WO2023098371A1 - Photoelectric device processing method and photoelectric device - Google Patents

Abstract

The present application provides a photoelectric device processing method and a photoelectric device. Residual organic matters and impurities on the surface of a film layer of the photoelectric device in the preparation process are removed by utilizing liquid and/or solid carbon dioxide. The organic matters can be taken away after liquid and solid carbon dioxide are volatilized, and extra impurity residues are avoided, so that the film-forming property of the prepared film layer is improved, thereby improving the performance of the device.

Description

Optoelectronic device processing method and optoelectronic device

This application claims priority to a Chinese patent application with application number 202111440988.X and titled "Optoelectronic device processing method and optoelectronic device" filed at the China Patent Office on November 30, 2021, the entire contents of which are incorporated by reference incorporated in this application.

technical field

The present application relates to the field of optoelectronic devices, in particular to a method for processing optoelectronic devices and an optoelectronic device.

Background technique

Optoelectronic devices are semiconductor devices based on organic or inorganic materials, and have a wide range of applications in new energy, sensing, communication, display, lighting and other fields.

QLED (Quantum Dots Light-Emitting Diode, Quantum Dot Light-Emitting Diode) is an emerging optoelectronic device, the structure is similar to OLED (Organic Light-Emitting Diode, organic light-emitting display), that is, hole transport layer, light-emitting layer and electron transport layer This is a new technology between liquid crystal and OLED. The core technology of QLED is "Quantum Dot (quantum dot)". Quantum dot is composed of zinc, cadmium, selenium and sulfur atoms. It is a kind of particle Particles with a diameter of less than 10 nm are composed of zinc, cadmium, sulfur, and selenium atoms. This substance has a very special property: when the quantum dot is stimulated by light, it will emit colored light, and the color is determined by the material making up the quantum dot and its size and shape. Because it has this property, it is able to change the color of the light emitted by the light source. The emission wavelength range of quantum dots is very narrow, and the color is relatively pure and adjustable, so the picture of quantum dot display will be clearer and brighter than that of liquid crystal display.

technical problem

Optoelectronic devices such as QLED still have many problems in the research and development process. For example, in experimental development or industrial production, the hole injection layer, hole transport layer, light emitting layer and electron transport layer have the problem of poor film-forming properties during preparation.

technical solution

Therefore, the present application provides a method for processing an optoelectronic device and an optoelectronic device.

An embodiment of the present application provides a method for processing a photoelectric device, the method comprising: providing a film layer of a photoelectric device, and treating the surface of the film layer with liquid carbon dioxide and/or solid carbon dioxide.

Optionally, in some embodiments of the present application, the treatment of the surface of the membrane layer with solid carbon dioxide includes: spraying solid carbon dioxide onto the surface of the membrane layer so that particles of the solid carbon dioxide impact the membrane layer s surface.

Optionally, in some embodiments of the present application, the injecting solid carbon dioxide onto the surface of the membrane layer, and causing the particles of the solid carbon dioxide to impact the surface of the membrane layer includes: ejecting carbon dioxide gas from a nozzle , the ejected carbon dioxide gas is transformed into solid carbon dioxide in the air and impacts the surface of the film layer.

Optionally, in some embodiments of the present application, the solid carbon dioxide is sprayed onto the surface of the membrane layer by using a dry ice particle spraying method.

Optionally, in some embodiments of the present application, the solid carbon dioxide injection time is 80s-120s.

Optionally, in some embodiments of the present application, the diameter of the solid carbon dioxide particles is 0.1 μm to 1 μm.

Optionally, in some embodiments of the present application, during the process of the particles of solid carbon dioxide impacting the surface of the membrane layer, ultrasonic treatment is also performed on the membrane layer.

Optionally, in some embodiments of the present application, during the ultrasonic treatment, the ultrasonic frequency is 200 kHz to 250 kHz.

Optionally, in some embodiments of the present application, ultrasonic waves act vertically on the film layer.

Optionally, in some embodiments of the present application, the ultrasonic treatment time is 15s to 30s.

Optionally, in some embodiments of the present application, the treating the surface of the film layer with liquid carbon dioxide includes: coating or soaking the film layer with liquid carbon dioxide, and then standing still until the carbon dioxide vaporizes and volatilizes.

Optionally, in some embodiments of the present application, an organic solvent is used during the preparation of the film layer of the optoelectronic device.

Optionally, in some embodiments of the present application, the film layer is at least one of an anode, a hole transport layer, a hole injection layer, a light emitting layer or an electron transport layer.

Correspondingly, the embodiment of the present application also provides a photoelectric device, including a photoelectric device, and the film layer of the photoelectric device is obtained by treating the surface of the film layer with liquid carbon dioxide and/or solid carbon dioxide, so that The film layer is at least one of the anode, hole transport layer, hole injection layer, light emitting layer or electron transport layer.

