CN108682752B - Manufacturing method of charge transport layer, ink and photoelectric device - Google Patents
Manufacturing method of charge transport layer, ink and photoelectric device Download PDFInfo
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- CN108682752B CN108682752B CN201810458159.6A CN201810458159A CN108682752B CN 108682752 B CN108682752 B CN 108682752B CN 201810458159 A CN201810458159 A CN 201810458159A CN 108682752 B CN108682752 B CN 108682752B
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Abstract
The application provides a manufacturing method of a charge transport layer, the charge transport layer, ink and a photoelectric device. The manufacturing method comprises the following steps: preparing nanoparticles, wherein the nanoparticles comprise a core body and a shell layer coated outside the core body, the core body is made of an insulating material and/or a semiconductor material, the shell layer is made of a semiconductor electron transport material or a hole transport material, and the forbidden bandwidth of the semiconductor material is greater than that of the shell layer; the nanoparticles are disposed on a substrate using a solution method to form a charge transport layer for transporting charges. The method is simple to operate and suitable for various solution process procedures, and the energy level of the charge transport layer obtained by manufacturing can reach a stable state in the crystallization process, so that the influence of the fusion of the nanocrystalline serving as a transport material in the crystallization process on the transport performance in the prior art is effectively reduced, and the stability of the device is improved.
Description
Technical Field
The application relates to the field of photoelectricity, in particular to a manufacturing method of a charge transport layer, the charge transport layer, ink and a photoelectric device.
Background
In the prior art, two types of charge transport layers are commonly used, the first type is a completely continuous conductive layer, and as shown in fig. 1, the charge transport layer 01 does not have the characteristics of a nano material.
The second is a film formed by the accumulation of conductive nanocrystals, as shown in fig. 2. The nanocrystal 02 as the material of the charge transport layer appeared prominent on the QLED and was suitable for solution processing. However, this charge transport layer has problems in actual fabrication, and is discussed in two cases.
In the first case, the nanocrystal surface is very stable, has a clear boundary, and does not have the problem of boundary fusion, but because the surface of each nanocrystal has a non-conductive ligand, the transmission performance between nanocrystals is poor, and charge transfer needs to be realized in a jumping manner.
In the second case, the surface of the nanocrystal is unstable, and after the nanocrystal is formed into a film, an oriented crystallization process exists, which can cause the crystal growth of the nanocrystal to become large, and the process is gradually performed and irreversible, so that fusion occurs between crystal grains, and a crystal grain with a larger size is formed. This aspect increases the conductivity of the charge transport layer; on the other hand, the performance of the charge transport layer is not stable enough due to the fact that the crystal growth of the nanocrystalline is increased, the quantum confinement effect is weakened, the energy level structure of the material of the charge transport layer is changed, the conduction band bottom is deepened, and the light emitting efficiency of the device is reduced due to the deepening of the conduction band bottom for a blue-green QLED device with high electronic injection requirements.
The above information disclosed in this background section is only for enhancement of understanding of the background of the technology described herein and, therefore, certain information may be included in the background that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
Disclosure of Invention
The application mainly aims to provide a manufacturing method of a charge transport layer, the charge transport layer, ink and a photoelectric device, so as to solve the problem that nanocrystals in the charge transport layer in the prior art are fused and agglomerated.
In order to achieve the above object, according to an aspect of the present application, there is provided a method of fabricating a charge transport layer, the method comprising: preparing a nanoparticle, wherein the nanoparticle comprises a core body and a shell layer coated outside the core body, the core body is made of an insulating material and/or a semiconductor material, the shell layer is made of a semiconductor electron transport material or a semiconductor hole transport material, and the forbidden band width of the semiconductor material is greater than that of the shell layer; the nanoparticles are disposed on a substrate by a solution method to form the charge transport layer for transporting charges.
Further, the above solution method includes one of a spin coating method, an ink jet printing method, a spray coating method, a screen printing method, a blade coating method, a droplet coating method, a brush coating method, a transfer method, a dip coating method, and a roll coating method.
Further, the solution method is a spin coating method, and the step of forming the charge transport layer by the spin coating method includes: step S1, preparing a spin-on solution, where the spin-on solution includes a spin-on solvent and the nanoparticles in the spin-on solvent; in step S2, the spin coating solution is spin coated on the surface of the substrate and dried to form the charge transport layer.
