CN116367584A - Film, preparation method thereof, photoelectric device and display device - Google Patents

Film, preparation method thereof, photoelectric device and display device Download PDF

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Publication number
CN116367584A
CN116367584A CN202111616627.6A CN202111616627A CN116367584A CN 116367584 A CN116367584 A CN 116367584A CN 202111616627 A CN202111616627 A CN 202111616627A CN 116367584 A CN116367584 A CN 116367584A
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solvent
electron transport
layer
film
polar
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张天朔
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TCL Technology Group Co Ltd
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TCL Technology Group Co Ltd
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Priority to CN202111616627.6A priority Critical patent/CN116367584A/en
Priority to PCT/CN2022/139615 priority patent/WO2023125074A1/en
Publication of CN116367584A publication Critical patent/CN116367584A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The application provides a film and a preparation method thereof, an optoelectronic device and a display device, wherein the method comprises the following steps: providing a bearing interface; forming an electron transport pre-layer on a support interface using a first solution comprising a first electron transport material and a first solvent; applying a second solvent to the surface of the electron transport pre-layer to obtain a thin film; the first electron transport material is a polar first material, the first solvent is a polar solvent, and the second solvent is a nonpolar solvent; alternatively, the first electron transport material is a nonpolar first material, the first solvent is a nonpolar solvent, and the second solvent is a polar solvent. The final film forming quality of the film is improved by controlling the unit cell size, so that carriers are easy to migrate, and the electron transmission capacity is improved.

Description

Film, preparation method thereof, photoelectric device and display device
Technical Field
The application relates to the technical field of display, in particular to a film and a preparation method thereof, a photoelectric device and a preparation method thereof and a display device.
Background
The quantum dot electroluminescent technology has the advantages of low cost, light weight, high response speed, high color saturation and the like, has wide development prospect, and becomes one of important research directions of the new generation of LED illumination.
The existing QLED mainly comprises a cathode, an anode, a hole/electron transport layer and a quantum dot luminescent layer, wherein the electron transport layer is used as an important carrier transport layer, and the morphology (film forming state) and mobility of the electron transport layer are parameters which have a certain influence on the overall performance of the device. The electron transport layer is typically prepared by solution deposition, and crystal overgrowth can result from non-uniformity in film formation, crystallization, and total deposition time. For example: in the film forming stage, when the solvent thoroughly dries the crystal, the growth is stopped, and the step is usually performed by baking after the spin coating is completed, but at this time, the crystal cells are already enlarged due to the spin coating in the latter half and slow evaporation in the baking stage, that is, the crystal cells excessively grow, the cell gaps are enlarged, and finally the required morphological requirements cannot be met, so that the flatness after the film formation is poor, and the transmission performance of the electron transport layer is affected.
Disclosure of Invention
The application provides a film and a preparation method thereof, an optoelectronic device and a preparation method thereof, and a display device, wherein the unit cell size of a first electron transport material is controlled, the crystallization state is improved, and the electron transport capacity of the film is improved.
In a first aspect, the present application provides a method for preparing a film, which includes the following steps:
providing a bearing interface;
forming an electron transport pre-layer on the support interface with a first solution comprising a first electron transport material and a first solvent;
applying a second solvent to the surface of the electron transport pre-layer to obtain a thin film;
the first electron transport material is a polar first material, the first solvent is a polar solvent, and the second solvent is a nonpolar solvent; alternatively, the first electron transport material is a nonpolar first material, the first solvent is a nonpolar solvent, and the second solvent is a polar solvent.
Optionally, in some embodiments of the present application, the forming an electron transport pre-layer on the support interface with the first solution includes: depositing the first solution on the bearing interface in a first direction by a wet film making mode;
the applying a second solvent to the electron transport pre-layer surface comprises: and depositing the second solvent on the electron transport pre-fabricated layer in a second direction by a wet film forming method, wherein the second direction is opposite to the first direction.
Optionally, in some embodiments of the present application, the first solution is deposited on the carrier interface in a first direction by using a wet film forming method, where a deposition time is 10s to 15s; and/or depositing the second solvent on the electron transport pre-fabricated layer in a second direction in a wet film forming manner, wherein the deposition time is 20 s-30 s.
Optionally, in some embodiments of the present application, the method for making a wet-process film deposits the first solution on the carrier interface in a first direction, wherein the method for making a wet-process film includes: spin coating, doctor blade, screen printing, spray, ink jet printing, dip coating; and/or
The method for preparing the film by wet method is characterized in that the second solvent is deposited on the electron transport pre-fabricated layer in a second direction, wherein the method for preparing the film by wet method comprises the following steps: spin coating, doctor blade, screen printing, spraying, ink jet printing, dip coating.
Optionally, in some embodiments of the present application, the method of using wet-method to form a film deposits the first solution on the carrier interface in a first direction, where spin-coating is performed according to the following spin-coating process parameters: the spin coating rotating speed is 3000 rpm-5000 rpm; and/or
The second solvent is deposited on the electron transport preformed layer in a second direction in a wet film forming mode, wherein when spin coating is adopted, spin coating process parameters are as follows: the spin coating rotational speed is 10000 rpm-12000 rpm.