Optionally, in some embodiments of the present application, the anode material includes one of metal, non-metal material, doped or undoped metal oxide; the metal or non-metal material is selected from nickel , platinum, gold, silver, iridium or carbon nanotubes, the doped or undoped metal oxide is selected from indium tin oxide, indium zinc oxide, indium tin zinc oxide, indium oxide One or more of copper, tin oxide, indium oxide, cadmium: zinc oxide, fluorine: tin oxide, indium: zinc oxide or gallium: tin oxide or zinc: aluminum oxide.

Optionally, in some embodiments of the present application, the cathode includes one of a metal material electrode, a carbon material electrode, a metal oxide electrode and a composite electrode, and the material of the metal material electrode includes Al, Ag, Cu One or more of , Mo, Au, Ba, Ca, Mg, the material of the carbon material electrode includes one or more of graphite, carbon nanotube, graphene, carbon fiber, the metal oxide electrode The material includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO /Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO ₂ /Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO ₂ /Ag/ One or more of TiO ₂ , TiO ₂ /Al/TiO ₂ .

Optionally, in some embodiments of the present application, the material of the light emitting layer includes a direct bandgap compound semiconductor or a perovskite semiconductor capable of emitting light: II-VI compound, III-V compound and I-III -one or more of group VI compounds selected from the group consisting of CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe , CdTeS; one or more of CdZnSeS, CdZnSeTe or CdZnSTe; the III-V group compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP or InAlNP One or more; the I-III-VI group compound is selected from one or more of CuInS ₂ , CuInSe ₂ or AgInS ₂ ; the perovskite semiconductor includes doped or non-doped inorganic calcium One or more of titanium type semiconductors and organic-inorganic hybrid perovskite semiconductors, the general structural formula of the inorganic perovskite semiconductors is AMX ₃ , and the organic-inorganic hybrid perovskite The general structural formula of the type semiconductor is BMX ₃ , wherein, A is Cs ⁺ ion, M is a divalent metal cation, and the divalent metal cation includes Pb ²⁺ , Sn ²⁺ , Cu ²⁺ , Ni ²⁺ , Cd ^{2 +} , Cr ²⁺ , Mn ²⁺ , Co ²⁺ , Fe ²⁺ , Ge ²⁺ , Yb ²⁺ , Eu ²⁺ , X is a halogen anion, and the halogen anion includes Cl ^- , Br ^- , One of ^I- , B is an organic amine cation, and the organic amine cation includes CH ₃ (CH ₂ ) _n-2 NH ³⁺ (n≥2) and NH ₃ (CH ₂ ) _n NH ₃ ²⁺ (n ≥ one of 2).

Optionally, in some embodiments of the present application, the hole injection layer material includes: one or more of PEDOT:PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide or transition metal chalcogenide kind.

Optionally, in some embodiments of the present application, the material of the hole transport layer includes: poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), poly Vinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N , N-phenyl-1,4-phenylenediamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 15N,N'-diphenyl-N , one or more of N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine or graphene or C ₆₀ .

Optionally, in some embodiments of the present application, the electron transport layer material includes: ZnO, TiO ₂ , SnO ₂ , Ta ₂ O ₃ , ZrO ₂ , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO or InSnO one or more of.

Beneficial effect

This application uses liquid carbon dioxide and/or solid carbon dioxide to treat the surface of the film layer of the photoelectric device to remove the residual organic matter and particle impurities on the surface of the film layer during the preparation process. After the liquid and solid carbon dioxide volatilize, the organic matter will be taken away and There will be no additional impurities remaining, which can improve the film-forming properties of the film layer prepared later, thereby improving the performance of the device; in addition, this application uses liquid and solid carbon dioxide in a low temperature state to treat the surface of the film layer, avoiding the use of high temperature Rapid thermal annealing is a method to remove impurities and prevent adverse effects of high temperature on devices.

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 flow chart of the film layer surface treatment method of the photoelectric device provided by the first embodiment of the present application;

Fig. 2 is a schematic structural diagram of a quantum dot light-emitting diode with an upright structure provided by an embodiment of the present application;

Fig. 3 is the schematic diagram that the Venturi nozzle provided by the embodiment of the present application ejects solid carbon dioxide;

Fig. 4 is the EL electroluminescent topography diagram of the second day of device preparation of Examples 1 to 3 and Comparative Example 1 provided in the examples of the present application;

Fig. 5 is the EL electroluminescent topography diagram of the 100th day of device preparation provided in the examples of the present application from Example 1 to Example 3 and Comparative Example 1;

Fig. 6 is a flow chart of the film surface treatment method of the photoelectric device provided in the second embodiment of the present application;

Fig. 7 is a flow chart of the film surface treatment method of the photoelectric device provided in the third embodiment of the present application;

FIG. 8 is a flow chart of a method for treating the surface of a film layer of an optoelectronic device according to the fourth 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.

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".

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.

In this application, "one or more" means one or more, and "multiple" means two or more. "One or more", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one item (unit) of a, b, or c", or "at least one item (unit) 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, and c can be single or multiple.

First, please refer to FIG. 1. FIG. 1 shows a method for processing an optoelectronic device provided by an embodiment of the present application. The method includes:

S10. Provide a film layer of an optoelectronic device.

