CN114939385A - Preparation method of metal oxide colloidal solution, thin film and light-emitting device - Google Patents
Preparation method of metal oxide colloidal solution, thin film and light-emitting device Download PDFInfo
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Abstract
The application discloses a preparation method of a metal oxide colloidal solution, a film and a light-emitting device. The preparation method of the metal oxide colloidal solution comprises the following steps: mixing polyacrylic acid with the first solution to obtain a second solution; and mixing the solution containing the metal oxide with the second solution to obtain a metal oxide colloidal solution. According to the preparation method of the metal oxide colloidal solution, the polyacrylic acid is utilized to improve the film forming property of the metal oxide, so that the metal oxide is deposited into a film in a continuous and conformal manner, and the formed film has an excellent conformal coating effect on particles.
Description
Technical Field
The application relates to the technical field of display, in particular to a preparation method of a metal oxide colloidal solution, a film and a light-emitting device.
Background
Organic Light Emitting Diode (OLED) devices have the characteristics of self-luminescence, high contrast, fast response speed, lightness, thinness, flexibility and the like, and have become the main trend of display technology. Compared with the method of manufacturing the OLED device by vacuum thermal evaporation, the inkjet printing technology has become a mainstream manufacturing scheme of the large-size OLED device and the display device due to the advantages of high material utilization rate (> 95%), no use of a Fine Metal Mask (FMM), capability of manufacturing the large-size OLED display device, and the like. The ink-jet printing quantum dot device QLED is higher than the first floor by three advantages of high color gamut, pure chromaticity and long color. The main structure of the inkjet printing QLED device is Anode (Anode)/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/light emitting layer (EML)/Electron Transport Layer (ETL)/Cathode (Cathode). The prior art still has the problems that: after the QD material is printed into a film and dried, the film is a solid granular film, the wrapping performance of particles (particles) appearing in the printing process is poor, so that cathode metal in the process of manufacturing an electron transport layer is directly contacted with the particles (particles), or the film is formed along the edge of the particles (particles), the short circuit of a cathode and an anode is caused, a dark spot is formed, and the performance of a device and the yield of a product are influenced. Therefore, it is desirable to provide a method for preparing a metal oxide colloidal solution to solve the above problems.
Disclosure of Invention
The present application aims to provide a method for preparing a metal oxide colloidal solution, which can improve the defects in the prior art.
The embodiment of the application provides a preparation method of a metal oxide colloidal solution, which comprises the following steps:
mixing polyacrylic acid (PAA) with the first solution to obtain a second solution;
and mixing the solution containing the metal oxide with the second solution to obtain a metal oxide colloidal solution.
Optionally, in some embodiments of the present application, the metal oxide comprises zinc oxide (ZnO), tin oxide (SnO) 2 ) Aluminum-doped zinc oxide (Al-ZnO), magnesium-doped zinc oxide (Mg-ZnO), indium oxide (In) 2 O 3 ) Tin-doped indium oxide (Sn-In) 2 O 3 ) Zinc-doped indium oxide (Zn-In) 2 O 3 ) One or more of the nanoparticles of (a).
Optionally, in some embodiments of the present application, the first solution comprises at least one of diethylene glycol, triethylene glycol dimethyl ether, and 2-benzyloxyethanol.
Optionally, in some embodiments herein, the volume ratio of the polyacrylic acid to the first solution is 0.1 to 1.5: 9.
optionally, in some embodiments herein, the volume ratio of the diethylene glycol, the triethylene glycol dimethyl ether, and the 2-benzyloxyethanol is 12-22.5: 22.5-33: 45.
optionally, in some embodiments of the present application, the mixing method is an upside-down operation.
Optionally, in some embodiments of the present application, the method for preparing the solution containing metal oxide includes the following steps:
mixing the metal oxide with a mixed solvent to obtain a solution containing the metal oxide; the concentration of the solution containing the metal oxide is 10-50 mg/mL.
Alternatively, in some embodiments herein, the mixed solvent comprises chloroform and methanol. The volume ratio of the chloroform to the methanol is 1-3: 7-9.