Optionally, in some embodiments of the present application, the concentration of the first solution is 35mg/mL to 40mg/mL; and/or
The volume ratio of the first solvent to the second solvent is (8-20): 1.
optionally, in some embodiments of the present application, the polar first material is a first electron transport material having a dielectric constant greater than 3; and/or
The polar solvent is an organic solvent with a dielectric constant greater than 3; and/or
The nonpolar first material is a first electron transport material with a dielectric constant less than 3; and/or
The nonpolar solvent is an organic solvent having a dielectric constant of less than 3.
Alternatively, in some embodiments of the present application, the polar first material is a metal oxide having a first ligand, wherein the first ligand is a first alkyl group comprising a first reactive group, wherein the first reactive group is any one of a hydroxyl group, a carboxyl group, an amine group, or an aldehyde group, and wherein a carbon number of the first alkyl group of 0-18,0 indicates that the first reactive group is directly attached to the metal oxide; and/or the metal oxide is any one of zinc oxide, titanium dioxide, barium titanate, aluminum-doped zinc oxide, lithium-doped zinc oxide or magnesium-doped zinc oxide; and/or
The polar solvent is any one of an amide compound, an acid compound, an aldehyde compound or an alcohol compound containing no more than four carbon atoms; and/or
The nonpolar solvent is any one of toluene, cyclohexane, carbon tetrachloride, trichloroethylene or chlorobenzene.
Optionally, in some embodiments of the present application, when the first active group is a hydroxyl group or an amine group, the carbon atom number of the first alkyl group is 0 to 18; and/or when the first active group is carboxyl or aldehyde, the carbon atom number of the first alkyl group is 2-18.
Alternatively, in some embodiments of the present application, the nonpolar first material is a metal oxide or an organic compound having a second ligand, wherein the second ligand is a second alkyl group including a second active group, the second active group is any one of halogen or nitro, and the carbon number of the second alkyl group is 0 to 18,0, which indicates that the second active group is directly connected to the metal oxide; and/or
The metal oxide is any one of zinc oxide, titanium dioxide, barium titanate, aluminum-doped zinc oxide, lithium-doped zinc oxide or magnesium-doped zinc oxide; and/or
The organic compound is any one or more than two of methyl C71-butyrate, C60 or [6,6] -phenyl-C61-butyrate; and/or
The nonpolar solvent is any one of toluene, cyclohexane, carbon tetrachloride, trichloroethylene or chlorobenzene; and/or
The polar solvent is any one of an amide compound, an acid compound, an aldehyde compound or an alcohol compound containing no more than four carbon atoms.
In a second aspect, the present application provides a film prepared by the film preparation method described above.
A third aspect of the present application provides an optoelectronic device comprising: the anode layer, the light-emitting layer, the electron transport layer and the cathode layer of the laminated structure, wherein the electron transport layer is prepared by the film preparation method, or the electron transport layer is the film.
A fourth aspect of the present application provides a method for preparing an optoelectronic device, including:
preparing a light emitting layer on an anode;
preparing a film on the light-emitting layer by adopting the preparation method of the film to obtain an electron transport layer; and
preparing a cathode on the electron transport layer to obtain a photoelectric device;
or preparing a film on the cathode by adopting the preparation method of the film to obtain an electron transport layer;
preparing a light emitting layer on the electron transport layer; and
and preparing an anode on the light-emitting layer to obtain the photoelectric device.
A fifth aspect of the present application provides a display apparatus, including the above-described photovoltaic device, or including a photovoltaic device manufactured by the above-described method of manufacturing a photovoltaic device.
The application has the following beneficial effects:
according to the method, the film forming process of the film is improved, the electron transmission prefabricated layer is formed firstly, the second solvent is applied to the electron transmission prefabricated layer, the second solvent which is in orthogonal relation with the polarity of the first electron transmission material at the lower layer is utilized to rapidly take away the first solvent in the electron transmission prefabricated layer, the first solvent is removed at the moment when the crystallization of the first electron transmission material is completed but the growth does not occur, the crystal of the first electron transmission material at the lower layer is immediately stopped from growing, the purpose of controlling the cell size is achieved, the baking and drying process in the traditional film forming stage is abandoned, the crystal is prevented from excessively growing in the spin coating and baking stages, the gap between the cells of the obtained film is reduced, the film layer formed is compact, the roughness is reduced to below 0.8nm, the flatness of the film is higher, the current carrier is easy to migrate, and the electron transmission capability of the film is improved.