S20. Using liquid carbon dioxide (CO ₂ ) and/or solid carbon dioxide to treat the surface of the membrane layer.

This application uses liquid and/or solid carbon dioxide to treat the surface of the film layer of the photoelectric device to remove the residual organic matter and particle impurities on the surface of the film layer during the preparation process. After the liquid and solid carbon dioxide volatilize, the organic matter will be taken away and will not There will be additional impurities remaining, which can improve the film-forming property of the film layer prepared later, improve the problem of short circuit of the device, thereby improving the performance of the device; in addition, this application uses liquid and solid carbon dioxide in a low temperature state to treat the surface of the film layer. Processing, avoid the method of using high temperature rapid thermal annealing to remove impurities, and prevent the adverse effects of high temperature on the device.

For the embodiment of the present application, the optoelectronic device in step S10 may be a quantum dot light emitting diode. For example, FIG. 2 shows a schematic structural diagram of a quantum dot light emitting diode with an upright structure, and the quantum dot light emitting diode includes: In the thickness direction of the quantum dot light-emitting diode, the substrate 1, the anode 2, the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, the electron transport layer 6, and the cathode 7 are sequentially stacked from bottom to top. The film layer of the photoelectric device in the step S10 can specifically be a functional layer such as the hole injection layer 3 , the hole transport layer 4 , the light emitting layer 5 or the electron transport layer 6 between the cathode 7 and the anode 2 . It should be noted that the above is only an example, and the quantum dot light-emitting diode can also be an inverted structure. In the inverted structure, the cathode is arranged on the substrate. Whether it is an inverted structure or an upright structure, the anode 2 and the cathode Other film layers such as a hole blocking layer, an electron blocking layer, and an electron injection layer may also be provided between 7, which are not specifically limited here.

In the embodiment of this application, the material of the film layer of the photoelectric device is a common material in the field, for example:

The substrate can be a rigid substrate or a flexible substrate. Specific materials may include one of glass, silicon wafer, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone or more.

The anode material is selected from but not limited to: nickel (Ni), platinum (Pt), gold (Au), silver (Ag), iridium (Ir) or carbon nanotube (CNT) metal or non-metallic materials. Can also include doped or undoped metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), indium copper oxide (ICO), tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), cadmium: zinc oxide (Cd: ZnO), fluorine: tin oxide (F: SnO ₂ ), indium: zinc oxide (In: SnO ₂ ), gallium: tin oxide (Ga : SnO ₂ ) or zinc: aluminum oxide (Al: ZnO; AZO).

The hole injection layer material is selected from, but not limited to: one or more of PEDOT:PSS, CuPc, F4-TCNQ, HATCN, transition metal oxides, and transition metal chalcogenides.

The hole transport layer material is selected from but not limited to: poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N,N'bis (4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-benzene diamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N, N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 15N,N'-diphenyl-N,N'-(1-naphthyl)- One or more of 1,1'-biphenyl-4,4'-diamine, graphene, and C60.

The material of the light-emitting layer can be a direct bandgap compound semiconductor with light-emitting ability, selected from but not limited to II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, One or more of I-III-VI compound, II-IV-VI compound or IV element. Specifically, the semiconductor materials used in the light-emitting layer include but are not limited to II-VI semiconductor nanocrystals, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and other two Yuan, ternary, quaternary II-VI compounds; nanocrystals of III-V semiconductors, such as GaP, GaAs, InP, InAs and other binary, ternary, quaternary III-V compounds; Materials for the light-emitting layer are not limited to II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds, IV simple substances, and the like. Wherein, the light-emitting layer material can also be a doped or non-doped inorganic perovskite semiconductor, and/or an organic-inorganic hybrid perovskite semiconductor; specifically, the inorganic perovskite semiconductor The general structural formula of the semiconductor is AMX ₃ , where A is Cs ⁺ ions, and M is a divalent metal cation, including but not limited to Pb ²⁺ , Sn ²⁺ , Cu ²⁺ , Ni ²⁺ , Cd ²⁺ , Cr ²⁺ , Mn ²⁺ , Co ²⁺ , Fe ²⁺ , Ge ²⁺ , Yb ²⁺ , Eu ²⁺ , X is a halogen anion, including but not limited to Cl ^- , Br ^- , I ^- ; the organic-inorganic hetero The general structural formula of perovskite semiconductor is BMX ₃ , where B is an organic amine cation, including but not limited to CH ₃ (CH ₂ ) _n-2 NH ³⁺ (n≥2) or NH ₃ (CH ₂ ) _n NH ₃ ²⁺ (n≥2). When n=2, the inorganic metal halide octahedron MX ₆₄ ^- is connected by a common top, the metal cation M is located at the body center of the halogen octahedron, and the organic amine cation B fills the gap between the octahedrons, forming an infinitely extending Three-dimensional structure; when n>2, the inorganic metal halide octahedron ^MX ₆₄ connected in a common top-extends in the two-dimensional direction to form a layered structure, and an organic amine cationic bilayer (protonated monoamine) is inserted between the layers Or organic amine cation monolayer (protonated diamine), the organic layer and the inorganic layer overlap each other to form a stable two-dimensional layered structure; M is a divalent metal cation, including but not limited to Pb ²⁺ , Sn ²⁺ , Cu ²⁺ , Ni ²⁺ , Cd ²⁺ , Cr ²⁺ , Mn ²⁺ , Co ²⁺ , ^Fe2+ , Ge ²⁺ , Yb ²⁺ , Eu ²⁺ ; X is a halogen anion, including but not limited to Cl ^- , Br ^- , I.