Further, the solution method is an ink-jet printing method, and the step of forming the charge transport layer by the ink-jet printing method includes: preparing printing ink, wherein the printing ink comprises a printing solvent and the nano particles in the printing solvent; and printing the printing ink on the surface of the substrate by adopting an ink-jet printing method and drying to form the charge transport layer.
Further, the preparation process of the nanoparticles comprises the following steps: mixing a core body, a dispersion solution, and a metal precursor of the electron transport material or the hole transport material, heating and stirring the mixture to form a mixed solution in which the core body is dispersed in the dispersion solution; and adding an alkali solution into the mixed solution, wherein the alkali solution reacts with the metal precursor to form a shell layer on the surface of the core body, so as to form the nano particles.
Further, the particle size of the core body is between 1 and 100nm, preferably between 3 and 10 nm; the thickness of the shell layer is 1 to 10nm, preferably 2 to 5 nm.
The material of the core body is a wide bandgap semiconductor material, the bandgap Eg of the wide bandgap semiconductor material is greater than or equal to 2.3eV, or the material of the core body is an insulating material, preferably the insulating material is selected from SiO2、ZrO2、HfO2、Al2O3And MgO.
Further, the electron transport material is selected from SnO2、TiO2、WO3And ZnO, the hole transport material is selected from CuO and Cu2At least one of O and NiO.
According to another aspect of the present application, there is provided a charge transport layer comprising a plurality of stacked nanoparticles, wherein the nanoparticles comprise a core and a shell coated outside the core, the core is made of an insulating material and/or a semiconductor material, the shell is made of a semiconductor electron transport material or a semiconductor hole transport material, and the semiconductor material has a higher energy gap than the material of the shell.
According to still another aspect of the present application, there is provided an ink including a nanoparticle and a solvent, wherein the nanoparticle includes a core and a shell coated outside the core, the core is made of an insulating material and/or a semiconductor material, the shell is made of a semiconductor electron transport material or a semiconductor hole transport material, and the semiconductor material has a higher energy gap than the material of the shell.
According to a further aspect of the present application, there is provided an optoelectronic device comprising a charge transport layer as described above.
By applying the technical scheme of the application and adopting the solution method to prepare the charge transport layer, the method is simple to operate and is suitable for various solution method manufacturing processes. The charge transport layer is formed to include a plurality of nanoparticles, each of which includes a core body and a shell layer, the shell layer uses a semiconductor charge transport material, i.e., an electron transport material or a hole transport material, and the core body uses a wide bandgap semiconductor or insulator material. The charge transport materials corresponding to the multiple shell layers are quasi-continuous honeycomb (or network) structures and play a role in transporting charges. In addition, the crystal grain size of the shell layer is limited in the crystallization process, namely the crystal grain size is slightly larger than 2 times of the thickness of the shell layer. Therefore, the energy level of the manufactured charge transport layer can reach a stable state in the crystallization process, the influence of the fusion of the nanocrystalline serving as a transport material in the crystallization process on the transport performance in the prior art is effectively reduced, and the stability of the device is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. In the drawings:
FIG. 1 shows a schematic structure of a charge transport layer in the prior art;
FIG. 2 shows a schematic structure of another charge transport layer in the prior art; and
fig. 3 shows a schematic structural diagram of an embodiment of a charge transport layer according to the present application.
Wherein the figures include the following reference numerals:
01. a charge transport layer; 02. a nanocrystal; 10. a charge transport layer; 11. a core body; 12. and (4) shell layer.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. Also, in the specification and claims, when an element is described as being "connected" to another element, the element may be "directly connected" to the other element or "connected" to the other element through a third element.
As described in the background art, in the prior art, the nanocrystals in the charge transport layer are easy to fuse and agglomerate, and in order to solve the above technical problems, the present application provides a method for manufacturing a charge transport layer, ink, and a photoelectric device.
In an exemplary embodiment of the present application, there is provided a method of fabricating a charge transport layer, the method including: preparing nanoparticles, as shown in fig. 3, wherein the nanoparticles comprise a core body 11 and a shell layer 12 coated outside the core body, the core body 11 is made of an insulating material and/or a semiconductor material, the shell layer 12 is made of a semiconductor electron transport material or a semiconductor hole transport material, and the material of the core body has a forbidden band width greater than that of the material of the shell layer; the nanoparticles are disposed on a substrate by a solution method to form the charge transport layer 10 for transporting charges as shown in fig. 3.