In addition, the upper layer second solvent is carried away from the lower layer first solvent, and the upper layer second solvent remains on the surface of the film layer of the film, but the polarity of the second solvent is in an orthogonal relationship with the polarity of the first electron transport material, so that the first electron transport material cannot be partially dissolved in the second solvent again, and the unit cell is enlarged; and the functional group in the second solvent at the upper layer can have an anchoring effect with oxygen vacancies at the interface, so that the surface defect of the film is filled, the probability of limiting carriers is lowered, and the electron transmission capability of the film is indirectly further 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 introduced 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 an AFM image of an electron transport layer of an optoelectronic device provided in example 1 of the present application;
FIG. 2 is an AFM image of an electron transport layer of an optoelectronic device provided in example 2 of the present application;
FIG. 3 is an AFM image of the electron transport layer of comparative example 1;
FIG. 4 is an AFM image of the electron transport layer of comparative example 2;
FIG. 5 is an AFM image of the electron transport layer of comparative example 3;
FIG. 6 is an AFM image of the electron transport layer of comparative example 4;
FIG. 7 is an AFM image of the electron transport layer of comparative example 5;
FIG. 8 is an AFM image of the electron transport layer of comparative example 6;
FIG. 9 is an AFM image of the electron transport layer of comparative example 7;
FIG. 10 is an AFM image of the electron transport layer of comparative example 8;
FIG. 11 is a schematic structural view of an optoelectronic device provided herein;
the label designation in fig. 11 is expressed as: an anode layer 10, a hole injection layer 11, a hole transport layer 12, a light emitting layer 13, an electron transport layer 14, and a cathode layer 15.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are within the scope of the protection of the present application, will be within the skill of the art without inventive effort.
The application provides a thin film and a preparation method thereof, an optoelectronic device and a preparation method thereof, and a display device, and the thin film and the preparation method thereof are respectively described in detail below. It should be noted that the following description order of the embodiments is not intended to limit the preferred order of the embodiments of the present application. In the following embodiments, the descriptions of the embodiments are focused on, and for the part that is not described in detail in a certain embodiment, reference may be made to the related descriptions of other embodiments.
The embodiment of the application provides a preparation method of a film, which comprises the following steps:
a load bearing interface is provided. The carrier interface may be a light emitting layer or a cathode layer of the optoelectronic device.
An electron transport pre-layer is formed on the support interface using a first solution comprising a first electron transport material and a first solvent.
A second solvent is applied to the surface of the electron transport pre-layer, which, when applied, carries the first solvent away from the electron transport pre-layer to obtain a thin film.
The first electron transport material is a polar first material, the first solvent is a polar solvent, the second solvent is a nonpolar solvent, or the first electron transport material is a nonpolar first material, the first solvent is a nonpolar solvent, and the second solvent is a polar solvent.
The term "polar" in the polar first material and the polar solvent means relatively polar, which may be weakly polar or strongly polar. The term "nonpolar" in the nonpolar first material and nonpolar solvent refers to being relatively nonpolar, which may be weakly polar or nonpolar. In some embodiments of the present application, the polar first material is a first electron transport material having a dielectric constant greater than 3; and/or the polar solvent is an organic solvent with a dielectric constant greater than 3; and/or the nonpolar first material is a first electron transport material having a dielectric constant less than 3; and/or the nonpolar solvent is an organic solvent having a dielectric constant less than 3.
The film forming process of the film is improved, an electron transmission prefabricated layer is formed firstly, a second solvent is applied to the electron transmission prefabricated layer, the second solvent which is in orthogonal relation with the polarity of a first electron transmission material at the lower layer is utilized to quickly take away the first solvent in the electron transmission prefabricated layer, the first solvent is removed at the moment when the crystallization of the first electron transmission material is completed but does not grow, the crystal of the first electron transmission material at the lower layer is immediately stopped from growing, the purpose of controlling the cell size is achieved, the baking and drying process in the traditional film forming stage is abandoned, the crystal is prevented from excessively growing in the spin coating and baking stages, the gap between the cells of the obtained film is reduced, the film layer formed is compact, the roughness is reduced to below 0.8nm, the flatness of the film is higher, the carriers are easy to migrate, and the electron transmission capability of the film is improved.
In addition, the upper layer second solvent is carried away from the lower layer first solvent, and the upper layer second solvent remains on the surface of the film layer of the film, but the polarity of the second solvent is in an orthogonal relationship with the polarity of the first electron transport material, so that the first electron transport material cannot be partially dissolved in the second solvent again, and the unit cell is enlarged; and the functional group in the second solvent at the upper layer can have an anchoring effect with oxygen vacancies at the interface, so that the surface defect of the film is filled, the probability of limiting carriers is lowered, and the electron transmission capability of the film is indirectly further improved.
In some embodiments of the present application, forming an electron transport pre-layer on a support interface with a first solution includes: depositing a first solution on a bearing interface in a first direction by a wet film making mode; the first direction may be a clockwise direction or a counter-clockwise direction.
Applying a second solvent to the electron transport pre-layer surface, comprising: a second solvent is deposited on the electron transport pre-formed layer in a second direction, wherein the second direction is opposite to the first direction, using a wet-process film. The second direction may be a counterclockwise direction or a clockwise direction.
In some embodiments of the present application, the first solution is deposited on the carrier interface in a first direction by wet-process film formation, wherein the deposition time is 10s to 15s, and the crystallization time of the first electron transport material is controlled by controlling the deposition time, so as to facilitate control of the unit cell size. The wet-process film forming method can comprise the following steps: spin coating, doctor blade, screen printing, spraying, ink jet printing, dip coating. When the spin coating mode is adopted, the spin coating process parameters are preferably as follows: the spin coating rotating speed is 3000 rpm-5000 rpm, which is favorable for the film formation of the first electron transport material.