The material of the electron transport layer can be an oxide semiconductor nanoparticle material with electron transport capability, selected from but not limited to ZnO, TiO ₂ , SnO ₂ , Ta ₂ O ₃ , ZrO ₂ , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, One or more of ZnLiO and InSnO.

The material of the cathode is selected from but not limited to: one or more of metal materials, carbon materials, and metal oxides. Wherein, the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Mg. The carbon material includes one or more of graphite, carbon nanotubes, graphene, and carbon fibers. The metal oxide can be doped or non-doped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, also including doped or non-doped transparent A composite electrode with metal sandwiched between metal oxides, wherein the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO /Al/ZnO, TiO ₂ /Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO ₂ /Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ one or more.

In the present application, each film layer of the photoelectric device in step S10 can be provided by preparation methods known in the art, such as chemical methods and physical methods, wherein chemical methods include: chemical vapor deposition, continuous ion layer adsorption and reaction method, anodic oxidation method, electrolytic deposition method, co-precipitation method. Physical methods include physical coating methods and solution processing methods. In particular, in the embodiment of the present application, the film layer is prepared by a solution method, and the solution method includes but not limited to a printing method, a spin coating method, and a coating method. The solution method generally dissolves the materials of each film layer in an organic solvent, and then deposits each film layer sequentially from the bottom up. When the film layer is prepared by the solution method, the film layer prepared later will be affected by the previous film layer. The impact of residual organic solvents, and liquid carbon dioxide can dissolve these organic solvents, so the surface treatment method of the present application has a more significant cleaning effect on each film layer prepared by the solution method.

In some embodiments, an organic solvent is used in the preparation process of the film layer of the optoelectronic device.

In some embodiments, the film layer in S10 can be at least one of the anode, hole transport layer, hole injection layer, light-emitting layer or electron transport layer, especially the electron transport layer, the electron transport layer It is made of electron transport film. When the film layer is an electron transport film, during the film preparation process, the electron transport film material molecules in the precursor solution of the electron transport film will perform Brownian motion in the solution, because the electron transport film The molecular surface defects of the material (larger surface energy) and the irregular molecular motion will make them attract each other and agglomerate. The diameter of the agglomerated large particle impurities can reach the micron level, and the thickness of the cathode on the surface of the electron transport film is generally below 40nm (nanometer), so when the macromolecular agglomeration occurs on the surface of the electron transport film, it will have an impact on the preparation of the electrode. Seriously, it will lead to short circuit or open circuit of the device; in addition, due to the existence of impurity particles, the electroluminescence morphology of the device will be deteriorated, which will affect the efficiency of the device. Therefore, compared with other film layers, the surface treatment method of this application is applied to For the electron transport thin film, it has a more significant positive effect on the device. The positive effect is mainly reflected in two aspects: on the one hand, it can make the film smoother and make the light-emitting area more uniform, and at the same time, the electron transport film without large particles of impurities can have a beneficial effect on the evaporation of the cathode. On the other hand, it can improve the electrical properties of the thin film caused by impurities in the molecular agglomeration, making the drive current in the light-emitting area of the device unstable or even short-circuited.

When the film layer is a hole transport layer, a hole injection layer or a light-emitting layer, since these film layers will have organic solvents remaining on the surface after film formation, the method of the present application is used to treat the impurities on the surface of these film layers, It can still make the surface of the film layer smoother and improve the performance of the device.

Please refer to FIG. 8, in some embodiments, in the S20, the use of liquid carbon dioxide and/or solid carbon dioxide to treat the surface of the film layer includes: step S22, using liquid carbon dioxide to treat the film layer Apply or soak, then let stand until the carbon dioxide evaporates. Liquid carbon dioxide has the characteristic of dissolving organic matter, so this solution can mainly remove the residual organic solvent on the surface of the membrane layer.

Please refer to FIG. 6. In some embodiments, in the S20, the use of liquid carbon dioxide and/or solid carbon dioxide to treat impurities on the surface of the membrane layer includes: step S21, injecting solid carbon dioxide into the The surface of the membrane layer is used to make the particles of the solid carbon dioxide impact the surface of the membrane layer. This solution is mainly used to remove particulate impurities on the surface of the film layer. Please refer further to FIG. 7 , in some specific embodiments, the injection of solid carbon dioxide onto the surface of the membrane layer, so that the particles of the solid carbon dioxide impact the surface of the membrane layer, includes: step S211, injecting high-pressure carbon dioxide gas Jetted out from the nozzle, the jetted high-pressure carbon dioxide gas is transformed into solid carbon dioxide in the air and impacts the surface of the film layer.

