WO2023041046A1 - Photoelectric device and manufacturing method therefor, and display device - Google Patents

Abstract

The present application discloses a photoelectric device and a manufacturing method therefor, and a display device. The photoelectric device comprises an anode, a light-emitting layer, an electron transport layer, and a cathode which are stacked; the material of the electron transport layer comprises a ZnO particle and a metal phthalocyanine complex attached to the surface of the ZnO particle. The electron transport layer of the photoelectric device has high electron transport efficiency, and it is beneficial to electron-hole injection balance of the photoelectric device, thereby improving the luminous efficiency of the photoelectric device and reducing the turn-on voltage of the photoelectric device.

Description

A kind of photoelectric device and its preparation method, display device

This application claims the priority of the Chinese patent application with the application number 202111112237.5 and the application title "An optoelectronic device and its preparation method and display device" filed at the China Patent Office on September 18, 2021, the entire content of which is passed References are incorporated in this application.

technical field

The present application relates to the field of display technology, in particular to an optoelectronic device, a manufacturing method thereof, and a display device.

Background technique

Optoelectronic devices refer to devices made according to the photoelectric effect, which have a wide range of applications in new energy, sensing, communication, display, lighting and other fields, such as solar cells, photodetectors, organic electroluminescent devices (OLED) or quantum dots Electroluminescent devices (QLEDs).

The structure of a traditional photoelectric device mainly includes an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer (ie, an electron transport layer), an electron injection layer, and a cathode. Under the action of the electric field, the holes generated by the anode of the photoelectric device and the electrons generated by the cathode move, inject into the hole transport layer and the electron transport layer respectively, and finally migrate to the light-emitting layer. When the two meet in the light-emitting layer, a Energy excitons, which excite light-emitting molecules and eventually produce visible light.

ZnO is an n-type semiconductor material with a direct bandgap. It has a wide band gap of 3.37eV and a low work function of 3.7eV. It has the advantages of good stability, high transparency, safety and non-toxicity, making ZnO an ideal choice for preparing optoelectronic devices. The main material of the electron transport layer. In addition, ZnO also has many potential advantages. For example, the exciton binding energy of ZnO is as high as 60meV, which is much higher than other wide-bandgap semiconductor materials (for example, the exciton binding energy of GaN is 2meV), and the exciton binding energy of ZnO is 2meV. The energy is 2.3 times that of the thermal energy (26meV) at room temperature, so the excitons of ZnO can exist stably at room temperature. In addition, ZnO nanomaterials also have the advantages of high electron mobility, simple preparation, and low cost, and are widely used in optoelectronic devices.

technical problem

Existing optoelectronic devices including ZnO electron transport layer have low luminous efficiency and high turn-on voltage, which affect the use of optoelectronic devices to a certain extent.

technical solution

Therefore, the present application provides an optoelectronic device, a manufacturing method thereof, and a display device.

The present application provides a photoelectric device, comprising a laminated anode, a light-emitting layer, an electron transport layer and a cathode, wherein the material of the electron transport layer includes ZnO particles and metal phthalocyanine complexes connected on the surface of the ZnO particles.

Optionally, the metal phthalocyanine complex is selected from one or more of zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine and copper phthalocyanine.

Optionally, in the material of the electron transport layer, the molar ratio of the metal phthalocyanine complex to the ZnO particles is in the range of 1:(0.01-0.2).

Optionally, the metal phthalocyanine complex is a fluorinated metal phthalocyanine complex.

Optionally, the fluorinated metal phthalocyanine complex is selected from one or more of fluorinated zinc phthalocyanine, fluorinated magnesium phthalocyanine, fluorinated cobalt phthalocyanine, fluorinated silver phthalocyanine and fluorinated copper phthalocyanine kind.

Optionally, the average particle diameter of the ZnO particles is in the range of 10-100 nm.

Optionally, the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and the material of the organic light-emitting layer is selected from diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, One or more of TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, the material of the quantum dot light-emitting layer is selected from one or more of single-structure quantum dots and core-shell structure quantum dots , the single-structure quantum dots are selected from one or more of II-VI group compounds, III-V group compounds and I-III-VI group compounds, and the II-VI group compounds are selected from CdSe, CdS, CdTe , ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe one or more, the III-V compound is selected from InP , InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP one or more, the I-III-VI compound is selected from CuInS ₂ , CuInSe ₂ and AgInS ₂ One or more, the core of the quantum dot with the core-shell structure is selected from one or more of the above-mentioned single-structure quantum dots, and the shell material of the quantum dot with the core-shell structure is selected from CdS, CdTe, One or more of CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS.