By applying the technical scheme of the application and adopting the solution method to prepare the charge transport layer, the method is simple to operate, and the formed charge transport layer is more uniform. The charge transport layer is formed to include a plurality of nanoparticles, each of which includes a core body and a shell layer, the shell layer uses a semiconductor charge transport material, i.e., an electron transport material or a hole transport material, and the core body uses a wide bandgap semiconductor or insulator material. The charge transport materials corresponding to the multiple shell layers are quasi-continuous honeycomb (or network) structures and play a role in transporting charges. In addition, the crystal grain size of the shell layer is limited in the crystallization process, namely the crystal grain size is slightly larger than 2 times of the thickness of the shell layer. Therefore, the energy level of the manufactured charge transport layer can reach a stable state in the crystallization process, the influence of the fusion of the nanocrystalline serving as a transport material in the crystallization process on the transport performance in the prior art is effectively reduced, and the stability of the device is improved.
It should be noted that the substrate may be a structural layer disposed in contact with the charge transport layer in a specific device, for example, for a light emitting device, the charge transport layer is often disposed in contact with the light emitting layer, and then the light emitting layer may serve as a substrate, so that the charge transport layer is actually formed directly on the light emitting layer. The substrate may not be a structural layer of the device, and may be used to provide a substrate for the charge transport layer, and after the charge transport layer is formed, the substrate may be removed by a suitable method, i.e. separated from the charge transport layer, to facilitate the application of the subsequent charge transport layer in the device.
The solution method of the present application may be any solution method available in the art, and those skilled in the art can select a suitable solution method to dispose the nanoparticles on the substrate according to actual conditions.
In order to improve efficiency and simplify the process, in one embodiment of the present application, the solution method includes one of a spin coating method, an inkjet printing method, a spray coating method, a screen printing method, a blade coating method, a drop coating method, a brush coating method, a transfer method, a dip coating method, and a roll coating method.
When the nano particles are arranged on the substrate by adopting a spin coating method to form the charge transport layer, the specific process comprises the following steps: step S1, preparing a spin-on solution, where the spin-on solution includes a spin-on solvent and the nanoparticles in the spin-on solvent; in step S2, the spin coating solution is spin coated on the surface of the substrate and dried to form the charge transport layer.
Specifically, the step S2 includes: dropping the spin-coating solution on the substrate placed on a spin-coating apparatus; controlling the rotating speed of the spin coater to be 1000-6000 revolutions per minute, and spin-coating the spin-coating solution for 60-120 seconds to form a spin-coating layer; the spin-coated layer is heated to be dried to form the charge transport layer, and in order to form a charge transport layer with good performance and reduce the influence on the substrate material, the heating temperature is preferably 50 to 150 ℃, and the heating time is preferably 20 to 180 min.
The spin-coating solvent can be any feasible solvent, and those skilled in the art can select a suitable solvent as the spin-coating solvent in the present application according to practical situations.
In a specific embodiment, the spin-coating solvent is selected from one or more of ethanol, butanol, methoxyethanol, and octane.
When the nanoparticle is disposed on the substrate by an ink-jet printing method to form the charge transport layer, the specific process includes: preparing printing ink, wherein the printing ink comprises a printing solvent and the nano particles in the printing solvent; and printing the printing ink on the surface of the substrate by adopting an ink-jet printing method and drying to form the charge transport layer.
Heating and drying the printing ink layer on the substrate to form the charge transport layer; in order to form a charge transport layer with good performance and reduce the influence on the substrate material, the heating temperature is preferably between 80 and 200 ℃, and the heating time is preferably between 20 and 180 min.
In a specific embodiment of the present application, the printing solvent includes one or more of n-hexanol, n-octanol, dodecane, and tetradecane. Therefore, the requirement of printing on the boiling point of the solvent can be met, and the physical properties such as the viscosity, the surface tension, the volatility and the like of the ink can be freely adjusted.
Of course, the printing solvent of the present application is not limited to the above-mentioned kind, and may be any other solvent available in the prior art, and those skilled in the art can select a suitable solvent as the printing solvent of the present application according to practical situations.
In another embodiment of the present application, the process for preparing the nanoparticle includes: mixing a core body, a dispersion solution, and an electron transport material or a metal precursor of the hole transport material, heating and stirring to form a mixed solution in which the core body is dispersed in the dispersion solution; and adding an alkali solution into the mixed solution, wherein the alkali solution reacts with the metal precursor to form a shell layer on the surface of the core body, so as to form the nano particles. The process is simple to operate and high in preparation speed, and the obtained nano particles with the core-shell structures are uniform in size distribution. Specifically, for example, when a ZnO shell is fabricated, the metal precursor is a dimethyl sulfoxide DMSO solution of zinc acetate, and the alkali solution is a tetramethyl ammonium hydroxide solution.