In some embodiments, spraying solid carbon dioxide onto the surface of the film layer can be achieved by dry ice particle spraying, as shown in FIG. 3 , which shows a Venturi nozzle 9 spraying solid carbon dioxide 8 to act on the electron transport layer 6. The schematic diagram of the surface, the dry ice particle spraying method uses liquid or gaseous carbon dioxide as the source. When the high-pressure carbon dioxide gas is sprayed out through the Venturi nozzle 9, due to the narrowing of the cross section, the flow rate increases and the pressure decreases. During the spraying process, the enthalpy value can be constant. In the case of expansion, the temperature of carbon dioxide gas drops sharply, and part of the gas is transformed into dry ice particles with a diameter of 0.1 μm to 1 μm (micron), forming a high-speed fluid 10 composed of carbon dioxide gas, solid and liquid.

For the embodiment of the present application, the dry ice particle blasting method mainly utilizes the transfer of energy and momentum between solid carbon dioxide and pollutants on the surface of the object, so as to remove impurity particles of various sizes. On the other hand, the ejected liquid carbon dioxide has a dissolving effect on the organic matter, and can remove the organic matter on the surface of the membrane layer.

In addition, carbon dioxide can also produce a small amount of carbonic acid with PPM water in the environment, which can accelerate the positive aging effect of light-emitting devices when attached to the surface of the device. It is manifested as an increase in the working life of the device.

In some embodiments, the injection time of the solid carbon dioxide is 80s to 120s (seconds). If the injection time is too long, too much carbonic acid generated during the injection process will change the performance of the device and reduce the effective storage time of the device. , so that its stability is reduced. If the spraying treatment time is too short, the film impurities cannot be effectively removed. It can be understood that the dry ice blasting time can be any value within the range of 80s ~ 120s, for example: 80s, 85s, 90s, 95s, 100s, 110s, 105s, 110s, 115s, 120s, etc., or other values within the range of 80s ~ 120s Value not listed.

In order to improve the efficiency of impurity removal, in some embodiments, during the process of the solid carbon dioxide particles impacting the surface of the membrane layer, ultrasonic treatment is also performed on the membrane layer. In this way, the processing time of the dry ice particle blasting method is greatly reduced, and the performance and stability of the device are significantly improved.

In this embodiment, ultrasonic treatment is used to assist the dry ice particle blasting method to remove impurities from the film layer. Because ultrasonic waves can vibrate substances and produce thermal effects when absorbed by the medium, it is difficult to implement high-power ultrasonic treatment on devices with high heat sensitivity. The embodiment of the present application uses ultrasonic waves to vibrate the material, which can effectively increase the contact frequency of liquid carbon dioxide and the film when the dry ice particle blasting method is used. It improves the efficiency of removing impurities by dry ice particle blasting, greatly reduces the processing time of dry ice particle blasting, and further prevents the problem of film cracking caused by dry ice contacting the surface of the film for too long. In addition, due to the low temperature environment provided by the dry ice particle blasting method, the ultrasonic treatment process will not cause thermal damage to the device.

In some embodiments, during the ultrasonic treatment, the ultrasonic frequency is 200kHz to 250kHz. If the frequency is too high, the device will be damaged, and if the frequency is too low, impurities cannot be effectively cleaned. It can be understood that the frequency of the ultrasonic wave can be any value within the range of 200kHz to 250kHz, for example: 200kHz, 210kHz, 220kHz, 230kHz, 240kHz or 250kHz, etc., or other unlisted values within the range of 200kHz to 250kHz.

In some embodiments, during the ultrasonic treatment, ultrasonic waves act perpendicularly to the film layer. Since ultrasonic waves have directivity, the common definition is the ratio of the sound pressure amplitude (Pa) θ in any direction to the sound pressure amplitude (Pa) θ=0 on the angle θ=0 axis, as shown in Equation 1 below.

Therefore, in the embodiment of the present application, placing the sound wave perpendicular to the device can further improve the efficiency of the surface treatment of the film layer.

In some embodiments, during the sonication process, the sonication time is 15s to 30s. In this time range, it is possible to effectively remove the time on the surface of the film layer, which improves the efficiency of impurity removal. If the ultrasonic treatment time is too long, the heat of the ultrasonic treatment will affect the performance of the device. If the ultrasonic treatment time is too short, the film impurities cannot be effectively removed. It can be understood that the ultrasonic treatment time can be any value within the range of 15s to 30s, for example: 15s, 16s, 17s, 18s, 19s, 20s, 21s, 22s, 23s, 24s, 25s, 26s, 27s, 28s, 29s, 30s, etc., or other values not listed in the range of 15s to 30s.

In some embodiments, the solid carbon dioxide particles have a diameter of 0.1 μm to 1 μm. At this size, the effect of removing impurities is better. If the size is too large, the device will be damaged, and if the size is too small, the film impurities cannot be effectively removed. It can be understood that the diameter of solid carbon dioxide particles can be any value within the range of 0.1 μm to 1 μm, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm , 1.0μm, etc., or other unlisted values within the range of 0.1μm to 1μm.