Optionally, the photoelectric device further includes a hole transport layer, and the hole transport layer is located between the anode and the light emitting layer.

Optionally, the material of the hole transport layer is selected from poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetra [N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline ], N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-diphenyl-4,4'-diamine, 4,4'-bis(N- carbazole)-1,1'-biphenyl, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl )) diphenylamine)], poly(9-vinylcarbazole), polytriphenylamine, PEDOT:PSS and 4,4',4"-tri(carbazol-9-yl) triphenylamine or one or more kind.

Correspondingly, the present application also provides a method for preparing a photoelectric device, comprising the following steps:

providing a first electrode;

forming a light emitting layer, the light emitting layer being formed on the first electrode;

forming a second electrode, the second electrode being formed on the light emitting layer;

The preparation method also includes: providing zinc salt, alkali and solvent, mixing to obtain a ZnO precursor solution, mixing the ZnO precursor solution with a metal phthalocyanine complex to obtain a material for an electron transport layer, and depositing the electron transport layer layer materials to obtain an electron transport layer, and the electron transport layer and the light emitting layer are stacked between the first electrode and the second electrode.

Optionally, the first electrode is an anode, the second electrode is a cathode, and the deposition of the material of the electron transport layer is performed between the formation of the light-emitting layer and the formation of the second electrode, and includes: The material of the electron transport layer is deposited on the light emitting layer.

Optionally, the first electrode is a cathode, and the second electrode is an anode, and the depositing the material of the electron transport layer is performed before the formation of the light-emitting layer, and includes: depositing on the first electrode The material of the electron transport layer.

Optionally, the zinc salt is selected from one or more of zinc acetate, zinc nitrate, zinc chloride and zinc acetate dihydrate.

Optionally, the alkali is selected from one or more of sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide, and the solvent is selected from one or more of methanol, ethanol and butanol.

Optionally, the molar ratio of OH ^- in the base to Zn ²⁺ in the zinc salt ranges from (1.5-3):1.

Optionally, the molar ratio of Zn ²⁺ in the ZnO precursor solution to the metal phthalocyanine complex ranges from 1:(0.01-0.2).

Optionally, the pH range of the ZnO precursor solution is 12-14.

Optionally, the metal phthalocyanine complex is selected from one or more of zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine and copper phthalocyanine.

Optionally, the metal phthalocyanine complex is a fluorinated metal phthalocyanine complex, and the fluorinated metal phthalocyanine complex is selected from fluorinated zinc phthalocyanine, fluorinated magnesium phthalocyanine, fluorinated cobalt phthalocyanine, fluorine One or more of silver phthalocyanine and fluorinated copper phthalocyanine.

Optionally, after the mixing, a step of stirring at 60-120° C. is also included.

Correspondingly, the present application also provides a display device, which includes the above-mentioned optoelectronic device.

Beneficial effect

The material of the electron transport layer of the optoelectronic device of the present application includes ZnO nanomaterials modified by metal phthalocyanine complexes, through the coordination effect of metal phthalocyanine, the Fermi energy level of ZnO is moved up into the conduction band, and the surface of ZnO is connected with M (Pc)-O-Zn bond and Zn-N(Pc) bond, and the M(Pc)-O-Zn bond and Zn-N(Pc) bond are composed of the 3d orbital and the subsurface Zn atom of ZnO The 2p orbital of the surface O atoms, so that the surface of ZnO is metallized, and ZnO presents a metallic state, thereby improving the conductivity of ZnO nanomaterials, promoting the electron transport of ZnO nanomaterials, and improving the electron transport efficiency of the electron transport layer. It is beneficial to the electron-hole injection balance of the photoelectric device, thereby improving the luminous efficiency of the photoelectric device and reducing the turn-on voltage of the photoelectric device.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.

Fig. 1 is a schematic structural diagram of an optoelectronic device provided by an embodiment of the present application;

Fig. 2 is a schematic structural diagram of another optoelectronic device provided by the embodiment of the present application;

Fig. 3 is a flow chart of a method for preparing an optoelectronic device provided in an embodiment of the present application;

Fig. 4 is a flow chart of another method for preparing an optoelectronic device provided in an embodiment of the present application.

Embodiment of this application

The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application.

The embodiment of the present application provides a photoelectric device and a preparation method thereof. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to".

In this application, expressions such as "one or more" refer to one or more of the listed items, and "multiple" refers to any combination of two or more of these items, including single items (species) ) or any combination of plural items (species), for example, "at least one (species) of a, b, or c" or "at least one (species) of a, b, and c" can mean: a ,b,c,a-b (that is, a and b),a-c,b-c, or a-b-c, where a,b,c can be single or multiple.