Optionally, in some embodiments of the present application, the step of preparing the zinc oxide nanoparticles includes: and (3) adding (dropwise) the potassium hydroxide alcoholic solution and the polyacrylic acid alcoholic solution into the zinc oxalate alcoholic solution, stirring for reaction, precipitating, filtering and washing to obtain a solid, namely the zinc oxide nano-particles.
Optionally, in some embodiments of the present application, the preparation of the alcoholic solution of zinc oxalate comprises the steps of: dissolving zinc oxalate in an alcohol solvent to obtain the zinc oxalate alcohol solution; wherein the concentration of the zinc oxalate alcoholic solution is 0.02-0.1 g/mL. The alcohol solvent comprises one or more of methanol, ethanol and isopropanol.
The preparation method of the potassium hydroxide alcoholic solution comprises the following steps: dissolving potassium hydroxide (KOH) in an alcohol solvent to obtain the potassium hydroxide alcohol solution; wherein the concentration of the potassium hydroxide alcoholic solution is 0.02-0.30 g/mL. The alcohol solvent comprises one or more of methanol, ethanol and isopropanol.
The preparation method of the polyacrylic acid alcoholic solution comprises the following steps: dissolving polyacrylic acid in an alcohol solvent to obtain a polyacrylic acid alcohol solution; wherein the volume ratio of the polyacrylic acid to the alcohol solvent is 0.5-5: 50. the alcohol solvent comprises one or more of methanol, ethanol and isopropanol.
Correspondingly, the embodiment of the application also provides a film, which is prepared by adopting the metal oxide colloidal solution obtained by the preparation method of the metal oxide colloidal solution.
In addition, the embodiment of the application also provides a light-emitting device which comprises an anode layer, a hole function layer, a light-emitting layer, an electronic function layer and a cathode layer, wherein the electronic function layer comprises the thin film.
The beneficial effect of this application lies in:
according to the preparation method of the metal oxide colloidal solution, the polyacrylic acid can improve the film-forming property of the metal oxide, so that the metal oxide can be deposited into a film in a continuous and conformal manner. Moreover, the film formed by the preparation method disclosed by the application also has an excellent conformal coating effect on the particles.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a QLED device provided in an embodiment of the present application;
FIG. 2 is a graph showing the first luminescence test result of test example 1 of the present application;
FIG. 3 is a second graph showing the results of luminescence test in test example 1 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. In addition, in the description of the present application, the term "including" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or an order of establishment. Various embodiments of the invention may exist in a range of versions; it should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within the range, such as 1, 2, 3, 4, 5, and 6, for example, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the indicated range.
In the course of research and practice on the prior art, the inventors of the present application found that zinc oxide nanocrystals as electron transport layers are widely used in high-performance QLEDs; zinc oxide (ZnO) is a typical n-type oxide semiconductor, has characteristics of high carrier mobility, adjustable energy band structure, high transmittance in visible light band, and the like, and the colloidal zinc oxide nanoparticles also have excellent solution processability.
The embodiment of the application provides a preparation method of a metal oxide colloidal solution, a film and a light-emitting device. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments.
The embodiment of the application provides a preparation method of a metal oxide colloidal solution, which comprises the following steps:
mixing polyacrylic acid (PAA) with the first solution to obtain a second solution;
and mixing the solution containing the metal oxide with the second solution to obtain a metal oxide colloidal solution.
Further, the metal oxide is a nanoparticle. The metal oxide is selected from zinc oxide (ZnO), tin oxide (SnO) 2 ) Aluminum-doped zinc oxide (Al-ZnO), magnesium-doped zinc oxide (Mg-ZnO), indium oxide (In) 2 O 3 ) Tin-doped indium oxide (Sn-In) 2 O 3 ) Zinc doped indium oxide (Zn-In) 2 O 3 ) May be selected according to actual requirements.
In the embodiment of the application, the polyacrylic acid can improve the film forming property of the metal oxide, so that the metal oxide is deposited to form a film in a continuous and conformal manner.