Based on the same idea, the present application also provides a photoelectric device, including a photoelectric device, the film layer of the photoelectric device is obtained by treating the surface of the film layer with liquid carbon dioxide and/or solid carbon dioxide. In a specific embodiment, the optoelectronic device is QLED (Quantum Dots Light-Emitting Diode, Quantum Dots Light-Emitting Diode).

The following examples will specifically describe the present application, and the following examples are only some examples of the present application, and are not intended to limit the present application.

Example 1:

This embodiment provides a quantum dot light-emitting diode, and the preparation method of the quantum dot light-emitting diode includes:

(1) On the ITO substrate, spin-coat PEDOT:PSS film at a speed of 5000rpm for 30 seconds, then heat at 150°C for 15 minutes, and let it cool for 5 minutes;

(2) Spin-coat TFB film (8 mg/mL) at 3000 rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(3) Spin-coat quantum dot film (20mg/mL) at a speed of 2000rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(4) Spin-coat ZnO film (30mg/mL) at 2000rpm for 30 seconds, then heat at 80°C for 20 minutes, and let it cool for 5 minutes;

(5) Use liquid CO ₂ to coat the ZnO film, and when the CO ₂ is completely vaporized, let it stand for 5 minutes to return the device to normal temperature;

(6) By thermal evaporation, the vacuum degree is not higher than 3 × 10 ^-4 Pa, vapor deposition of Ag, the speed is 1 Angstrom / second, the time is 200 seconds, and the thickness is 20nm, to obtain a top-emitting positive quantum dot light-emitting diode, and to The device is packaged.

Example 2:

This embodiment provides a quantum dot light-emitting diode, and the preparation method of the quantum dot light-emitting diode includes:

(1) On the ITO substrate, spin-coat PEDOT:PSS film at a speed of 5000rpm for 30 seconds, then heat at 150°C for 15 minutes, and let it cool for 5 minutes;

(2) Spin-coat TFB film (8 mg/mL) at 3000 rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(3) Spin-coat quantum dot film (20mg/mL) at a speed of 2000rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(4) Spin-coat ZnO film (30mg/mL) at 2000rpm for 30 seconds, then heat at 80°C for 20 minutes, and let it cool for 5 minutes;

(5) The ZnO thin film of the device is processed by the dry ice particle blasting method, the incident angle is 45°, the distance between the spout and the cleaning point is 43nm, and the processing time is 90s;

(6) By thermal evaporation, the vacuum degree is not higher than 3 × 10 ^-4 Pa, vapor deposition of Ag, the speed is 1 Angstrom / second, the time is 200 seconds, and the thickness is 20nm, to obtain a top-emitting positive quantum dot light-emitting diode, and to The device is packaged.

Example 3:

This embodiment provides a quantum dot light-emitting diode, and the preparation method of the quantum dot light-emitting diode includes:

(1) On the ITO substrate, spin-coat PEDOT:PSS film at a speed of 5000rpm for 30 seconds, then heat at 150°C for 15 minutes, and let it cool for 5 minutes;

(2) Spin-coat TFB film (8 mg/mL) at 3000 rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(3) Spin-coat quantum dot film (20mg/mL) at a speed of 2000rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(4) Spin-coat ZnO film (30mg/mL) at 2000rpm for 30 seconds, then heat at 80°C for 20 minutes, and let it cool for 5 minutes;

(5) The ZnO thin film of the device was treated by dry ice particle jetting, the incident angle was 45°, the distance between the nozzle and the cleaning point was 43nm, and the treatment time was 20s. At the same time, the device was subjected to high-frequency ultrasonic treatment with an intensity of 200 kHz and a treatment time of 20 s. The sound wave direction is perpendicular to the film;

(6) By thermal evaporation, the vacuum degree is not higher than 3 × 10 ^-4 Pa, vapor deposition of Ag, the speed is 1 Angstrom / second, the time is 200 seconds, and the thickness is 20nm, to obtain a top-emitting positive quantum dot light-emitting diode, and to The device is packaged.

Comparative example 1:

This comparative example provides a quantum dot light-emitting diode, and the preparation method of the quantum dot light-emitting diode includes:

(1) On the ITO substrate, spin-coat PEDOT:PSS film at a speed of 5000rpm for 30 seconds, then heat at 150°C for 15 minutes, and let it cool for 5 minutes;

(2) Spin-coat TFB film (8 mg/mL) at 3000 rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(3) Spin-coat quantum dot film (20mg/mL) at a speed of 2000rpm for 30 seconds, then heat at 80°C for 10 minutes, and let it cool for 5 minutes;

(4) Spin-coat ZnO film (30mg/mL) at 2000rpm for 30 seconds, then heat at 80°C for 20 minutes, and let it cool for 5 minutes;

(5) By thermal evaporation, the vacuum degree is not higher than 3 × 10 ^-4 Pa, evaporate Ag, the speed is 1 Angstrom/second, the time is 200 seconds, and the thickness is 20nm, to obtain a top-emitting positive quantum dot light-emitting diode, and to The device is packaged.