Various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the application; therefore, the described range should be regarded as The description has specifically disclosed all possible subranges as well as individual values within that range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, 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., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.

Referring to FIG. 1 , an embodiment of the present application provides an optoelectronic device 100 , and the optoelectronic device 100 may be a solar cell, a photodetector, an organic electroluminescent device (OLED) or a quantum dot electroluminescent device (QLED). The optoelectronic device 100 includes an anode 10 , a light emitting layer 20 , an electron transport layer 30 and a cathode 40 stacked in sequence.

The material of the electron transport layer 30 includes ZnO nanomaterials modified by metal phthalocyanine complexes, that is, MPc-ZnO, wherein M is metal and Pc is phthalocyanine. In other words, the material of the electron transport layer 30 includes ZnO nanomaterials and metal phthalocyanine complexes connected on the surface of the ZnO nanomaterials.

The metal phthalocyanine complex may be selected from, but not limited to, one or more of zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine and copper phthalocyanine.

The ZnO nanomaterials are ZnO nanomaterials known in the art to be used for electron transport layers. In one embodiment, the particle diameter of the ZnO nanomaterial is ZnO nanoparticles in the range of 10-100 nm. If the particle size of the ZnO nanoparticles is too small, there will be more surface defects on the ZnO surface, which will affect the electron transport performance of the electron transport layer 30; The film uniformity, in turn, affects the electron transport performance of the electron transport layer 30 .

The ZnO nanomaterial modified by the metal phthalocyanine complex moves the Fermi energy level of ZnO upwards and enters the conduction band through the coordination effect of metal phthalocyanine, so that the surface of ZnO is connected with M(Pc)-O-Zn bonds and Zn -N(Pc) bond, and the M(Pc)-O-Zn bond and Zn-N(Pc) bond are composed of the 3d orbital of the ZnO surface and the subsurface Zn atom and the 2p orbital of the surface O atom, thus Metallize the surface of ZnO so that ZnO presents a metallic state, thereby improving the conductivity of ZnO nanomaterials, promoting the electron transport of ZnO nanomaterials, and improving the electron transport efficiency of the electron transport layer 30, which is conducive to including the electron transport layer 30. The electron-hole injection of the optoelectronic device 100 is balanced, thereby improving the luminous efficiency of the optoelectronic device 100 and reducing the turn-on voltage of the optoelectronic device 100 .

In the ZnO nanomaterial modified by the metal phthalocyanine complex, that is, in the material of the electron transport layer 30, the molar ratio of the metal phthalocyanine complex to the ZnO nano material is in the range of 1:(0.01- 0.2). If the content of the metal phthalocyanine complex is too low, it is difficult to improve the electron transport efficiency of the electron transport layer 30; if the content of the metal phthalocyanine complex is too high, the charge transport performance of the electron transport layer 30 will be reduced.

In one embodiment, the metal phthalocyanine complex is a fluorinated metal phthalocyanine complex, namely F-MPc-ZnO. The fluorinated metal phthalocyanine complex can be selected from but not limited to one or more of fluorinated zinc phthalocyanine, fluorinated magnesium phthalocyanine, fluorinated cobalt phthalocyanine, fluorinated silver phthalocyanine and fluorinated copper phthalocyanine kind.

The fluorinated metal phthalocyanine complex uses fluorine atoms or fluorine-containing groups to chemically modify the benzene ring in the metal phthalocyanine complex, and utilizes the electron-withdrawing effect of the fluorine atoms to reduce The electron cloud density makes it easier for the central metal atom of the metal phthalocyanine complex to combine with the oxygen vacancies on the ZnO surface to induce electron localization through coordination, thereby enhancing the metallicity of the ZnO surface, reducing the work function of ZnO, and making ZnO The work function of is more matched with the work function of the cathode, so that the electron transport layer 30 has good conductivity. In this way, an ohmic contact can be formed by evaporating an electrode on the electron transport layer 30 comprising the ZnO nanomaterial modified by the metal phthalocyanine complex, thereby effectively improving the electron injection of the optoelectronic device 100.

In addition, the N atoms on the metal phthalocyanine complex coordinate with the Zn dangling bonds in ZnO, the metal atoms on the metal phthalocyanine complex coordinate with the oxygen vacancies in ZnO, and the introduction of fluorine can enhance the The solubility in the solvent can passivate the surface defects of ZnO, reduce the capture of electrons by ZnO, and thus promote the effective injection of electrons into the light-emitting layer of the optoelectronic device 100 .