In the method, the addition amount and the reaction time of the metal precursor and the alkali solution are controlled to obtain the nano particles coated with shell layers with different thicknesses.
Of course, the process for preparing nanoparticles of the present application is not limited to the above process, and may be other methods in the prior art, such as a one-pot method.
In an embodiment of this application, the particle size of above-mentioned nuclear body 11 is between 1 ~ 100nm, can guarantee like this that charge transport is unobstructed not obstructed better, has guaranteed the good transmission performance of this charge transport layer. In order to further improve the transport performance of the charge transport layer, the particle size of the core body 11 is preferably 3-10 nm.
In order to further ensure that the transmission rate of the carriers in the charge transport layer is high and the elapsed time of the carriers in the charge transport layer is short, in an embodiment of the present application, the thickness of the shell layer is between 1nm and 10nm, preferably between 2nm and 5 nm.
In order to further ensure that a good quantum confinement effect can be formed in the charge transport layer, in an embodiment of the present application, the material of the core body is a wide bandgap semiconductor material, and the bandgap Eg of the wide bandgap semiconductor material is greater than or equal to 2.3eV, such as ZnS, CdS and ZnSe.
Of course, the material of the above-mentioned core body of the present application is not necessarily a wide bandgap semiconductor material, but may be an insulating material, and specifically, the insulating material may be selected from SiO2、ZrO2、HfO2、Al2O3And MgO. The insulating material may also be polymeric nanoparticles.
Of course, when the material of the core body is an insulating material, the specific kind of the insulating material is not limited to the above-mentioned insulating material, and may be other insulating materials in the prior art, and those skilled in the art may select an appropriate insulating material to form the core body of the present application according to actual situations, and will not be described herein again.
When the charge transport material includes the above-mentioned electron transport material, the above-mentioned electron transport material is an n-type semiconductor material in order to increase the mobility rate of electrons and further shorten the transport time of electrons in the charge transport layer.
In a specific embodiment, the n-type semiconductor material includes In2O3、SnO2、ITO、TiO2、V2O5、MoO3、WO3And ZnO, specifically, the n-type semiconductor material may be one of the above materials, or a mixture of the materials, and one skilled in the art can select a suitable material to form the charge transport layer according to practical situations. The Fermi level of the n-type semiconductor materials is distributed between-7 eV and-4 eV, the mobility distribution is wide, and different requirements of different devices on the charge transport layer can be met.
Of course, the n-type semiconductor material of the present application is not limited to the above-mentioned ones, and may be any n-type semiconductor material that can be used as an electron transport material in the prior art, and those skilled in the art can select a suitable n-type semiconductor material to form the above-mentioned charge transport layer of the present application according to practical situations, for example, select ZnO doped with Al.
When the charge transport material includes the hole transport material, the hole transport material is a p-type semiconductor material in order to increase the mobility rate of holes and further shorten the transport time of holes in the charge transport layer.
The p-type semiconductor material can be any p-type semiconductor material which can be used as a hole transport material in the prior art, and a person skilled in the art can select a suitable p-type semiconductor material to form the charge transport layer according to practical situations,
in a specific embodiment, the p-type semiconductor material includes CuO and Cu2At least one of O and NiO, and likewise, the p-type semiconductor material may be one of these three materials or a mixture of these three materials, and those skilled in the art can select a suitable material to form the charge transport layer of the present application according to actual circumstances. The Fermi level of the p-type semiconductor materials is distributed between-7 eV and-4 eV, the mobility distribution is wide, and different requirements of different devices on the charge transport layer can be met.
The shape of the nucleus of the present application is spherical, cubic, regular tetrahedral or octahedral. The shapes have higher symmetry, and the performance of the charge transport layer can be further ensured to be more uniform.
Of course, the nucleus of the present application is not limited to the several shapes mentioned above, but may be any other shape, such as an irregular shape, and the like.
The shapes of the nuclei in the same charge transport layer may be the same or different, and those skilled in the art can select nuclei of the same shape or nuclei of different shapes according to actual conditions.