In order to illustrate the impact of the surface treatment of the film layer of the device on the performance of the device in the embodiment of the present application, the JVL data of each embodiment and comparative example were tested respectively, the electrical performance of the device was determined, and the electroluminescence morphology of the device was photographed. The results As shown in Table 1, Figure 4 and Figure 5. In FIG. 4 , from top to bottom are the EL electroluminescence topography diagrams of the devices of Example 1, Example 2, Example 3 and Comparative Example 1 on the second day after device preparation. In FIG. 5 , from top to bottom are the EL electroluminescence topography diagrams of the devices of Example 1, Example 2, Example 3 and Comparative Example 1 on the 100th day after the device was prepared.

Table 1

Remarks: L represents the brightness of the device. Under the same current, the higher the brightness of the device, the better the efficiency of the device. T95 indicates the time it takes for the brightness of the device to decay from 100% to 95%. Under the same current, the longer the T95 time of the device, the better the performance and stability of the device. T95-1K indicates the time it takes for the brightness to decay from 100% to 95% when the device is under 1000nit brightness. This value is calculated from the value of L and T95. C.E represents the current efficiency of the device. Under the premise that the area of the light-emitting area is consistent with the driving current, the higher the C and E, the better the performance of the device. Rq represents the root mean square roughness of the device, and the smaller the value of Rq, the lower the roughness of the film.

As shown in Table 1, it can be seen from Table 1 that the L value, T95 value, T95-1K value, C.E value and Rq value of Examples 1 to 3 are greater than those of Comparative Example 1. It can be seen from Figure 4 and Figure 5 that due to the residue of organic impurities in Comparative Example 1, the phenomenon of uneven light emitting area occurs, and at the same time, there are black spots on the surface of the film due to polymer agglomeration and floating dust, while the black spots in Example 1 Compared with Comparative Example 1, the dots are reduced, and there are basically no black dots on the surface of the film layers of Examples 2 and 3, and there are still no black dots in Example 3 100 days after the preparation of the device. It shows that the performance and stability of the device are significantly improved after the surface treatment of the film layer with solid and gaseous carbon dioxide. This is due to the volatilization of liquid and solid carbon dioxide will take away the residual organic matter on the surface of the film layer and improve the film-forming properties of the film layer prepared later.

In addition, it can also be seen from Table 1, Figure 4 and Figure 5 that the performance of the device of Example 2 is better than that of Example 1, indicating that the use of dry ice particle blasting to treat the surface of the film layer can further improve the performance of the device. It is caused by the fact that the dry ice particle blasting method can remove large particles of impurities on the surface of the film layer, thereby preventing the short circuit of the device and improving the efficiency of the device. The performance of the device in Example 3 is better than that in Example 2, which shows that the use of ultrasonic-assisted dry ice particle blasting to remove impurities can further improve the performance of the device. This is because the particle impurities on the surface of the film are easier to Falling off, and it can also prevent the damage caused by dry ice to the film.

In summary, the present application provides a photoelectric device processing method and a photoelectric device, the method uses liquid carbon dioxide and/or solid carbon dioxide to treat the surface of the film layer of the photoelectric device, so as to remove the residual surface of the film layer during the preparation process. Organic matter and particle impurities, after the liquid and solid carbon dioxide volatilize, the organic matter will be taken away without additional impurities remaining, which can improve the film-forming properties of the film layer prepared later, thereby improving the performance of devices and optoelectronic devices; in addition, this The application is to use low-temperature liquid and solid carbon dioxide to treat the surface of the film layer, avoiding the method of removing impurities by using high-temperature rapid thermal annealing, and preventing the adverse effects of high temperature on the device. The stability, service life and efficiency of the optoelectronic device obtained through the method provided in the present application are all improved, and the application prospect is broad.

The processing method of a kind of optoelectronic device provided by the embodiment of the present application and the optoelectronic device have been introduced in detail above. In this paper, specific examples have been used to illustrate the principle and implementation of the present application. The description of the above embodiment is only used to help Understand the technical solution of the present application and its core idea; those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or The replacement does not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.