Furthermore, the fluorine-containing groups act as ligands to modify the metal phthalocyanine complex, which can reduce the surface roughness of the ZnO film, improve the contact interface between ZnO and the cathode, and synergistically improve the electron injection efficiency. This is beneficial to the electron-hole injection balance of the optoelectronic device 100 including the electron transport layer 30 , thereby improving the luminous efficiency of the optoelectronic device 100 and reducing the turn-on voltage of the optoelectronic device 100 .

In one embodiment, the material of the electron transport layer is the ZnO nanomaterial modified by the metal phthalocyanine complex.

The material of the electron transport layer may also include nano-metal oxides or doped nano-metal oxides. Nano-metal oxides include but are not limited to ZnO, TiO ₂ , SnO ₂ , Ta ₂ O ₃ , ZrO ₂ , NiO, One or more of TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO and InSnO, the doping element in the doped nano metal oxide is one or more of magnesium, aluminum, gallium, lithium, indium, tin and molybdenum Various. In one embodiment, the material of the electron transport layer is composed of the ZnO nanomaterial modified by the metal phthalocyanine complex and the nano metal oxide or doped nano metal oxide.

The material of the anode 10 is known in the art for anode materials, for example, can be selected from but not limited to doped metal oxide electrodes, composite electrodes and the like. The doped metal oxide electrode may be selected from but not limited to indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO), One or more of gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO) and aluminum-doped magnesium oxide (AMO). The composite electrode is a composite electrode with a metal sandwiched between doped or non-doped transparent metal oxides, such as 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, etc. Wherein, "/" means a laminated layer, for example, AZO/Ag/AZO means a composite electrode formed by sequentially stacking AZO, Ag, and AZO.

The light emitting layer 20 can be an organic light emitting layer or a quantum dot light emitting layer. When the light emitting layer 20 is an organic light emitting layer, the optoelectronic device 100 may be an organic electroluminescent device. When the light emitting layer 20 is a quantum dot light emitting layer, the optoelectronic device 100 may be a quantum dot electroluminescent device.

The material of the organic light-emitting layer is a material known in the art to use an organic light-emitting layer, for example, it can be selected from but not limited to diaryl anthracene derivatives, distyryl aromatic derivatives, pyrene derivatives or fluorene derivatives, One or more of TBPe fluorescent material emitting blue light, TTPA fluorescent material emitting green light, TBRb fluorescent material emitting orange light, and DBP fluorescent material emitting red light.

The material of the quantum dot light-emitting layer is a quantum dot material known in the art for the quantum dot light-emitting layer of an optoelectronic device, for example, it can be selected from but not limited to one or more of a single-structure quantum dot and a core-shell structure quantum dot Various. The single-structure quantum dots may be selected from, but not limited to, one or more of II-VI compounds, III-V compounds and I-III-VI compounds. As an example, the II-VI group compound can be selected from but not limited to CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, One or more of CdZnSeTe and CdZnSTe; the III-V compound can be selected from but not limited to one of InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP one or more; the I-III-VI compound may be selected from but not limited to one or more of CuInS ₂ , CuInSe ₂ and AgInS ₂ . The core of the quantum dot of the core-shell structure can be selected from one or more of the above-mentioned single-structure quantum dots, and the shell material of the quantum dot of the core-shell structure can be selected from but not limited to CdS, CdTe, CdSeTe, One or more of CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS, and ZnS. As an example, the quantum dots of the core-shell structure can be selected from but not limited to CdZnSe/CdZnS/ZnS, CdZnSe/ZnSe/ZnS, CdSe/ZnS, CdSe/ZnSe/ZnS, ZnSe/ZnS, ZnSeTe/ZnS, CdSe/CdZnSeS One or more of ZnS, InP/ZnSe/ZnS and InP/ZnSeS/ZnS.

The cathode 40 is a cathode known in the art for electroluminescent devices, for example, may be selected from but not limited to one or more of Ag electrodes, Al electrodes, Au electrodes, Pt electrodes or alloy electrodes.

Please refer to FIG. 2 , in one embodiment, the photoelectric device 100 further includes a hole transport layer 50 , and the hole transport layer 50 is located between the anode 10 and the light emitting layer 20 .

The material of the hole transport layer 50 can also be a material known in the art for the hole transport layer, for example, can be selected from but not limited to poly[bis(4-phenyl)(2,4,6-tri Methylphenyl)amine] (PTAA), 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro -omeTAD), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline](TAPC), N,N'-bis(1-naphthyl)-N,N'- Diphenyl-1,1'-diphenyl-4,4'-diamine (NPB), 4,4'-bis(N-carbazole)-1,1'-biphenyl (CBP), poly[ (9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)](TFB), poly(9- One or more of vinyl carbazole) (PVK), polytriphenylamine (Poly-TPD), PEDOT:PSS and 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA) kind.