In some embodiments of the present application, the volume ratio of the polyacrylic acid to the first solution may be 0.1: 9. 0.2: 9. 0.5: 9. 0.8: 9. 1.0: 9. 1.2: 9. 1.4: 9 or 1.5: 9.
in some embodiments of the present application, the first solution comprises at least one of diethylene glycol, triethylene glycol dimethyl ether, and 2-benzyloxyethanol. Further, when the first solution comprises diethylene glycol, triethylene glycol dimethyl ether and 2-benzyloxyethanol, the volume ratio of the diethylene glycol, the triethylene glycol dimethyl ether to the 2-benzyloxyethanol is 12-22.5: 22.5-33: 45, a first step of; for example, the ratio of 12: 22.5: 45. 22.5: 33: 45. 12: 33: 45. 22.5: 22.5: 45. 16: 28: 45. 13: 30: 45. 20: 24: 45 or 18: 27: 45. the volume ratio may be arbitrarily selected within the range.
In the embodiment of the application, the mixing method can be an up-down inversion operation, and the up-down inversion time can be 3-10 min. For example, the time for inversion may be 3min, 4min, 5min, 6min, 7min, 8min, 9min, or 10 min.
In some embodiments, the method for preparing a metal oxide colloidal solution comprises the steps of:
mixing 1.8mL of diethylene glycol, 2.7mL of triethylene glycol dimethyl ether and 4.5mL of 2-benzyloxyethanol, and inverting the mixture up and down for 3-10 min to obtain a first solution;
adding 0.1mL of polyacrylic acid into the first solution, and inverting the solution up and down for 5min to mix the solution uniformly to obtain a second solution;
and mixing the second solution with a solution containing zinc oxide nanoparticles, and inverting the second solution from top to bottom for 5min to obtain a metal oxide colloidal solution.
In some embodiments of the present application, the method for preparing the metal oxide-containing solution comprises the following steps: and mixing the metal oxide and the mixed solvent to obtain a solution containing the metal oxide.
The concentration of the metal oxide containing solution may be 10 to 50mg/mL, which may be adjusted as desired. For example, the metal oxide can be present in the metal oxide in an amount of 10mg/mL, 15mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 45mg/mL, or 50 mg/mL. Further, the mixed solvent includes chloroform and methanol. Further, the volume ratio of the chloroform to the methanol may be 1: 9. 1: 7. 3: 7 or 1: 3.
in some embodiments of the present application, the metal oxide may be zinc oxide nanoparticles.
In some embodiments of the present application, the step of preparing the zinc oxide nanoparticles comprises: adding KOH alcoholic solution and polyacrylic acid alcoholic solution into zinc oxalate alcoholic solution, stirring for reaction, precipitating, filtering, washing to obtain solid, and obtaining the zinc oxide nano-particles. Further, the KOH alcoholic solution and the polyacrylic acid alcoholic solution are dripped into the zinc oxalate alcoholic solution, and the dripping time can be 20min, 25min, 30min, 35min or 40 min. The stirring reaction time can be 0.5h, 1h or 1.5 h. The precipitation can be standing for 20min, 25min, 28min, 30min, 32min, 35min or 40 min. For example, the washing includes: adding 50mL of methanol into the solid obtained by precipitation, stirring for 5min, and removing liquid; this was repeated several times, leaving a washed solid. For example, it may be repeated 2 times, 3 times, 4 times, 5 times, etc.
In some embodiments, the alcoholic zinc oxalate solution is prepared by the steps of: dissolving zinc oxalate in an alcohol solvent to obtain the zinc oxalate alcohol solution. Furthermore, the concentration of the zinc oxalate alcoholic solution is 0.02-0.1 g/mL. The weight volume ratio of the zinc oxalate to the alcohol solvent is 2-10: 100 (g/mL). Further, the operation of dissolving zinc oxalate in the alcohol solvent is as follows: mixing zinc oxalate with an alcohol solvent, and stirring for 3-10 min at 55-65 ℃. For example, stirring is carried out at 60 ℃ for 5 min. Further, the alcohol solvent comprises one or more of methanol, ethanol and isopropanol.
In some embodiments, the alcoholic potassium hydroxide solution is prepared by: dissolving KOH in an alcohol solvent to obtain the potassium hydroxide alcohol solution. The concentration of the potassium hydroxide alcoholic solution is 0.02-0.30 g/mL. It can also be said that the weight volume ratio of the KOH to the alcohol solvent is 1-15: 50 (g/mL). Further, the operation of dissolving KOH in the alcohol solvent is as follows: mixing KOH and an alcohol solvent, and stirring for 3-10 min at 55-65 ℃. For example, stirring is carried out at 60 ℃ for 5 min. Further, the alcohol solvent comprises one or more of methanol, ethanol and isopropanol.