And depositing a second solvent on the electron transport pre-fabricated layer in a second direction by a wet film forming mode, wherein the deposition time is 20-30 s. The wet-process film forming method can comprise the following steps: spin coating, doctor blade, screen printing, spray, ink jet printing, dip coating; most preferably, spin coating is used, and centrifugal force is used to rapidly spin out the upper layer second solvent and the lower layer first solvent, thereby facilitating control of the unit cell size. The spin coating process parameters are preferably as follows: the spin coating speed is 10000 rpm-12000 rpm, and the second solvent can be ensured not to form a film within the speed range, so that the second solvent on the upper layer can be quickly taken away from the first solvent on the lower layer.
In some embodiments of the present application, the concentration of the first solution is 35mg/mL to 40mg/mL. For example, the concentration of the first solution may be 35mg/mL, 36mg/mL, 37mg/mL, 38mg/mL, 39mg/mL, 40mg/mL, or the like. In this concentration range, film formation is facilitated, and film formation quality is improved, otherwise film formation is not facilitated.
In some embodiments of the present application, the volume ratio of the first solvent to the second solvent is (8-20): 1. for example, the volume ratio of the first solvent to the second solvent is 8: 1. 10: 1. 15:1 or 20:1, etc. If the volume ratio is too low, the second solvent is likely to form a film during application; if the volume ratio is too high, the second solvent is not easily carried away from the underlying first solvent.
In some embodiments of the present application, the polar first material is a metal oxide having a first ligand, wherein the first ligand is a first alkyl group comprising a first reactive group, wherein the first reactive group is any one of a hydroxyl group, a carboxyl group, an amine group, or an aldehyde group, and a carbon number of the first alkyl group of 0-18,0 indicates that the first reactive group is directly attached to the metal oxide; and/or the metal oxide is zinc oxide (ZnO), titanium dioxide (TiO 2 ) Barium titanate (BaTiO) 3 ) Any one of aluminum doped zinc oxide (AZO), lithium doped zinc oxide (LZO) or magnesium doped zinc oxide (MZO); and/or the polar solvent is any one of amide compounds, acid compounds, aldehyde compounds or alcohol compounds containing no more than four carbon atoms, wherein the amide compounds can be formamide or acetamide, the acid compounds can be acetic acid, propionic acid or butyric acid, the aldehyde compounds can be formaldehyde, acetaldehyde or butyraldehyde, and the alcohol compounds can be methanol. And/or the nonpolar solvent is any one of toluene, cyclohexane, carbon tetrachloride, trichloroethylene or chlorobenzene.
Of course, the polar first material in the present application is not limited to the metal oxide, but an organic compound may be used, but the organic compound as the polar first material is not advantageous for electron transport, and the above-described embodiment is not to be construed as limiting the present application.
In some embodiments of the present application, when the first reactive group is a hydroxyl group or an amine group, the number of carbon atoms of the first alkyl group is 0 to 18,0, which means that the first reactive group is directly connected to the metal oxide; and/or, when the first active group is carboxyl or aldehyde, the carbon number of the first alkyl group is 2-18.
In some embodiments of the present application, the non-polar first material is a metal oxide or organic compound having a second ligand, wherein the second ligand is a second alkyl group comprising a second reactive group, the second reactive group being any one of halogen or nitro, the second alkyl group having from 0 to 18,0 carbon atoms indicating that the second reactive group is directly attached to the metal oxide; and/or the metal oxide is any one of zinc oxide, titanium dioxide, barium titanate, aluminum-doped zinc oxide, lithium-doped zinc oxide or magnesium-doped zinc oxide; and/or the organic compound is any one or more than two of methyl C71-butyrate, carbon 60 or [6,6] -phenyl-C61-butyrate; and/or the nonpolar solvent is any one of toluene, cyclohexane, carbon tetrachloride, trichloroethylene or chlorobenzene; and/or the polar solvent is any one of amide compounds, acid compounds, aldehyde compounds or alcohol compounds containing no more than four carbon atoms, wherein the amide compounds can be formamide or acetamide, the acid compounds can be acetic acid, propionic acid or butyric acid, the aldehyde compounds can be formaldehyde, acetaldehyde or butyraldehyde, and the alcohol compounds can be methanol.
Accordingly, embodiments of the present application provide a film made by the method of making a film as described above. Embodiments of the present application also provide an optoelectronic device comprising: an anode layer, a light-emitting layer, an electron transport layer and a cathode layer of a laminated structure, wherein the electron transport layer is prepared by the preparation method of the thin film, or the electron transport layer is the thin film. The film can be applied to the preparation of an electron transport layer of a photoelectric device so as to improve the film forming quality of the electron transport layer and improve the electron transport capacity.
Accordingly, embodiments of the present application provide a method for manufacturing an optoelectronic device, including:
preparing a light emitting layer on an anode;
preparing a film on the light-emitting layer by adopting the preparation method of the film to obtain an electron transport layer; and
preparing a cathode on the electron transport layer to obtain a photoelectric device;
or preparing a film on the cathode by adopting the preparation method of the film to obtain an electron transport layer;
preparing a light emitting layer on the electron transport layer; and
and preparing an anode on the light-emitting layer to obtain the photoelectric device.