In another exemplary embodiment of the present application, a charge transport layer is provided, as shown in fig. 3, which is manufactured by any one of the above-mentioned manufacturing methods. The nanoparticles in the dried charge transport layer may be stacked, that is, at least a part of two adjacent nanoparticles are in direct contact with each other. The packing of the nanoparticles is largely dependent on the concentration of nanoparticles in the charge transport ink.
The charge transport layer comprises a plurality of nanoparticles, each of which comprises a core body 11 and a shell layer 12, the shell layer uses a semiconductor charge transport material, i.e., an electron transport material or a hole transport material, and the core body uses a wide bandgap semiconductor or insulator material. The charge transport materials corresponding to the multiple shell layers are quasi-continuous honeycomb (or network) structures and play a role in transporting charges. In addition, the crystal grain size of the shell layer is limited in the crystallization process, namely the crystal grain size is slightly larger than 2 times of the thickness of the shell layer. Therefore, the energy level of the manufactured charge transport layer can reach a stable state in the crystallization process, the influence of the fusion of the nanocrystalline serving as a transport material in the crystallization process on the transport performance in the prior art is effectively reduced, and the stability of the device is improved.
In another exemplary embodiment of the present application, there is provided a charge transport layer 10 comprising a plurality of stacked nanoparticles, the nanoparticles comprising a core body 11 and a shell layer 12 coated outside the core body 11, the core body 11 being made of an insulating material and/or a semiconductor material, the shell layer 12 being made of a semiconductor electron transport material or a semiconductor hole transport material, and the semiconductor material having a higher forbidden band width than the material of the shell layer 12. The transport material in the charge transport layer has stability, thereby improving the stability of the device having the charge transport layer.
In another exemplary embodiment of the present application, an ink is provided, the ink including nanoparticles and a solvent, the nanoparticles including a core body and a shell layer coated outside the core body, the core body being made of an insulating material and/or a semiconductor material, the shell layer being made of a semiconductor electron transport material or a semiconductor hole transport material, and the semiconductor material having a higher energy gap than the material of the shell layer. The charge transport layer prepared by using the charge transport ink has stability, so that the stability of a device with the charge transport layer is improved.
In another exemplary embodiment of the present application, there is provided an optoelectronic device comprising a charge transport layer, the charge transport layer being any one of the charge transport layers described above.
The photoelectric device comprises the charge transport layer, so that the transmission efficiency of electrons and/or holes is extremely high and stable. The optoelectronic device may be a solar cell or an electroluminescent device. The solar cell has higher photoelectric conversion efficiency, and the electroluminescent device has better external quantum efficiency.
The photoelectric device may include one charge transport layer, or may include a plurality of charge transport layers, and when a plurality of charge transport layers are included, the plurality of charge transport layers may be the same or different, and may be specifically configured according to actual conditions. For example, the light emitting device includes two charge transport layers, one of which is an electron charge transport layer and the charge transport material of which is an electron transport material; the other charge transport layer is a hole charge transport layer, the charge transport material is a hole transport material, and the two charge transport layers can be respectively arranged on two sides of the light emitting layer.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described below with reference to specific embodiments.
Example 1
Manufacturing the electron charge transport layer, wherein the specific manufacturing process comprises the following steps:
preparing nano particles: mixing 0.2g of core body, 30ml of dispersion solution and 0.8g of metal precursor, heating and stirring to form a mixed solution, wherein in the mixed solution, the core body is dispersed in the dispersion solution, the core body is made of insulating material zirconium oxide, is spherical and has the particle size of 1nm, the dispersion solution is a DMSO solution, and the metal precursor is zinc acetate; adding 3.2ml of aqueous alkali tetramethyl ammonium hydroxide methanol into the mixed solution, reacting the aqueous alkali with the metal precursor for 10min to form a ZnO shell layer on the surface of the core body, wherein the thickness of the shell layer is 1nm, and thus forming the nano particles.
Preparing printing ink: the 1g of nanoparticles prepared above and 10ml of printing solvent were mixed to form a printing ink.
And printing the printing ink on the surface of the substrate by adopting an ink-jet printing method to form a printing ink layer.
And heating the printing ink layer on the substrate to dry to form the charge transport layer, wherein the heating temperature is 80 ℃, the heating time is 180min, and the thickness of the formed charge transport layer is 40 nm.
The substrate is a quantum dot light-emitting layer, and the finally formed light-emitting device comprises an anode, a hole injection layer, a hole charge transport layer, a light-emitting layer, an electron charge transport layer and a cathode which are sequentially arranged.