In some embodiments, the preparation of the hydroalcoholic solution comprises: dissolving polyacrylic acid in an alcohol solvent to obtain the polyacrylic acid alcohol solution. The volume ratio of the polyacrylic acid to the alcohol solvent may be 0.5 to 5: 50; for example, the volume ratio may be 0.5: 50. 0.8: 50. 1: 50. 2: 50. 3: 50. 4: 50 or 5: 50. further, the operation of dissolving the polyacrylic acid in the alcohol solvent is as follows: mixing polyacrylic acid with an alcohol solvent, and stirring for 3-10 min at 55-65 ℃. For example, stirring is carried out at 60 ℃ for 5 min. Further, the alcohol solvent comprises one or more of methanol, ethanol and isopropanol.
In a specific embodiment, the preparation method of the solution containing zinc oxide nanoparticles comprises the following steps:
mixing zinc oxalate (3g) with methanol (100mL), and stirring at 60 ℃ for 5min to dissolve the zinc oxalate in the methanol to obtain a zinc oxalate alcoholic solution;
mixing KOH (1.5g) and methanol (50mL), stirring at 60 deg.C for 5min to dissolve KOH in methanol to obtain KOH alcoholic solution;
mixing polyacrylic acid PAA (1mL) with methanol (50mL), and stirring at 60 ℃ for 5min to dissolve the polyacrylic acid in the methanol to obtain a polyacrylic acid alcohol solution;
dripping the KOH alcoholic solution and the polyacrylic acid alcoholic solution into the zinc oxalate alcoholic solution for 30 min;
stirring for 1h, and standing for 30 min;
pouring off the liquid, leaving the solid, adding 50mL of methanol, stirring for 5min, and pouring off the liquid; repeating for several times to leave solid;
mixing the solid 10mg with chloroform 0.3mL, and adding methanol 0.7mL to obtain the solution containing zinc oxide nanoparticles.
The application specifically provides a method for preparing ZnO nanoparticles and a method for preparing a colloidal ZnO solution, which are used for solving the problem of dark spots of a QLED device and providing a manufacturing scheme of an ink-jet printing QLED device and a display device.
In the application, the metal oxide colloid solution contains polyacrylic acid (PAA) and metal oxide, the polyacrylic acid (PAA) forms a strong cross-linking structure when being heated, and the PAA-stabilized ZnO is deposited on the surface of the QD EML in a continuous and conformal mode after being dried to form a film, and has a conformal coating mode on particles. Due to the conformal coating, the Particle can be completely covered, and the short circuit of the cathode and the anode is avoided.
In addition, the functional group of the polyacrylic acid has strong hydrogen bonds and coordination bonds with the metal surface, and can also form covalent coordination bonds with the metal of the luminescent layer quantum dots and the cathode metal, so that all layers of the device are integrated, namely, the layers and the process, and the display technology and the bending resistance of the flexible QLED device in the future are greatly facilitated.
The embodiment of the application also provides a film, which is prepared by adopting the metal oxide colloidal solution obtained by the preparation method of the metal oxide colloidal solution.
Embodiments also provide a light emitting device including an anode layer, a hole functional layer, a light emitting layer, an electron functional layer, and a cathode layer, wherein the electron functional layer includes a thin film as described above, such as PAA-ZnO.
Referring to fig. 1, the light emitting device is a QLED device, and includes a TFT device, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, a PAA-ZnO layer, a cathode, and an encapsulation layer on the TFT device.
The present application has been repeated several times, and the present invention will now be described in further detail with reference to some test results, which will be described in detail below with reference to specific examples.