It can be understood that, in addition to the above-mentioned functional layers, the optoelectronic device 100 can also add some functional layers that are conventionally used in optoelectronic devices to help improve the performance of optoelectronic devices, such as electron blocking layers, hole blocking layers, electron injection layers, Hole injection layer, interface modification layer, etc.

It can be understood that the material of each layer of the optoelectronic device 100 can be adjusted according to the light emission requirements of the optoelectronic device 100 .

It can be understood that the optoelectronic device 100 may be a positive optoelectronic device or an inverted optoelectronic device.

Please refer to FIG. 3 , the embodiment of the present application also provides a method for preparing the optoelectronic device 100, including the following steps:

Step S11: providing a first electrode, and forming a light-emitting layer 20 on the first electrode;

Step S12: forming an electron transport layer 30 on the light-emitting layer 20, specifically:

A. Provide zinc salt, alkali and solvent, and mix to obtain ZnO precursor solution;

B. The ZnO precursor solution is mixed with the metal phthalocyanine complex and reacted to obtain the ZnO nanomaterial modified by the metal phthalocyanine complex, i.e. the material of the electron transport layer;

C. disposing the ZnO nanomaterial modified by the metal phthalocyanine complex on the light-emitting layer 20 to obtain the electron transport layer 30 .

Step S13 : forming a second electrode on the electron transport layer 30 .

It can be understood that at this time, the first electrode is the anode 10 , and the second electrode is the cathode 40 .

It can be understood that when the optoelectronic device 100 further includes a hole transport layer 50 , the step S11 is: providing a first electrode, and sequentially forming a stacked hole transport layer 50 and a light emitting layer 20 on the first electrode.

Please refer to FIG. 4, the embodiment of the present application also provides another method for preparing the optoelectronic device 100, which includes the following steps:

Step S21: providing a first electrode;

Step S22: forming an electron transport layer 30 on the first electrode, specifically:

A. Provide zinc salt, alkali and solvent, and mix to obtain ZnO precursor solution;

B. The ZnO precursor solution is mixed with the metal phthalocyanine complex and reacted to obtain the ZnO nanomaterial modified by the metal phthalocyanine complex, i.e. the material of the electron transport layer;

C. Arranging the ZnO nanomaterial modified by the metal phthalocyanine complex on the cathode 40 to obtain the electron transport layer 30 .

Step S23 : sequentially forming a laminated light emitting layer 20 and a second electrode on the electron transport layer 30 .

It can be understood that, at this time, the first electrode is the cathode 40 , and the second electrode is the anode 10 .

It can be understood that when the optoelectronic device 100 further includes a hole transport layer 50 , the step S23 is: sequentially forming a stacked light emitting layer 20 , a hole transport layer 50 and a second electrode on the electron transport layer 30 .

In the above two preparation methods:

In the step A, the zinc salt can be selected from but not limited to one or more of soluble inorganic zinc salts and soluble organic zinc salts, for example, can be selected from but not limited to zinc acetate, zinc nitrate, zinc chloride and one or more of zinc acetate dihydrate.

The base may be selected from but not limited to one or more of sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide.

The solvent may be an organic solvent. The organic solvent may be selected from but not limited to one or more of methanol, ethanol and butanol.

The range of the molar ratio of ^OH- in the alkali to Zn ²⁺ in the zinc salt is (1.5-3):1. The pH range of the ZnO precursor solution is 12-14. Alkaline environment is conducive to the synthesis of ZnO nanometer material, and the pH of described alkali is too low, and the surface of ZnO nanomaterial easily forms more hydroxyl ligands; The diameter is too small and has more surface defects.

In one embodiment, the mixing method of the salt, alkali and solvent is as follows: add an appropriate amount of zinc salt to 50ml of solvent to form a solution with a concentration of 0.1-1M, stir to dissolve, then add 10ml of alcoholic lye, and continue to stir 10min-2h to get a clear and transparent solution, which is the ZnO precursor solution. The alcohol may be selected from but not limited to one or more of methanol, ethanol and butanol.