The embodiment of the application also provides a display device comprising the photoelectric device or the photoelectric device manufactured by the manufacturing method of the photoelectric device.
In some embodiments of the present application, there is provided an optoelectronic device, as shown with reference to fig. 11, comprising: the light-emitting device comprises an anode layer 10, a hole injection layer 11, a hole transport layer 12, a light-emitting layer 13, an electron transport layer 14 and a cathode layer 15, wherein the hole injection layer 11 is arranged on the anode layer 10, the hole transport layer 12 is arranged on the hole injection layer 11, the light-emitting layer 13 is arranged on the hole transport layer 12, the electron transport layer 14 is arranged on the light-emitting layer 13, and the cathode layer 15 is arranged on the electron transport layer 14. The electron transport layer 14 is the thin film described above.
In other embodiments, the anode layer may be made of a material selected from, but not limited to: indium doped tin oxide (ITO). The hole injection layer material may be selected from but not limited to: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) and s-MoO incorporated therein 3 Derivatives of (PEDOT: PSS: s-MoO) 3 ) One of them. The hole transport layer material may be selected from but not limited to: poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4, 4' - (N- (p-butylphenyl)) diphenylamine)]One of (TFB), poly (9-vinylcarbazole) (PVK), poly-TPD, NPB. The quantum dot material of the light emitting layer may be selected from but not limited to: II-VI (CdSe, cdS, znSe, cdS, pbS, pbSe) semiconductor nanocrystals and one or more of their core-shell structures. The cathode layer may be made of a material selected from, but not limited to: al or Ag.
The surface roughness of the electron transport layer of the photoelectric device is reduced to below 1 nm; the external quantum efficiency is improved to 8% -10%. The whole device tends to be balanced, and the external quantum efficiency is improved.
Further, the above-described photovoltaic device may be prepared by a method comprising the steps of:
s1, sequentially depositing a hole injection layer, a hole transport layer and a light emitting layer on the surface of an anode substrate from bottom to top.
S2, preparing an electron transport layer on the light emitting layer, comprising:
spin-coating a first solution on the light-emitting layer in a clockwise direction to form an electron transport pre-fabricated layer, wherein the first solution comprises a first electron transport material and a first solvent, the first electron transport material is a polar first material, and the first solvent is a polar solvent; the spin coating can be performed by the following process parameters: the spin coating time is 10 s-15 s; the spin coating rotation speed is 3000 rpm-5000 rpm.
Spin-coating a non-polar solvent on the electron transport pre-layer in a counter-clockwise direction, the non-polar solvent, when applied, carrying the polar solvent away from the electron transport pre-layer, removing the polar solvent from the electron transport pre-layer to obtain the electron transport layer, wherein the spin-coating may employ the following process parameters: the spin coating time is 20 s-30 s, and the spin coating rotating speed is 10000 rpm-12000 rpm.
And S3, forming a cathode on the electron transport layer, and packaging to obtain the photoelectric device.
Further, the above-mentioned photovoltaic device may also be prepared by a method comprising the steps of:
s1, sequentially depositing a hole injection layer, a hole transport layer and a light emitting layer on the surface of an anode substrate from bottom to top.
S2, preparing an electron transport layer on the light emitting layer, comprising:
spin-coating a first solution on the light-emitting layer in a counterclockwise direction to form an electron transport pre-fabricated layer, wherein the first solution comprises a nonpolar first material and a nonpolar solvent, and the spin-coating can adopt the following technological parameters: the spin coating time is 10 s-15 s; the spin coating rotation speed is 3000 rpm-5000 rpm.
And spin-coating a polar solvent on the electron transport pre-fabricated layer in a clockwise direction, wherein the polar solvent brings the nonpolar solvent away from the electron transport pre-fabricated layer when the polar solvent is applied, and the nonpolar solvent in the electron transport pre-fabricated layer is removed to obtain the electron transport layer, wherein the spin-coating time is 20 s-30 s, and the spin-coating rotating speed is 10000 rpm-12000 rpm.
And S3, forming a cathode on the electron transport layer, and packaging to obtain the photoelectric device.
The following describes the improvement of the crystalline state of the electron transport layer of the present application with reference to specific examples and comparative examples. The devices were uniformly prepared and external quantum efficiency performance values of the devices of each example, comparative example were calculated using JVL test equipment (current voltage brightness) after the end of the preparation, wherein the electrical performance data monitoring was selected on the first day after the end of the device preparation. The same processing mode of each device is used for preparing an electron transport layer by AFM (atomic force microscope) and calculating Rq roughness to verify the film forming quality.
Example 1
The embodiment provides a method for manufacturing an optoelectronic device, which comprises the following steps:
s11, spin-coating a layer of PEDOT (polyether-ether-ketone) PSS (polyether-ether-ketone) S-MoO on the ITO substrate 3 The hole injection layer is annealed in air.
S12, spin-coating a 30nm PVK hole transport layer on the hole injection layer in a nitrogen atmosphere and annealing at 140 ℃.
S13, spin coating a 30nm CdSe/ZnS luminescent layer on the hole transport layer.