The anode is made of ITO (indium tin oxide) and has the thickness of 150nm, the quantum dot layer is made of CdSe/ZnS red core-shell quantum dots, and the quantum dot layer is 20nm thick; the hole functional layer is poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid PEDOT: (ii) a superposed layer of structural layers of PSS and Poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD), the thicknesses of the two structural layers being 40nm and 30nm, respectively; the cathode is made of Ag and has a thickness of 100 nm.
Example 2
The differences from example 1 are:
preparing nano particles: mixing 5g of core body, 30ml of dispersion solution and 2g of metal precursor, wherein the core body is an insulating material wide-bandgap semiconductor material zinc sulfide, the forbidden bandwidth is 3.59eV, and the particle size is 50nm, adding 8ml of alkaline solution tetramethyl ammonium hydroxide methanol into the mixed solution, and reacting the alkaline solution with the metal precursor for 120min to form a ZnO shell layer on the surface of the core body, wherein the thickness of the shell layer is 5nm, so as to form the nano particles.
The 1g of nanoparticles prepared above and 10ml of printing solvent were mixed to form a printing ink.
The temperature for heating the printing ink layer on the substrate was 130 ℃ for 100 min. The charge transport layer was formed to a thickness of 40 nm.
Example 3
The differences from example 1 are:
preparing nano particles: mixing 5g of core body, 30ml of dispersion solution and 2g of metal precursor, wherein the core body is an insulating material wide-bandgap semiconductor material zinc sulfide, the forbidden bandwidth is 3.59eV, and the particle size is 100nm, adding 8ml of alkaline solution tetramethyl ammonium hydroxide methanol into the mixed solution, and reacting the alkaline solution with the metal precursor for 120min to form a ZnO shell layer on the surface of the core body, wherein the thickness of the shell layer is 10nm, so as to form the nano particles.
The 1g of nanoparticles prepared above and 10ml of printing solvent were mixed to form a printing ink.
The temperature for heating the printing ink layer on the substrate is 200 ℃ and the time is 20 min. The charge transport layer was formed to a thickness of 30 nm.
Example 4
The differences from example 2 are:
preparing a nanocrystal: mixing 1g of core body, 30ml of dispersion solution and 2g of metal precursor, wherein the core body is an insulating material wide-bandgap semiconductor material zinc sulfide, the forbidden band width is 3.59eV, and the particle size is 3nm, adding 8ml of alkaline solution tetramethyl ammonium hydroxide methanol into the mixed solution, reacting the alkaline solution with the metal precursor for 30min, and forming a ZnO shell layer on the surface of the core body, wherein the thickness of the shell layer is 2nm, so as to form the nanocrystal.
Example 5
The differences from example 2 are:
preparing a nanocrystal: mixing 2g of core body, 30ml of dispersion solution and 2g of metal precursor, wherein the core body is an insulating material wide-bandgap semiconductor material zinc sulfide, the forbidden band width is 3.59eV, and the particle size is 8nm, adding 8ml of alkaline solution tetramethyl ammonium hydroxide methanol into the mixed solution, reacting the alkaline solution with the metal precursor for 40min, and forming a ZnO shell layer on the surface of the core body, wherein the thickness of the shell layer is 5nm, so as to form the nanocrystalline.
Example 6
The differences from example 4 are: adding 30ml of alkali solution tetramethyl ammonium hydroxide methanol into the mixed solution, and reacting the alkali solution with the metal precursor for 180min to form a ZnO shell layer on the surface of the core body, wherein the thickness of the shell layer is 10 nm.
Example 7
The differences from example 4 are: the particle size of the nucleus is 110 nm.
Example 8
The difference from example 1 is that: and manufacturing the hole injection layer, wherein the specific manufacturing process comprises the following steps:
preparing nano particles: mixing 0.2g of nucleome, 30ml of tert-butyl alcohol solution and 0.8g of nickel acetylacetonate in a 50ml hydrothermal reaction kettle, and heating and reacting for 20 hours at 200 ℃ to obtain the target core-shell structure nano particle with the shell thickness of 1 nm.
Preparing printing ink: the 1g of nanoparticles prepared above and 10ml of printing solvent were mixed to form a printing ink.
And printing the printing ink on the surface of the substrate by adopting an ink-jet printing method to form a printing ink layer.
And heating the printing ink layer on the substrate to dry to form the charge transport layer, wherein the heating temperature is 80 ℃, the heating time is 180min, and the thickness of the formed charge transport layer is 15 nm.
