite semiconductor is AMX 3 Wherein A is Cs + Ions, M is a divalent metal cation, including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2+ X is a halogen anion including but not limited to Cl - 、Br - 、I - The method comprises the steps of carrying out a first treatment on the surface of the The structural general formula of the organic-inorganic hybridization perovskite type semiconductor is BMX 3 Wherein B is an organic amine cation including, but not limited to CH 3 (CH 2 ) n-2 NH 3+ Or NH 3 (CH 2 ) n NH 3 2+ Wherein n is greater than or equal to 2; m is a divalent metal cation including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2 + 、Ge 2+ 、Yb 2+ 、Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the X is a halogen anion including but not limited to Cl - 、Br - 、I - The method comprises the steps of carrying out a first treatment on the surface of the And/or
The hole functional layer comprises a hole transport layer and/or a hole injection layer, wherein the material of the hole transport layer is selected from 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-carbazol) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped graphene, C60, niO, moO 3 、WO 3 、V 2 O 5 P-type gallium nitride, crO 3 、CuO、MoS x 、MoSe x 、WSx、WSe x And one or more of CuS, cuSCN; the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiOx, moOx, WOx, crOx, cuO and the metal chalcogenide comprises one or more of MoSx, moSex, WSx, WSex, cuS; and/or
The materials of the anode, the pretreatment electrode and the cathode are respectively and independently selected from a metal electrode, a carbon electrode and a composite electrode formed by one or more of doped or undoped metal oxide electrodes; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 At least one of them.
13. An optoelectronic device produced by the method of producing an optoelectronic device according to any one of claims 1 to 12.
14. A display device comprising the optoelectronic device of claim 13.
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