In said step A, the step of stirring at constant temperature is also included after mixing. Wherein, the temperature range of constant temperature is 60-120°C. The stirring time is not limited, and the stirring can be stopped after obtaining a clear and transparent solution. In one embodiment, the stirring time range is 10min-2h. The constant temperature stirring can reduce the reaction barrier, increase the activity of reactants, and then accelerate the reaction. If the temperature is too low, the effect is not good, and if the temperature is too high, the solvent evaporates quickly and affects the reaction.

In the step B, the metal phthalocyanine complex can be selected from but not limited to one or more of zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine and copper phthalocyanine.

In one embodiment, the metal phthalocyanine complex is a fluorinated metal phthalocyanine complex. The fluorinated metal phthalocyanine complex can be selected from but not limited to one or more of fluorinated zinc phthalocyanine, fluorinated magnesium phthalocyanine, fluorinated cobalt phthalocyanine, fluorinated silver phthalocyanine and fluorinated copper phthalocyanine kind.

The range of the molar ratio of Zn ²⁺ in the ZnO precursor solution to the metal phthalocyanine complex is 1:(0.01-0.2).

It can be understood that the type of the substrate is not limited. In one embodiment, the substrate is a cathode substrate, and the cathode can be selected from but not limited to one or more of Ag electrodes, Al electrodes, Au electrodes, Pt electrodes or alloy electrodes, and the substrate can be The conventionally used substrate such as glass, the ZnO nanometer material modified by the metal phthalocyanine complex is arranged on the cathode. In yet another embodiment, the substrate includes a laminated anode and a light emitting layer, and the ZnO nanomaterial modified by the metal phthalocyanine complex is disposed on the light emitting layer.

The step B, after mixing the ZnO precursor solution and the metal phthalocyanine complex, further includes: stirring the ZnO precursor solution and the metal phthalocyanine complex to react to obtain a reaction product, and then using a precipitation agent to precipitate the reaction product . In one embodiment, the reaction time is 1-4h. The eluting agent can be selected from but not limited to one or more of acetone, ethyl acetate, hexane and heptane.

In the step C, the method of arranging the ZnO nanomaterial modified by the metal phthalocyanine complex on the substrate may be a chemical method or a physical method. Among them, the chemical method can be chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodic oxidation method, electrolytic deposition method and co-precipitation method, etc. The physical method can be physical coating method or solution processing method, and the physical coating method can be thermal evaporation coating method CVD, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method PVD, atomic layer deposition method and pulse laser deposition method, etc.; the solution processing method can be spin coating method, printing method, inkjet printing method, scraping method, printing method, dipping method, soaking method, spraying method, roller coating method, casting method, Slot coating method and strip coating method, etc.

In one embodiment, the method of arranging the ZnO nanomaterial modified by the metal phthalocyanine complex on the substrate is a solution method. At this time, the ZnO nano material modified by the metal phthalocyanine complex needs to be used first. The dispersant is dispersed to obtain the metal phthalocyanine complex modified ZnO nano material dispersion, and then the metal phthalocyanine complex modified ZnO nano material dispersion is arranged on the substrate by a solution method. The dispersant may be selected from but not limited to one or more of methanol, ethanol, butanol and pentanol.

The methods for forming the anode 10 , the hole transport layer 50 , the light emitting layer 20 and the cathode 40 can be realized by conventional techniques in the art, such as chemical or physical methods. The chemical method or physical method can be referred to above, and will not be repeated here.

It can be understood that when the photoelectric device 100 further includes other functional layers such as an electron blocking layer, a hole blocking layer, an electron injection layer, a hole injection layer or an interface modification layer, the preparation method of the photoelectric device 100 also includes forming the Describe the steps of each functional layer.

The embodiment of the present application also provides a display device, which includes the optoelectronic device 100 .

The present application will be described in detail through specific examples below, and the following examples are only part of the examples of the present application, and are not intended to limit the present application.

Example 1

Provide a glass substrate with an ITO anode 10, wherein the thickness of the anode 10 is 50nm;

Spin coating TFB material on the anode 10 to obtain a hole transport layer 50 with a thickness of 30 nm;

Spin-coat blue quantum dots with a CdSe/ZnS core-shell structure on the hole transport layer 50 to obtain a light-emitting layer 20 with a thickness of 40 nm;

Add an appropriate amount of zinc chloride into 30ml of methanol, stir and dissolve to form a solution with a total concentration of 0.5M, and then add 10ml of methanol lye, wherein the OH in the lye ^and the Zn ²⁺ in the zinc chloride The molar ratio is 1.5:1, and the stirring is continued for 1 hour to obtain a clear and transparent solution, which is the ZnO precursor solution;

