CN113130772A - Nanocomposite material, preparation method thereof, solution composition and light emitting diode - Google Patents
Nanocomposite material, preparation method thereof, solution composition and light emitting diode Download PDFInfo
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- CN113130772A CN113130772A CN201911394125.6A CN201911394125A CN113130772A CN 113130772 A CN113130772 A CN 113130772A CN 201911394125 A CN201911394125 A CN 201911394125A CN 113130772 A CN113130772 A CN 113130772A
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Abstract
The invention belongs to the technical field of display, and particularly relates to a nano composite material, a preparation method thereof, a solution composition and a light-emitting diode. The preparation method of the nano composite material provided by the invention comprises the following steps: under the atmosphere of inert gas, the metal oxide nano-particles and a precursor containing trifluoromethyl react in a solution under an acidic condition to prepare the metal oxide nano-particles with the surface modified with at least one trifluoromethyl. The method is simple and convenient to operate, the trifluoromethyl is modified on the surface of the prepared nano composite material, the electron cloud state of the surface of the metal oxide nano particle is improved, the defect of the surface of the metal oxide nano particle is filled, when the nano composite material is applied to the preparation of an electron transport layer in a light-emitting device, the transmission efficiency of electrons in a transport film layer can be improved, the defect luminescence of the film layer is reduced, and the contact interface between the film layer and a luminescent layer can be optimized, so that the luminescence performance of the light-emitting device is improved.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a nano composite material, a preparation method thereof, a solution composition and a light-emitting diode.
Background
Quantum Dot Light Emitting Diodes (QLEDs) are an electroluminescent device, and have the advantages of high luminous efficiency, high color purity, narrow Light emission spectrum, adjustable emission wavelength, and the like, so that they are a new generation of excellent display technology. The light emitting mechanism of the currently studied quantum dot light emitting diode (QLED) device is: electrons injected from the cathode are transmitted into the quantum dot light-emitting layer through the electron transmission layer and are subjected to composite radiation light-emitting with the holes.
In recent years, the use of metal oxide nanoparticles with wide band gaps as electron transport layers has become a relatively hot research content, and in order to improve the application performance of materials, surface chemical modification of metal oxide nanoparticles is attempted by using some small molecular ligands, which are mainly thiols, fatty acids, amines, organic phosphoric acids, and the like, and the use of these small molecular ligands for surface modification of metal oxide nanoparticles can improve the dispersibility of metal oxide nanoparticles in non-polar solvents, but the electron mobility of metal oxide nanoparticles with such ligands modified on the surface is generally low.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a nano composite material, aiming at solving the problem of low electron mobility of the existing metal oxide nano particles.
It is another object of the present invention to provide a solution composition.
It is still another object of the present invention to provide a nanocomposite prepared by the above preparation method.
It is another object of the present invention to provide a light emitting diode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing a nanocomposite comprising: under the atmosphere of inert gas, the metal oxide nano-particles and a precursor containing trifluoromethyl react in a solution under an acidic condition to prepare the metal oxide nano-particles with the surface modified with at least one trifluoromethyl.
According to the preparation method of the nano composite material, metal oxide nano particles and a precursor react in a solution under an acidic condition, so that the precursor is decomposed to form free trifluoromethyl, and the free trifluoromethyl is combined with the metal oxide nano particles, so that the metal oxide nano particles with the surfaces modified with the trifluoromethyl are prepared. The method provided by the invention is simple, simple and convenient to operate, easy to control and suitable for large-scale mass production of the nano composite material. The surface of the nano composite material prepared by the method is modified with trifluoromethyl, on one hand, the trifluoromethyl has high-density electron cloud, and the electron cloud density on the surface of the metal oxide nano particle can be increased, so that the electron mobility is improved; on the other hand, the trifluoromethyl can be combined with a dangling bond on the surface of the metal oxide nano particle to form a passivation effect on the surface, and when the trifluoromethyl is applied to preparing an electron transport layer, a carrier recombination center caused by a defect state at an interface can be reduced, so that defect luminescence of the electron transport layer is reduced, and the luminous efficiency of a luminescent device is improved; in another aspect, the introduction of trifluoromethyl improves the polarity, dipole moment, stability and lipophilicity of the material, improves the stability of the metal oxide nanoparticles in solution and the film forming property thereof, and when the trifluoromethyl is applied to the preparation of an electron transport layer in a light-emitting device, the lipophilicity can reduce the interface repulsion between the electron transport layer and a light-emitting layer of an oily material, improve the interface contact efficiency, improve the charge transport between the film layers, and further improve the light-emitting efficiency of the light-emitting device.