S14, spin-coating a first solution with the concentration of 35mg/mL on the CdSe/ZnS light-emitting layer in a clockwise direction to form an electron transport pre-fabricated layer, wherein the first solution comprises: aluminum-doped zinc oxide and acetic acid solvent which are mainly hydroxyl ligands; the spin coating process parameters were spin coating time of 10s and spin coating speed of 4000rpm.
S15, performing spin coating in a anticlockwise direction for 20S after the spin coating is performed for 10S in S14, and spin-coating a toluene solvent (the volume ratio of the acetic acid solvent to the toluene solvent is 15:1) on the electron transport pre-fabricated layer, wherein the toluene solvent is used for carrying away the acetic acid solvent from the electron transport pre-fabricated layer during the spin coating so as to obtain an electron transport layer; the spin coating process parameter is spin coating time of 20s and spin coating rotation speed of 10000rpm.
S16, evaporating a 105nm Ag electrode on the electron transport layer.
S17, packaging to obtain the photoelectric device.
As can be seen from fig. 1, the electron transport layer forms a flat, dense film with a roughness of 0.36nm; from the AFM image, the unit cell size of the first electron transport material stopped growing at 4nm-5nm, and the gap between unit cells was small. Whereas comparative example 1 adopts a conventional scheme (without using the method for preparing an electron transport layer provided herein), the first electron transport material has a unit cell size as long as 7nm or more after spin coating is completed.
The external quantum efficiency was 9.84% by test. Compared with comparative examples 1-8, the surface roughness of the electron transport layer is reduced, the film forming quality is better, and the external quantum efficiency is obviously improved.
Example 2
The embodiment provides a method for manufacturing an optoelectronic device, which comprises the following steps:
s21, spin-coating a layer of PEDOT: PSS: S-MoO on the ITO substrate 3 The hole injection layer is annealed in air.
S22, spin-coating a 30nm PVK hole transport layer on the hole injection layer in a nitrogen atmosphere and annealing at 140 ℃.
S23, spin coating a 30nm CdSe/ZnS luminescent layer on the hole transport layer.
S24, spin-coating a first solution with a concentration of 40mg/mL on the CdSe/ZnS light-emitting layer in a clockwise direction to form an electron transport pre-fabricated layer, wherein the first solution comprises carbon 60 and cyclohexane solvent, spin-coating process parameters are spin-coating time of 15S and spin-coating rotating speed of 3000rpm.
S25, performing anticlockwise spin coating for 30S after 15S in S24, and spin-coating a formamide solvent (the volume ratio of the cyclohexane solvent to the formamide solvent is 13:1) on the electron transport pre-fabricated layer, wherein the formamide solvent is used for carrying the cyclohexane solvent away from the electron transport pre-fabricated layer during spin coating so as to obtain an electron transport layer; the spin coating process parameters were spin coating time of 30s and spin coating speed of 12000rpm.
S26, evaporating a 105nm Ag electrode on the electron transport layer.
S27, packaging to obtain the photoelectric device.
As can be seen from fig. 2, the electron transport layer forms a flat, dense film with a roughness of 0.32nm; from the AFM image, the growth of the carbon 60 nonpolar first material unit cell size stops at 4nm-5nm, and the gap between unit cells is small. As in comparative example 1, the unit cell length was as long as 7nm or more after the spin coating was completed, using a conventional scheme.
The external quantum efficiency was tested to be 8.99%.
Compared with comparative examples 1-8, the surface roughness of the electron transport layer is reduced, the film forming quality is better, and the external quantum efficiency is obviously improved.
Comparative example 1
There is provided a conventional standard device preparation, i.e., in example 1, step S15 of example 1 is removed, and the spin-coating time 10S in S14 is replaced with 30S, and the remaining steps are the same as in example 1.
As can be seen in FIG. 3, larger particles are agglomerated, indicating a larger cell size, above about 7nm, and a clear boundary for each cell, indicating a larger cell-to-cell gap. The roughness of the electron transport layer was 1.19nm.
The external quantum efficiency was tested to be 6.51%.
This demonstrates that the electron transport layer obtained in comparative example 1 has inferior film formation quality, lower flatness, high surface roughness, and low external quantum efficiency, as compared with example 1.
Comparative example 2
There is provided a production of an optoelectronic device, namely, in example 1, the spin-coating time 10S of step S14 of example 1 is replaced with 5S, the spin-coating time 20S of step S15 is replaced with 25S, and the other steps are the same as those of example 1.
As can be seen from fig. 4, the first electron transport material is not film-formed. The roughness was 2.08nm.
The external quantum efficiency was 3.75% by test.
This demonstrates that the polar first material has not formed a film, i.e. is washed away by the upper solvent, resulting in a crystallization time that is too short and the unit cell stops growing when the unit cell size is too small. Compared to example 1, the roughness was higher and the external quantum efficiency was lower.
Comparative example 3
There is provided a production of an optoelectronic device, namely, in example 1, the spin-coating solvent toluene of step S15 of example 1 is replaced with acetic acid, and the other steps are the same as in example 1.
As can be seen from fig. 5, no crystals are formed. The roughness was 5.94nm.