Mix the above ZnO precursor solution with fluorinated zinc phthalocyanine, wherein the molar ratio of Zn in the ZnO precursor solution to fluorinated zinc phthalocyanine is 1:0.1, stir for 1 h, and precipitate the reaction product with acetone to obtain fluorinated phthalocyanine Zinc cyanine-modified ZnO nanoparticles, wherein the ZnO nanoparticles have a particle size of 10-100 nm and are dispersed with ethanol to obtain a ZnO nanomaterial dispersion liquid modified with fluorinated zinc phthalocyanine;

Spin-coating the ZnO nanomaterial dispersion modified with fluorinated zinc phthalocyanine on the light-emitting layer 20 to obtain an electron transport layer 30 with a thickness of 40 nm;

Evaporating Al on the electron transport layer 30 to obtain a cathode 40 with a thickness of 100 nm;

packaged to obtain the photoelectric device 100 .

Example 2

This embodiment is basically the same as Embodiment 1, the difference is that in this embodiment, the ZnO precursor solution is mixed with fluorinated cobalt phthalocyanine, wherein the molar ratio of Zn in the ZnO precursor solution to fluorinated cobalt phthalocyanine is 1:0.05.

Example 3

This embodiment is basically the same as Embodiment 1, the difference is that in this embodiment, the ZnO precursor solution is mixed with fluorinated magnesium phthalocyanine, wherein the molar ratio of Zn in the ZnO precursor solution to fluorinated magnesium phthalocyanine is 1:0.05.

Example 4

This embodiment is basically the same as Embodiment 1, the difference is that in this embodiment, the ZnO precursor solution is mixed with zinc phthalocyanine, wherein the molar ratio of Zn in the ZnO precursor solution to zinc phthalocyanine is 1:0.1, The ZnO nanometer particles modified by the zinc phthalocyanine and the ZnO nanometer material dispersion liquid modified by the zinc phthalocyanine are obtained.

comparative example

Provide a glass substrate with an ITO anode, wherein the thickness of the anode is 50 nm;

Spin coating TFB material on the anode to obtain a hole transport layer with a thickness of 30nm;

Spin-coat blue quantum dots with a CdSe/ZnS core-shell structure on the hole transport layer to obtain a light-emitting layer with a thickness of 40 nm;

Provide ZnO nanomaterials, wherein the ZnO nanomaterials have a particle size of 10-100nm, and disperse them with ethanol to obtain a ZnO nanomaterial dispersion;

Spin-coating the ZnO nanomaterial dispersion on the light-emitting layer to obtain an electron transport layer with a thickness of 40 nm;

Evaporating Al on the electron transport layer to obtain a cathode with a thickness of 100 nm;

Encapsulate to obtain an optoelectronic device.

The external quantum efficiency EQE and turn-on voltage of the photoelectric device 100 of the above-mentioned Examples 1-4 and the photoelectric device of the comparative example were tested. Among them, the external quantum efficiency EQE and the turn-on voltage are measured by EQE optical testing equipment. Wherein, the turn-on voltage is the voltage when the brightness of the device is 1 nits. The test results are shown in Table 1.

Table I:

the	EQE(%)	Turn on voltage (V)
comparative example	2.77	5.59
Example 1	6.81	2.21
Example 2	6.47	2.20
Example 3	6.12	2.23
Example 4	4.81	4.44

As can be seen from Table 1, compared with the optoelectronic device in which the electron transport layer material is ZnO nanomaterial, the optoelectronic device 100 in which the electron transport layer 30 material of Examples 1-4 is a ZnO nanomaterial modified by a metal phthalocyanine complex has a higher External quantum efficiency and lower turn-on voltage.

The optoelectronic device provided by the embodiment of the present application and its preparation method have been introduced in detail above. The principles and implementation methods of the present application have been explained by using specific examples in this paper. The description of the above embodiments is only used to help understand the application. method and its core idea; at the same time, for those skilled in the art, according to the idea of this application, there will be changes in the specific implementation and application scope. limits.

Claims (20)