Accordingly, a solution composition comprising: the metal oxide nanoparticle comprises a solvent and metal oxide nanoparticles dispersed in the solvent, wherein the surfaces of the metal oxide nanoparticles are modified with trifluoromethyl.
The present invention provides a solution composition comprising: the metal oxide nano particles with the trifluoromethyl modified on the surfaces are modified with the trifluoromethyl, so that the electron cloud state of the surfaces of the metal oxide nano particles is improved, the defects of the surfaces of the metal oxide nano particles are filled, when the metal oxide nano particles are applied to the preparation of an electron transmission layer in a light-emitting device, the transmission efficiency of electrons on a transmission film layer can be improved, the defects of the film layer are reduced, light is emitted, and the contact interface between the film layer and a light-emitting layer can be optimized, so that the light-emitting performance of the light-emitting device is improved.
Correspondingly, the nano composite material is prepared by the preparation method, and comprises the following steps: metal oxide nanoparticles and trifluoromethyl groups modified on the surface of the metal oxide nanoparticles. .
According to the nano composite material provided by the invention, the trifluoromethyl is modified on the surface of the metal oxide nano particle, the electron cloud state of the surface of the metal oxide nano particle is improved, the defect of the surface of the metal oxide nano particle is filled, when the nano composite material is applied to the preparation of an electron transmission layer in a light-emitting device, the transmission efficiency of electrons in a transmission film layer can be improved, the defect luminescence of the film layer is reduced, and the contact interface between the film layer and a luminescent layer can be optimized, so that the luminescence performance of the light-emitting device is improved.
Correspondingly, the light-emitting diode comprises a cathode and an anode which are oppositely arranged, a light-emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the light-emitting layer, wherein the material of the electron transport layer comprises: the nanocomposite material prepared by the foregoing preparation method.
According to the light-emitting diode provided by the invention, the material of the electron transport layer comprises the nano composite material prepared by the method, the electron transfer efficiency is good, the interface contact with the light-emitting layer is good, and the light-emitting performance is excellent.
Drawings
FIG. 1 is a flow chart of a method for preparing a nanocomposite according to an embodiment of the present invention;
fig. 2 is a cross-sectional view of a light emitting diode according to an embodiment of the invention.
Reference numerals: an anode L01, a hole injection layer L02, a hole transport layer L03, a metal oxide nanoparticle light-emitting layer L04, an electron transport layer L05 and a cathode L06.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method of preparing a nanocomposite comprising: under the atmosphere of inert gas, the metal oxide nano-particles and a precursor containing trifluoromethyl react in a solution under an acidic condition to prepare the metal oxide nano-particles with the surface modified with at least one trifluoromethyl.
Specifically, metal oxide nanoparticles and a trifluoromethyl-containing precursor are reacted in a solution under an acidic condition, so that the precursor is decomposed to form free trifluoromethyl, and the free trifluoromethyl is combined with the metal oxide nanoparticles, thereby preparing the metal oxide nanoparticles with the surfaces modified with trifluoromethyl. The metal oxide nano-particles and the precursor containing trifluoromethyl are subjected to synchronous reaction in the solution under an acidic condition, so that free trifluoromethyl formed by acid hydrolysis can be combined with the metal oxide nano-particles in time, the decomposition of the precursor is promoted to a certain extent, and the reaction efficiency is improved.
The reaction between the metal oxide nano-particles and the precursor is controlled to be carried out under the inert gas atmosphere, so that the influence of air on the synthesis of the metal oxide nano-particles modified with trifluoromethyl on the surface can be avoided. The inert gas atmosphere includes, but is not limited to, nitrogen, helium, argon, and the like, and in some embodiments, the inert gas atmosphere is an argon atmosphere.