Example 1
The embodiment provides a preparation method of a metal oxide colloidal solution, which comprises the following steps:
step 1: dissolving zinc oxalate (3g) in methanol (100mL), and stirring at 60 ℃ for 5min to obtain a zinc oxalate alcoholic solution;
step 2: KOH (1.5g) was dissolved in methanol (50mL), and the mixture was stirred at 60 ℃ for 5min to give a KOH alcoholic solution;
and step 3: dissolving polyacrylic acid (1mL) in methanol (50mL), and stirring at 60 deg.C for 5min to obtain polyacrylic acid alcoholic solution;
and 4, step 4: dripping the KOH alcoholic solution in the step 2 and the polyacrylic acid alcoholic solution in the step 3 into the zinc oxalate alcoholic solution in the step 1, and controlling the dripping time to be 30 min;
and 5: stirring for 1 h; standing for 30 min;
step 6: pouring off the liquid, leaving the solid, adding 50mL of methanol, stirring for 5min, and pouring off the liquid;
and 7: repeating the step 6 twice, and leaving solid to obtain ZnO nanoparticles;
and 8: taking 10mg of the ZnO nanoparticles obtained in the step 7, adding 0.3mL of chloroform, adding 0.7mL of methanol, and mixing to obtain a solution containing metal oxide;
and step 9: taking 1.8mL of diethylene glycol, 2.7mL of triethylene glycol dimethyl ether and 4.5mL of 2-benzyloxyethanol, inverting the mixture up and down for 5min, and mixing to obtain a first solution;
step 10: adding 0.1mL of polyacrylic acid PAA into the first solution obtained in the step 9, inverting the mixture up and down for 5min, and mixing to obtain a second solution;
step 11: and (3) adding the second solution obtained in the step (10) into the solution containing the metal oxide obtained in the step (8), inverting the solution for 5min, and mixing to obtain a metal oxide colloidal solution.
The above process can be used for proportional production.
Example 2
The embodiment provides a preparation method of a metal oxide colloidal solution, which comprises the following steps:
step 1: dissolving zinc oxalate (2.5g) in methanol (100mL), and stirring at 65 ℃ for 5min to obtain a zinc oxalate alcoholic solution;
step 2: dissolving KOH (1.2g) in methanol (50mL), and stirring at 55 deg.C for 10min to obtain KOH alcoholic solution;
and step 3: dissolving polyacrylic acid PAA (1mL) in methanol (50mL), and stirring at 65 deg.C for 5min to obtain polyacrylic acid alcoholic solution;
and 4, step 4: dripping the KOH alcoholic solution in the step 2 and the polyacrylic acid alcoholic solution in the step 3 into the zinc oxalate alcoholic solution in the step 1 for 30 min;
and 5: stirring for 1 h; standing for 30 min;
step 6: pouring off the liquid, leaving the solid, adding 50mL of methanol, stirring for 5min, and pouring off the liquid;
and 7: repeating the step 6 for three times, and leaving solid to obtain ZnO nanoparticles;
and 8: taking 15mg of the ZnO nanoparticles obtained in the step 7, adding 0.3mL of chloroform and 0.7mL of methanol, and mixing to obtain a solution containing metal oxide;
and step 9: taking 1.8mL of diethylene glycol, 2.7mL of triethylene glycol dimethyl ether and 4.5mL of 2-benzyloxyethanol, inverting the mixture up and down for 5min, and mixing to obtain a first solution;
step 10: adding 0.1mL of polyacrylic acid PAA into the first solution obtained in the step 9, inverting the mixture up and down for 5min, and mixing to obtain a second solution;
step 11: and (3) adding the second solution obtained in the step (10) into the solution containing the metal oxide obtained in the step (8), inverting the solution for 5min, and mixing to obtain a metal oxide colloidal solution.
The above process can be used for proportional production.