The substrate is an anode, and the finally formed light-emitting device comprises an anode, a hole injection layer, a hole charge transport layer, a light-emitting layer, an electron charge transport layer and a cathode which are sequentially arranged.
The anode is made of ITO (indium tin oxide) and has the thickness of 150nm, the quantum dot layer is made of CdSe/ZnS red core-shell quantum dots, and the quantum dot layer is 20nm thick; the hole charge transport layer is Poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD) with a thickness of 30 nm; the electron charge transmission layer is formed by accumulating 4nm colloid ZnO nano particles, and the thickness is 40 nm; the cathode is made of Ag and has a thickness of 100 nm.
Example 9
The differences from example 4 are: the particle size of the nucleus is 10 nm.
Comparative example 1
The differences from example 1 are: the material of the electron charge transport layer is ZnO.
Comparative example 2
The differences from example 1 are: the electron charge transport layer is formed by stacking ZnO conductive nanocrystals, the nanocrystals are spheres, and the average particle size is 4 nm.
The performance of the quantum dot electroluminescent devices of the above examples and comparative examples was tested by measuring the current density-voltage curve of the quantum dot electroluminescent device with Keithley2400, measuring the luminance of the quantum dot electroluminescent device with an integrating sphere (FOIS-1) in combination with an ocean optical spectrometer (QE-6500), and calculating the external quantum efficiency of the quantum dot electroluminescent device according to the measured current density and luminance, where the external quantum efficiency represents the ratio between the number of photons emitted from the luminescent device and the number of electrons injected into the device in the observation direction, which is an important parameter for the luminous efficiency of the light-emitting device of the characterizer, and the higher the external quantum efficiency, the higher the luminous efficiency of the device. The specific test results are shown in table 1.
TABLE 1
As can be seen from the data in table 1, compared to the comparative example, each example is superior to the comparative example in terms of comprehensive consideration of efficiency and stability, and there is no unilateral high efficiency or unilateral good stability. Example 7 the particle size of the core body was larger, and the initial external quantum efficiency and the luminance/initial luminance (%) after 100 hours of operation were smaller as compared with example 4.
From the above description, it can be seen that the above-described embodiments of the present application achieve the following technical effects:
1) in the manufacturing method, the charge transport layer is prepared by a solution method, the method is simple to operate, and the formed charge transport layer is more uniform. The charge transport layer is formed of a plurality of nanocrystals each including a core and a shell layer, and thus, the charge transport layer is formed of two parts of the core and the shell layers, the plurality of shell layers forming a honeycomb structure, the shell layers using a charge transport material, i.e., an electron transport material or a hole transport material, and the core using a wide bandgap semiconductor or insulator material. The charge transmission materials corresponding to the plurality of shell layers are of a continuous honeycomb (or network) structure, so that smooth and unimpeded charge transmission is guaranteed. And because a plurality of nucleuses exist between the charge transport materials, the actual crystal size of the charge transport materials is limited by the spacing between the nucleuses, and the charge transport materials have quantum confinement effect and can show the performance of the nano materials.
In addition, the crystal grain size of the shell layer is limited in the crystallization process, namely the crystal grain size is slightly larger than 2 times of the thickness of the shell layer. Therefore, the energy level of the manufactured charge transport layer can reach a stable state in the crystallization process, the problem of fusion and agglomeration of the shell layers in the crystallization process is avoided, and all the shell layers are connected into a whole, so that good conductivity can be kept.
2) The charge transport layer is formed by a core body and shell layers, wherein the shell layers form a honeycomb structure, the shell layers are made of charge transport materials, namely electron transport materials or hole transport materials, and the core body is made of a wide-bandgap semiconductor or insulator material. The charge transmission materials corresponding to the plurality of shell layers are of a continuous honeycomb (or network) structure, so that smooth and unimpeded charge transmission is guaranteed. And because a plurality of nucleuses exist between the charge transport materials, the actual crystal size of the charge transport materials is limited by the spacing between the nucleuses, and the charge transport materials have quantum confinement effect and can show the performance of the nano materials.
3) The ink is used as a raw material of the charge transport layer, so that the charge transport layer obtained by manufacturing has stability, and the stability of a device with the charge transport layer is improved.