The external quantum efficiency was tested to be 0.49%.
Thus, the polar solvent of the same polarity is reversely spin-coated on the polar first material, and the polar first material is dissolved in the polar solvent, so that the polar first material is washed away by the polar solvent. The external quantum efficiency is only 0.49%, the electron mobility is very low, and the electron transmission is not facilitated.
Comparative example 4
There is provided a production of an optoelectronic device, namely, in example 1, the spin-coating direction is changed to the clockwise direction in step S15 of example 1, and the other steps are the same as those of example 1.
As can be seen in fig. 6, larger particles are agglomerated, indicating a larger cell size, and each cell boundary is clear, indicating a larger cell-to-cell gap. The roughness was 1.72nm.
The external quantum efficiency was tested to be 6.62%.
Therefore, the upper polar solvent does not carry out reverse spin coating, the effect of improving the crystallization condition of the first electron transport material is poor, the film forming evenness is low, and the film forming quality is poor. Compared with example 1, the roughness was higher and the external quantum efficiency was lower.
Comparative example 5
An optoelectronic device was prepared by replacing the volume ratio of acetic acid solvent to toluene solvent of step S15 of example 1 with 5:1 in example 1, and the remaining steps were the same as in example 1.
As can be seen from FIG. 7, the film was formed after spin-coating with toluene solvent. The roughness was 2.91nm.
The external quantum efficiency was tested to be 2.42%.
This demonstrates that too high a volume of the upper polar solvent can result in the formation of a film from the toluene solvent during spin coating. Compared with example 1, the external quantum efficiency is lower, the electron mobility is very low, and the electron transport is not favored.
Comparative example 6
An optoelectronic device was prepared by replacing the volume ratio of acetic acid solvent to toluene solvent of step S15 of example 1 with 40:1 in example 1, and the remaining steps were the same as in example 1.
As can be seen in fig. 8, larger particles are agglomerated, indicating a larger cell size, and each cell boundary is clear, indicating a larger cell-to-cell gap; the roughness was 1.35nm.
The external quantum efficiency was tested to be 7.31%.
This demonstrates that the crystalline state improvement effect on the first electron transport material is poor when the volume of the reverse spin-coated upper toluene solvent is low. Compared with the present example 1, the roughness was higher and the external quantum efficiency was lower.
Comparative example 7
There is provided a production of an optoelectronic device, namely, in example 1, the rotational speed 10000rpm of toluene in step S15 of example 1 is changed to 5000rpm, and the other steps are the same as in example 1.
As can be seen from FIG. 9, the film was formed after spin-coating with toluene solvent. The roughness was 2.66nm.
The external quantum efficiency was tested to be 1.83%.
It can be seen that when the spin speed of the upper toluene solvent is too low, the toluene solvent is caused to form a film during the spin coating. Compared with example 1, the external quantum efficiency is lower, the electron mobility is very low, and the electron transport is not favored.
Comparative example 8
This example provides a preparation of an optoelectronic device, namely in example 1, the rotational speed of toluene is changed to 20000rpm in step S15 of this example, and the other steps are the same as in example 1.
As can be seen in FIG. 10, the larger agglomerated particles show a larger cell size and the boundaries of each cell are clear, indicating a larger cell-to-cell gap. The roughness was 1.44nm.
The external quantum efficiency was tested to be 7.1%.
From this, it can be seen that when the rotational speed of the upper toluene solvent of the reverse spin coating is too high, the toluene solvent of the upper layer cannot be taken away from the acetic acid solvent of the lower layer, and thus the effect of improving the crystalline state of the first electron transport material is poor. Compared with example 1, the roughness was higher and the external quantum efficiency was lower.
In summary, it can be demonstrated by comparing the present examples 1-2 with comparative examples 1-8 that the purpose of controlling the unit cell size is achieved by improving the thin film forming process, the crystalline state of the first electron transport material is improved, the surface roughness is reduced, the film forming quality of the electron transport layer is improved, and the external quantum efficiency is improved, thereby improving the electron transport capability of the electron transport layer.
The foregoing has outlined rather broadly the more detailed description of the present application, wherein specific examples have been provided to illustrate the principles and embodiments of the present application, the description of the examples being provided solely to assist in the understanding of the method of the present application and the core concepts thereof; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.

Claims (14)

1. The preparation method of the film is characterized by comprising the following steps:
providing a bearing interface;
forming an electron transport pre-layer on the support interface with a first solution comprising a first electron transport material and a first solvent;
applying a second solvent to the surface of the electron transport pre-layer to obtain a thin film;
the first electron transport material is a polar first material, the first solvent is a polar solvent, and the second solvent is a nonpolar solvent; alternatively, the first electron transport material is a nonpolar first material, the first solvent is a nonpolar solvent, and the second solvent is a polar solvent.
2. The method of preparing a thin film according to claim 1, wherein forming an electron transport pre-layer on the support interface using the first solution comprises: depositing the first solution on the bearing interface in a first direction by a wet film making mode;
the applying a second solvent to the electron transport pre-layer surface comprises: and depositing the second solvent on the electron transport pre-fabricated layer in a second direction by a wet film forming method, wherein the second direction is opposite to the first direction.