Example 3
The embodiment provides a preparation method of a metal oxide colloidal solution, which comprises the following steps:
step 1: dissolving zinc oxalate (10g) in methanol (100mL), and stirring at 60 ℃ for 5min to obtain a zinc oxalate alcoholic solution;
and 2, step: dissolving KOH (2g) in methanol (50mL), and stirring at 60 deg.C for 5min to obtain KOH alcoholic solution;
and step 3: dissolving polyacrylic acid (2mL) in methanol (50mL), and stirring at 60 deg.C for 5min to obtain polyacrylic acid alcoholic solution;
and 4, step 4: dripping the KOH alcoholic solution in the step 2 and the polyacrylic acid alcoholic solution in the step 3 into the zinc oxalate alcoholic solution in the step 1, and controlling the dripping time to be 30 min;
and 5: stirring for 1 h; standing for 30 min;
step 6: pouring off the liquid, leaving the solid, adding 50mL of methanol, stirring for 5min, and pouring off the liquid;
and 7: repeating the step 6 twice, and reserving solid to obtain ZnO nanoparticles;
and 8: taking 50mg of the ZnO nanoparticles obtained in the step 7, adding 0.3mL of chloroform and 0.7mL of methanol, and mixing to obtain a solution containing metal oxide;
and step 9: taking 1.8mL of diethylene glycol, 2.7mL of triethylene glycol dimethyl ether and 4.5mL of 2-benzyloxyethanol, inverting the mixture up and down for 5min, and mixing to obtain a first solution;
step 10: adding 0.1mL of polyacrylic acid PAA into the first solution obtained in the step 9, inverting the mixture up and down for 5min, and mixing to obtain a second solution;
step 11: and (3) adding the second solution obtained in the step (10) into the solution containing the metal oxide obtained in the step (8), inverting the solution for 5min, and mixing to obtain a metal oxide colloidal solution.
The above process can be produced in equal proportion.
Example 4
The embodiment provides a preparation method of a metal oxide colloidal solution, which comprises the following steps:
step 1: dissolving zinc oxalate (3g) in methanol (100mL), and stirring at 60 ℃ for 5min to obtain a zinc oxalate alcoholic solution;
step 2: dissolving KOH (3g) in methanol (50mL), and stirring at 60 deg.C for 5min to obtain KOH alcoholic solution;
and step 3: dissolving polyacrylic acid (5mL) in methanol (50mL), and stirring at 60 ℃ for 5min to obtain a polyacrylic acid alcohol solution;
and 4, step 4: dripping the KOH alcoholic solution obtained in the step (2) and the polyacrylic acid alcoholic solution obtained in the step (3) into the zinc oxalate alcoholic solution obtained in the step (1), and controlling the dripping time to be 30 min;
and 5: stirring for 1 h; standing for 30 min;
step 6: pouring out the liquid, leaving the solid, adding 50mL of methanol, stirring for 5min, and pouring out the liquid;
and 7: repeating the step 6 twice, and reserving solid to obtain ZnO nanoparticles;
and 8: taking 30mg of the ZnO nanoparticles obtained in the step 7, adding 0.3mL of chloroform and 0.7mL of methanol, and mixing to obtain a solution containing metal oxide;
and step 9: taking 1.8mL of diethylene glycol, 2.7mL of triethylene glycol dimethyl ether and 4.5mL of 2-benzyloxyethanol, inverting the mixture up and down for 5min, and mixing to obtain a first solution;
step 10: adding 0.1mL of polyacrylic acid PAA into the first solution obtained in the step 9, inverting the mixture up and down for 5min, and mixing to obtain a second solution;
step 11: and (3) adding the second solution obtained in the step (10) into the solution containing the metal oxide obtained in the step (8), inverting the solution for 5min, and mixing to obtain a metal oxide colloidal solution.
The above process can be produced in equal proportion.
Comparative example 1
This comparative example provides a conventional colloidal solution of ZnO nanoparticles, which is different from example 1 in that: no polyacrylic acid of the present application was added.
Device example 1
The embodiment of the device provides a QLED device, which comprises a TFT device, an anode, a hole injection layer, a hole transport layer, a luminescent layer, a PAA-ZnO layer, a cathode and an encapsulation layer, wherein the anode, the hole injection layer, the hole transport layer, the luminescent layer, the PAA-ZnO layer and the cathode are positioned on the TFT device; wherein, the PAA-ZnO layer adopts the metal oxide colloid solution of any one of the embodiments 1 to 4.
Test example 1
In this test example, the devices of example 1 and comparative example 1 of the present application were used to detect the emission of light, and the occurrence of dark spots was observed.
The results are shown in FIGS. 2 and 3. Fig. 2 is a graph showing the result of the luminescence test of the scheme of the comparative example, and dark spots caused by short-circuiting the cathode and anode are within the circle in fig. 2. Fig. 3 is a graph showing the results of the luminescence test of the embodiment of example 1 of the present application, with very few dark spots.