4) The photoelectric optical device comprises the charge transmission layer, so that the external quantum efficiency is high, and the performance of the photoelectric optical device is stable.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (14)
1. A method of fabricating a charge transport layer, the method comprising:
preparing nanoparticles, wherein the nanoparticles comprise a core body and a shell layer wrapped outside the core body, the core body is made of an insulating material and/or a semiconductor material, the shell layer is made of a semiconductor electron transport material or a semiconductor hole transport material, and the forbidden band width of the semiconductor material is greater than that of the shell layer;
and disposing the nanoparticles on a substrate by a solution method to form the charge transport layer for transporting charges.
2. The method of manufacturing according to claim 1, wherein the solution method includes one of a spin coating method, an inkjet printing method, a spray coating method, a screen printing method, a blade coating method, a drop coating method, a brush coating method, a transfer method, a dip coating method, and a roll coating method.
3. The manufacturing method according to claim 1, wherein the solution method is a spin coating method, and the process of forming the charge transport layer by using the spin coating method includes:
step S1, preparing a spin-on solution, wherein the spin-on solution comprises a spin-on solvent and the nanoparticles in the spin-on solvent; and
step S2, spin-coating the spin-coating solution on the surface of the substrate and drying to form the charge transport layer.
4. The production method according to claim 1, wherein the solution method is an inkjet printing method, and the process of forming the charge transport layer by the inkjet printing method comprises:
configuring a printing ink comprising a printing solvent and the nanoparticles in the printing solvent;
and printing the printing ink on the surface of the substrate by adopting an ink-jet printing method and drying to form the charge transport layer.
5. The method of claim 1, wherein the nanoparticle is prepared by a process comprising:
mixing a core body, a dispersion solution and a metal precursor of the electron transport material or the hole transport material, heating and stirring to form a mixed solution, wherein in the mixed solution, the core body is dispersed in the dispersion solution; and
and adding an alkali solution into the mixed solution, wherein the alkali solution reacts with the metal precursor to form a shell layer on the surface of the core body so as to form the nano particles.
6. The method according to claim 1, wherein the particle size of the core body is 1 to 100 nm; the thickness of the shell layer is 1-10 nm.
7. The method according to claim 1, wherein the particle diameter of the core body is 3 to 10 nm.
8. The method as claimed in claim 1, wherein the shell layer has a thickness of 2 to 5 nm.
9. The manufacturing method according to claim 1, wherein the material of the core body is a wide bandgap semiconductor material, the bandgap of the wide bandgap semiconductor material is greater than or equal to 2.3eV, or the material of the core body is an insulating material.
10. Method for manufacturing according to claim 9, characterized in that said insulating material is chosen from SiO2、ZrO2、HfO2、Al2O3And MgO.
11. The method of claim 1, wherein the electron transport material is selected from SnO2、TiO2、WO3And ZnO, the hole transport material is selected from CuO and Cu2At least one of O and NiO.
12. A charge transport layer, characterized in that the charge transport layer (10) comprises a plurality of stacked nanoparticles, the nanoparticles comprise a core body (11) and a shell layer (12) wrapping the core body (11), the material of the core body (11) is an insulating material and/or a semiconductor material, the material of the shell layer (12) is a semiconductor electron transport material or a semiconductor hole transport material, and the forbidden band width of the semiconductor material is larger than that of the material of the shell layer (12).
13. The ink is characterized by comprising nanoparticles and a solvent, wherein the nanoparticles comprise a core body and a shell layer coated outside the core body, the material of the core body is an insulating material and/or a semiconductor material, the material of the shell layer is a semiconductor electron transport material or a semiconductor hole transport material, and the forbidden bandwidth of the semiconductor material is greater than that of the material of the shell layer.
14. An optoelectronic device comprising a charge transport layer, wherein the charge transport layer is according to claim 12.
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| CN113054062B (en) * | 2019-12-28 | 2022-06-14 | Tcl科技集团股份有限公司 | Nano material and preparation method thereof, quantum dot light-emitting diode and light-emitting device |
| CN111952476A (en) * | 2020-08-18 | 2020-11-17 | 福州大学 | Preparation method of CdSe quantum dot light-emitting diode device |
| CN112164741B (en) * | 2020-09-28 | 2022-02-01 | 深圳市华星光电半导体显示技术有限公司 | Charge transport layer and light emitting device |
| WO2022120655A1 (en) * | 2020-12-09 | 2022-06-16 | 京东方科技集团股份有限公司 | Quantum dot and preparation method therefor, quantum dot light-emitting device, and display apparatus |
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