1. A photoelectric device, comprising a laminated anode, a light-emitting layer, an electron transport layer and a cathode, wherein the material of the electron transport layer includes ZnO particles and metal phthalocyanine complexes connected on the surface of the ZnO particles.
2. The optoelectronic device according to claim 1, wherein the metal phthalocyanine complex is selected from one or more of zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine and copper phthalocyanine.
3. The photoelectric device according to claim 1, wherein, in the material of the electron transport layer, the molar ratio of the metal phthalocyanine complex to the ZnO particles is in the range of 1:(0.01-0.2).
4. The photoelectric device according to claim 1, wherein the metal phthalocyanine complex is a fluorinated metal phthalocyanine complex.
5. The optoelectronic device according to claim 4, wherein said fluorinated metal phthalocyanine complex is selected from the group consisting of fluorinated zinc phthalocyanine, magnesium fluorinated phthalocyanine, cobalt fluorinated phthalocyanine, silver fluorinated phthalocyanine and fluorinated phthalocyanine One or more of copper cyanides.
6. The photoelectric device according to claim 1, wherein the average particle diameter of the ZnO particles is in the range of 10-100 nm.
7. The optoelectronic device according to claim 1, wherein the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and the material of the organic light-emitting layer is selected from diaryl anthracene derivatives, stilbene aromatic derivatives, One or more of pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, the material of the quantum dot light-emitting layer is selected from single-structure quantum dots and core-shell structure quantum dots One or more of the dots, the single-structure quantum dots are selected from one or more of II-VI group compounds, III-V group compounds and I-III-VI group compounds, and the II-VI group The compound is selected from one or more of CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe, the The III-V group compound is selected from one or more of InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP, and the I-III-VI group compound is selected from CuInS _2. One or more of CuInSe ₂ and AgInS ₂ , the core of the quantum dot with the core-shell structure is selected from one or more of the above-mentioned single-structure quantum dots, and the shell of the quantum dot with the core-shell structure The layer material is selected from one or more of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS.
8. The photoelectric device according to claim 1, wherein the photoelectric device further comprises a hole transport layer, the hole transport layer is located between the anode and the light-emitting layer, and the material of the hole transport layer is selected from Self-poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl) base)amino]-9,9'-spirobifluorene, 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], N,N'-bis(1-naphthyl )-N,N'-diphenyl-1,1'-diphenyl-4,4'-diamine, 4,4'-bis(N-carbazole)-1,1'-biphenyl, poly [(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)], poly(9-vinyl One or more of carbazole), polytriphenylamine, PEDOT:PSS and 4,4',4"-tris(carbazol-9-yl)triphenylamine.
9. A method for preparing an optoelectronic device, comprising the steps of:

   providing a first electrode;

   forming a light emitting layer, the light emitting layer being formed on the first electrode;

   forming a second electrode, the second electrode being formed on the light emitting layer;

   The preparation method also includes: providing zinc salt, alkali and solvent, mixing to obtain a ZnO precursor solution, mixing the ZnO precursor solution with a metal phthalocyanine complex to obtain a material for an electron transport layer, and depositing the electron transport layer layer materials to obtain an electron transport layer, and the electron transport layer and the light emitting layer are stacked between the first electrode and the second electrode.
10. The preparation method as claimed in claim 9, wherein,

    The first electrode is an anode, the second electrode is a cathode, and the deposition of the material of the electron transport layer is performed between the formation of the light emitting layer and the formation of the second electrode, and includes: The material of the electron transport layer is deposited on the layer.
11. The preparation method according to claim 9, wherein the first electrode is a cathode, and the second electrode is an anode, and the deposition of the material of the electron transport layer is performed before the formation of the light-emitting layer, and includes: The material of the electron transport layer is deposited on the first electrode.
12. The preparation method according to claim 9, wherein the zinc salt is selected from one or more of zinc acetate, zinc nitrate, zinc chloride and zinc acetate dihydrate.
13. The preparation method according to claim 9, wherein the alkali is selected from one or more of sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide, and the solvent is selected from methanol, ethanol and butanol one or more of.
14. The preparation method according to claim 9, wherein the molar ratio of ^OH in the alkali to Zn in the zinc salt ranges from ( ^1.5-3 ):1.
15. The preparation method according to claim 9, wherein the molar ratio of Zn ²⁺ in the ZnO precursor solution to the metal phthalocyanine complex is in the range of 1:(0.01-0.2).
16. The preparation method according to claim 9, wherein the pH range of the ZnO precursor solution is 12-14.
17. The preparation method according to claim 9, wherein the metal phthalocyanine complex is selected from one or more of zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine and copper phthalocyanine.
18. The preparation method according to claim 9, wherein the metal phthalocyanine complex is a fluorinated metal phthalocyanine complex, and the fluorinated metal phthalocyanine complex is selected from the group consisting of fluorinated zinc phthalocyanine and fluorinated magnesium phthalocyanine One or more of fluorinated cobalt phthalocyanine, fluorinated silver phthalocyanine and fluorinated copper phthalocyanine.
19. The preparation method according to claim 9, wherein, after the mixing, a step of stirring at 60-120° C. is also included.
20. A display device, wherein the display device comprises the optoelectronic device according to any one of claims 1-8.

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