It can be seen that the dark spots of the examples of the present application are significantly less than those of the comparative examples. Therefore, the cathode and anode short circuit phenomenon caused by particles can be obviously reduced, and the generation of dark spots is further reduced.
In summary, the preparation method of the present application can make the film-forming property of the metal oxide particles, and the formed film has excellent conformal coating effect on the particles. The material obtained by the method is applied to devices, so that the dark spot phenomenon caused by the short circuit phenomenon of the cathode and the anode is greatly reduced.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The preparation method of the metal oxide colloidal solution, the thin film and the light emitting device provided in the embodiments of the present application are described in detail above, and the principle and the implementation manner of the present application are explained in the present application by applying specific examples, and the description of the above embodiments is only used to help understanding the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (11)
1. A method for preparing a metal oxide colloidal solution, comprising the steps of:
mixing polyacrylic acid with the first solution to obtain a second solution;
and mixing the solution containing the metal oxide with the second solution to obtain a metal oxide colloid solution.
2. The method of claim 1, wherein the metal oxide comprises one or more of nanoparticles of zinc oxide, tin oxide, aluminum-doped zinc oxide, magnesium-doped zinc oxide, indium oxide, tin-doped indium oxide, and zinc-doped indium oxide.
3. The method of preparing a metal oxide colloidal solution according to claim 1, wherein the first solution comprises at least one of diethylene glycol, triethylene glycol dimethyl ether, and 2-benzyloxyethanol.
4. The method of preparing a metal oxide colloidal solution according to claim 1, wherein the volume ratio of the polyacrylic acid to the first solution is 0.1 to 1.5: 9.
5. the method for preparing a metal oxide colloidal solution according to claim 3, wherein the first solution comprises diethylene glycol, triethylene glycol dimethyl ether and 2-benzyloxyethanol, and the volume ratio of the diethylene glycol, the triethylene glycol dimethyl ether and the 2-benzyloxyethanol is 12-22.5: 22.5-33: 45.
6. the method for preparing a metal oxide colloidal solution according to claim 1, wherein the method for preparing a metal oxide-containing solution comprises the steps of:
mixing the metal oxide with a mixed solvent to obtain a solution containing the metal oxide; the concentration of the solution containing the metal oxide is 10-50 mg/mL.
7. The method for preparing a metal oxide colloidal solution according to claim 1, wherein the mixed solvent comprises chloroform and methanol; the volume ratio of the chloroform to the methanol is 1-3: 7-9.
8. The method for preparing a metal oxide colloidal solution according to claim 2, wherein the step of preparing the zinc oxide nanoparticles comprises: adding a potassium hydroxide alcoholic solution and a polyacrylic acid alcoholic solution into a zinc oxalate alcoholic solution, stirring for reaction, precipitating, filtering, and washing to obtain a solid, namely the zinc oxide nano-particles.
9. The method for preparing a colloidal solution of metal oxides as defined in claim 8, wherein the alcoholic solution of zinc oxalate is prepared by the steps of: dissolving zinc oxalate in an alcohol solvent to obtain the zinc oxalate alcohol solution; wherein the concentration of the zinc oxalate alcoholic solution is 0.02-0.1 g/mL; and/or
The preparation method of the potassium hydroxide alcoholic solution comprises the following steps: dissolving potassium hydroxide in an alcohol solvent to obtain the potassium hydroxide alcohol solution; wherein the concentration of the potassium hydroxide alcoholic solution is 0.02-0.30 g/mL; and/or
The preparation method of the polyacrylic acid alcoholic solution comprises the following steps: dissolving polyacrylic acid in an alcohol solvent to obtain a polyacrylic acid alcohol solution; wherein the volume ratio of the polyacrylic acid to the alcohol solvent is 0.5-5: 50.
10. a film produced by using the metal oxide colloidal solution obtained by the method for producing a metal oxide colloidal solution according to any one of claims 1 to 9.
11. A light-emitting device comprising an anode layer, a hole-functional layer, a light-emitting layer, an electron-functional layer and a cathode layer, the electron-functional layer comprising the thin film according to claim 10.
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