Claims (20)

A method for processing a photoelectric device, wherein the method includes: providing a film layer of a photoelectric device, and treating the surface of the film layer with liquid carbon dioxide and/or solid carbon dioxide. The method according to claim 1, wherein said treating the surface of the membrane layer with solid carbon dioxide comprises: spraying solid carbon dioxide onto the surface of the membrane layer so that particles of the solid carbon dioxide impact the surface of the membrane layer . The method according to claim 2, wherein said injecting solid carbon dioxide onto the surface of the membrane layer, causing particles of the solid carbon dioxide to impact the surface of the membrane layer, comprises: ejecting carbon dioxide gas from a nozzle, injecting The released carbon dioxide gas is converted into solid carbon dioxide in the air and impacts the surface of the membrane layer. The method according to claim 2, wherein the solid carbon dioxide is sprayed onto the surface of the membrane layer by using a dry ice particle spraying method. The method according to any one of claims 2 to 4, wherein the injection time of the solid carbon dioxide is 80s-120s. The method according to any one of claims 2 to 5, wherein the particles of solid carbon dioxide have a diameter of 0.1 μm to 1 μm. The method according to any one of claims 2 to 6, wherein, during the impact of the particles of solid carbon dioxide on the surface of the membrane layer, ultrasonic treatment is also performed on the membrane layer. The method according to claim 7, wherein, during the ultrasonic treatment, the ultrasonic frequency is 200kHz to 250kHz. The method according to claim 7 or 8, wherein the ultrasound is applied perpendicularly to the film layer. The method according to any one of claims 7 to 9, wherein the time of ultrasonic treatment is 15s to 30s. The method according to claim 1, wherein the treating the surface of the film layer with liquid carbon dioxide comprises: coating or soaking the film layer with liquid carbon dioxide, and then standing still until the carbon dioxide gasifies and volatilizes. The method according to any one of claims 1 to 11, wherein, in the preparation process of the film layer of the photoelectric device, an organic solvent is utilized. The method according to any one of claims 1 to 12, wherein the film layer is at least one layer of an anode, a hole transport layer, a hole injection layer, a light emitting layer or an electron transport layer. A photoelectric device, including a photoelectric device, the film layer of the photoelectric device is a film layer obtained by treating the surface of the film layer with liquid carbon dioxide and/or solid carbon dioxide, and the film layer is an anode, an air At least one of a hole transport layer, a hole injection layer, a light emitting layer or an electron transport layer. The optoelectronic device according to claim 14, wherein the anode material comprises one of metal, non-metallic material, doped or undoped metal oxide; the metal or non-metallic material is selected from nickel, One or more of platinum, gold, silver, iridium or carbon nanotubes, the doped or undoped metal oxide is selected from indium tin oxide, indium zinc oxide, indium tin zinc oxide, indium copper oxide One or more of , tin oxide, indium oxide, cadmium: zinc oxide, fluorine: tin oxide, indium: zinc oxide or gallium: tin oxide or zinc: aluminum oxide. The optoelectronic device according to claim 14 or 15, wherein the cathode comprises one of a metal material electrode, a carbon material electrode, a metal oxide electrode and a composite electrode, and the material of the metal material electrode comprises Al, Ag, One or more of Cu, Mo, Au, Ba, Ca, Mg, the material of the carbon material electrode includes one or more of graphite, carbon nanotubes, graphene, carbon fiber, the metal oxide The electrode material includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO ₂ /Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO ₂ /Ag One or more of /TiO ₂ , TiO ₂ /Al/TiO ₂ . The optoelectronic device according to any one of claims 14 to 16, wherein the light-emitting layer material comprises a direct bandgap compound semiconductor or a perovskite semiconductor with light-emitting capability: II-VI compound, III-V compound And one or more of I-III-VI group compounds, the II-VI group compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS , CdSeS, CdSeTe, CdTeS; one or more of CdZnSeS, CdZnSeTe or CdZnSTe; the III-V group compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP or one or more of InAlNP; the I-III-VI group compound is selected from one or more of CuInS ₂ , CuInSe ₂ or AgInS ₂ ; the perovskite semiconductor includes doped or non-doped One or more of heterogeneous inorganic perovskite semiconductors and organic-inorganic hybrid perovskite semiconductors, the general structural formula of the inorganic perovskite semiconductors is AMX ₃ , and the organic-inorganic hybrid The general structural formula of perovskite semiconductor is BMX ₃ , where A is Cs ⁺ ion, M is a divalent metal cation, and the divalent metal cation includes Pb ²⁺ , Sn ²⁺ , Cu ²⁺ , Ni ^{2 +} , Cd ²⁺ , Cr ²⁺ , Mn ²⁺ , Co ²⁺ , Fe ²⁺ , Ge ²⁺ , Yb ²⁺ , Eu ²⁺ , X is a halogen anion, and the halogen anion includes Cl ^- , Br ^- , one of I ^- , B is an organic amine cation, and the organic amine cation includes CH ₃ (CH ₂ ) _n-2 NH ³⁺ (n≥2) and NH ₃ (CH ₂ ) _n NH ₃ One of ²⁺ (n≥2). The photoelectric device according to any one of claims 14 to 17, wherein the hole injection layer material comprises: PEDOT:PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide or transition metal chalcogenide one or more. The photoelectric device according to any one of claims 14 to 18, wherein the hole transport layer material comprises: poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl) di aniline), polyvinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co -bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole ) biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 15N,N'-bis One or more of phenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine or graphene or _C60 . The photoelectric device according to any one of claims 14 to 19, wherein the electron transport layer material comprises: ZnO, TiO ₂ , SnO ₂ , Ta ₂ O ₃ , ZrO ₂ , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO , one or more of ZnLiO or InSnO.

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