The metal oxide nanoparticles refer to a type of n-type semiconductor metal oxide with a wide forbidden bandwidth, such as zinc oxide, zirconium oxide, titanium oxide, and the like. In one embodiment, the metal oxide nanoparticles are selected from at least one of zinc oxide, zirconium oxide, and titanium oxide. In some embodiments, the metal oxide nanoparticles have a particle size of 3-12nm, and the metal oxide nanoparticles in the particle size range can be dispersed in a colloidal solution with a uniform layer, so that the film forming property is good, and a uniform and flat film layer can be formed, thereby improving the light emitting property of the light emitting device.
The precursor refers to a kind of organic matter capable of forming free trifluoromethyl through decomposition reaction, and as one embodiment, the precursor is selected from at least one of 2-chloro-4- (trifluoromethoxy) aniline, sodium trifluoromethanesulfonate, trifluoromethyl diazomethane, silver fluorosulfonyl difluoroacetate and copper fluorosulfonyl difluoroacetate. The precursor can be hydrolyzed to generate free trifluoromethyl under the acidic condition through simple reaction conditions, such as proper heating, the free trifluoromethyl is combined with oxygen atoms of the metal oxide nanoparticles to form the metal oxide nanoparticles with the trifluoromethyl modified surfaces, strict reaction conditions or special chemical reagents are not needed, the operation is simple and convenient, the control is easy, and the large-scale mass production of the metal oxide nanoparticles with the trifluoromethyl modified surfaces can be promoted.
The solvent of the solution is preferably a non-coordinating solvent, and the solute may be selected from at least one of metal oxide nanoparticles, precursors, and acidic species. In some embodiments, the solution is dissolved with an acidic substance. In some embodiments, the solution is dissolved with a precursor. In some embodiments, the solution is dissolved with metal oxide nanoparticles.
In one embodiment, in the step of reacting the metal oxide nanoparticles and the precursor in a solution under acidic conditions, the weight ratio of the metal oxide nanoparticles to the precursor is (5-10): 1. The proportion of the precursor is too high, so that excessive modification is easily caused, the trifluoromethyl groups are excessive, the interparticle repulsion is increased, and the subsequent film-forming property is influenced; when the proportion of the precursor is too low, the surface modification effect of the metal oxide nanoparticles is poor.
As one embodiment, in the step of reacting the metal oxide nanoparticles and the precursor in a solution under acidic conditions, the metal oxide nanoparticles and the trifluoromethyl group-containing precursor are reacted in a solution under acidic conditions, and the molar concentration of the metal oxide nanoparticles dispersed in the solution is 0.5 to 5 mol/L. Under the concentration range, the metal oxide nanoparticles can be completely dispersed in the solution to form uniform colloidal solution, which is beneficial to improving the subsequent reaction rate in the solution. When the concentration of the metal oxide nanoparticles is too high, the particles are dispersed unevenly, and even suspension liquid is formed; when the concentration of the metal oxide nanoparticles is too low, subsequent separation and precipitation cleaning are not facilitated, and the process difficulty is increased.
As one embodiment, as shown in fig. 1, the step of reacting the metal oxide nanoparticles and the precursor in a solution under acidic conditions comprises:
s01, dissolving the metal oxide nano particles in a non-coordination solvent to form a metal oxide solution;
s02, adding an acid reagent and the trifluoromethyl-containing precursor into the metal oxide solution, and reacting under heating.
The metal oxide nanoparticles are dissolved in the non-coordination solvent, and then the acid reagent and the precursor are added, so that the metal oxide nanoparticles, the acid reagent and the precursor are promoted to be fully contacted, and the reaction efficiency is favorably improved.
In step S01, the step of dissolving the metal oxide nanoparticles in the non-coordinating solvent may refer to operations conventional in the art, for example, dispersing the metal oxide nanoparticles in the non-coordinating solvent, and heating and stirring under an inert gas atmosphere until the metal oxide nanoparticles are completely dissolved.
The non-coordinating solvent as a reaction solvent for binding the surface ligand to the metal oxide nanoparticles refers to a class of organic solvents that does not contain lone electrons capable of coordinating with the metal of the metal oxide nanoparticles, and reference may be made to non-coordinating solvents conventional in the art, such as, in some embodiments, at least one selected from alkanes, alkenes, ethers, and aromatics. In some embodiments, the non-coordinating solvent is selected from at least one of toluene, benzene, xylene, tetrahydrofuran, dichloroethane, dichloromethane, n-hexane, cyclohexane, chloroform, carbon tetrachloride, and n-octane, which is capable of uniformly dispersing the metal oxide nanoparticles and surface ligands without affecting the properties of the metal oxide nanoparticles and without affecting the coordination bonding of the surface ligands to the metal oxide nanoparticles.