3. The method for preparing a thin film according to claim 2, wherein the first solution is deposited on the carrying interface in a first direction by a wet film forming method, wherein the deposition time is 10s to 15s; and/or
And depositing the second solvent on the electron transport pre-fabricated layer in a second direction in a wet film forming mode, wherein the deposition time is 20-30 s.
4. The method of claim 2, wherein the first solution is deposited on the support interface in a first direction by a wet-process film process, wherein the wet-process film process comprises: spin coating, doctor blade, screen printing, spray, ink jet printing, dip coating; and/or
The method for preparing the film by wet method is characterized in that the second solvent is deposited on the electron transport pre-fabricated layer in a second direction, wherein the method for preparing the film by wet method comprises the following steps: spin coating, doctor blade, screen printing, spraying, ink jet printing, dip coating.
5. The method according to claim 4, wherein the first solution is deposited on the carrier interface in a first direction by wet film forming, and wherein spin coating is performed by the following spin coating process parameters: the spin coating rotating speed is 3000 rpm-5000 rpm; and/or
The second solvent is deposited on the electron transport preformed layer in a second direction in a wet film forming mode, wherein when spin coating is adopted, spin coating process parameters are as follows: the spin coating rotational speed is 10000 rpm-12000 rpm.
6. The method of producing a film according to any one of claims 1 to 5, wherein the concentration of the first solution is 35mg/mL to 40mg/mL; and/or
The volume ratio of the first solvent to the second solvent is (8-20): 1.
7. the method for producing a film according to any one of claim 1 to 5, wherein,
the polar first material is a first electron transport material with a dielectric constant greater than 3; and/or
The polar solvent is an organic solvent with a dielectric constant greater than 3; and/or
The nonpolar first material is a first electron transport material with a dielectric constant less than 3; and/or
The nonpolar solvent is an organic solvent having a dielectric constant of less than 3.
8. The method of any one of claims 1-5, wherein the polar first material is a metal oxide having a first ligand, wherein the first ligand is a first alkyl group comprising a first reactive group, wherein the first reactive group is any one of a hydroxyl group, a carboxyl group, an amine group, or an aldehyde group, and wherein a carbon number of the first alkyl group of 0-18,0 indicates that the first reactive group is directly attached to the metal oxide; and/or the metal oxide is any one of zinc oxide, titanium dioxide, barium titanate, aluminum-doped zinc oxide, lithium-doped zinc oxide or magnesium-doped zinc oxide; and/or
The polar solvent is any one of an amide compound, an acid compound, an aldehyde compound or an alcohol compound containing no more than four carbon atoms; and/or
The nonpolar solvent is any one of toluene, cyclohexane, carbon tetrachloride, trichloroethylene or chlorobenzene.
9. The method according to claim 8, wherein when the first active group is a hydroxyl group or an amine group, the first alkyl group has 0 to 18 carbon atoms; and/or
When the first active group is carboxyl or aldehyde, the carbon number of the first alkyl group is 2-18.
10. The method of any one of claims 1 to 5, wherein the nonpolar first material is a metal oxide or an organic compound having a second ligand, wherein the second ligand is a second alkyl group including a second active group, the second active group is any one of halogen or nitro, and a carbon number of the second alkyl group is 0 to 18,0, which means that the second active group is directly connected to the metal oxide; and/or the metal oxide is any one of zinc oxide, titanium dioxide, barium titanate, aluminum-doped zinc oxide, lithium-doped zinc oxide or magnesium-doped zinc oxide; and/or the organic compound is any one or more than two of methyl C71-butyrate, carbon 60 or [6,6] -phenyl-C61-butyrate; and/or
The nonpolar solvent is any one of toluene, cyclohexane, carbon tetrachloride, trichloroethylene or chlorobenzene; and/or
The polar solvent is any one of an amide compound, an acid compound, an aldehyde compound or an alcohol compound containing no more than four carbon atoms.
11. A film produced by the method of producing a film according to any one of claims 1 to 10.
12. An optoelectronic device, comprising: an anode layer, a light-emitting layer, an electron transport layer and a cathode layer of a laminated structure, wherein the electron transport layer is produced by the method for producing a film according to any one of claims 1 to 10, or the electron transport layer is a film according to claim 11.
13. A method of fabricating an optoelectronic device, comprising:
preparing a light emitting layer on an anode;
preparing a thin film on the light-emitting layer by the thin film preparation method according to any one of claims 1 to 10, to obtain an electron transport layer; and
preparing a cathode on the electron transport layer to obtain a photoelectric device;
alternatively, a thin film is prepared on a cathode by the thin film preparation method according to any one of claims 1 to 10, to obtain an electron transport layer;
preparing a light emitting layer on the electron transport layer; and
and preparing an anode on the light-emitting layer to obtain the photoelectric device.
14. A display apparatus comprising the photovoltaic device according to claim 12 or comprising the photovoltaic device produced by the production method of the photovoltaic device according to claim 13.
CN202111616627.6A 2021-12-27 2021-12-27 Film, preparation method thereof, photoelectric device and display device Pending CN116367584A (en)

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