In step S02, an acid reagent and the precursor are added to the metal oxide solution to form a reaction system to prepare the metal oxide nanoparticles with the trifluoromethyl modified surface, where the addition sequence of the acid reagent and the precursor is not specifically limited in the embodiments of the present invention, and the operation can be flexibly performed according to actual situations.
The reaction is carried out under the heating condition to promote the decomposition of the precursor to form free trifluoromethyl and promote the combination of the free trifluoromethyl and the metal oxide nano-particles, thereby greatly improving the reaction efficiency.
As an embodiment, in the step of carrying out the reaction under heating, the reaction temperature is 35 ℃ to 100 ℃ and the reaction time is 30 to 60 minutes.
As an embodiment, after the step of reacting the metal oxide nanoparticles and the precursor in the solution under acidic conditions, the method further comprises: separating the prepared metal oxide nano particles with the surfaces modified with trifluoromethyl from the solution. In some embodiments, after the reaction is complete, the nanocomposite ink is prepared by adding a precipitant to the substrate nanocomposite, then washing and redispersing the nanocomposite in solution. In a further embodiment, the precipitant is preferably at least one of ethyl acetate, ethanol, acetone.
In summary, the preparation method of the nanocomposite provided by the embodiment of the invention does not need strict reaction conditions or special chemical reagents, is simple and convenient to operate, is easy to control, and is suitable for large-scale mass production of the nanocomposite.
Based on the technical scheme, the embodiment of the invention also provides a solution composition, a nano composite material and a light-emitting diode.
Accordingly, a solution composition comprising: the metal oxide nanoparticle comprises a solvent and metal oxide nanoparticles dispersed in the solvent, wherein the surfaces of the metal oxide nanoparticles are modified with trifluoromethyl.
The solution composition provided by the embodiment of the invention comprises: the metal oxide nano particles with the trifluoromethyl modified on the surfaces are modified with the trifluoromethyl, so that the electron cloud state of the surfaces of the metal oxide nano particles is improved, the defects of the surfaces of the metal oxide nano particles are filled, when the metal oxide nano particles are applied to the preparation of an electron transmission layer in a light-emitting device, the transmission efficiency of electrons on a transmission film layer can be improved, the defects of the film layer are reduced, light is emitted, and the contact interface between the film layer and a light-emitting layer can be optimized, so that the light-emitting performance of the light-emitting device is improved.
Wherein, the metal oxide nanoparticles are the same as the metal oxide nanoparticles described in the above preparation method, and are not repeated herein for the sake of brevity.
The solvent serves as a dispersion medium for the metal oxide nanoparticles, and may be selected from non-coordinating solvents conventional in the art, such as at least one selected from alkanes, alkenes, ethers, and aromatics, including but not limited to toluene, benzene, xylene, tetrahydrofuran, dichloroethane, dichloromethane, n-hexane, cyclohexane, chloroform, carbon tetrachloride, n-octane, and the like, in some embodiments.
The concentration of the metal oxide nanoparticles in the solution composition can be flexibly adjusted according to the actual product requirements, and the embodiment of the invention is not particularly limited. It will be appreciated that the solution composition described above may be used for ink jet printing.
The surface of the metal oxide nano-particles is modified with trifluoromethyl, and as one embodiment, the weight ratio of the metal oxide nano-particles to the trifluoromethyl is (5-10): 1.
Correspondingly, the nano composite material is prepared by the preparation method, and comprises the following steps: and metal oxide nanoparticles with trifluoromethyl modified on the surface.
The nano composite material provided by the embodiment of the invention is prepared by the preparation method, the trifluoromethyl is modified on the surface of the metal oxide nano particle, the electron cloud state of the surface of the metal oxide nano particle is improved, the defect of the surface of the metal oxide nano particle is filled, when the nano composite material is applied to the preparation of an electron transmission layer in a light-emitting device, the transmission efficiency of electrons in a transmission film layer can be improved, the defect luminescence of the film layer is reduced, and the contact interface of the film layer and a luminescent layer can be optimized, so that the luminescence performance of the light-emitting device is improved.
Wherein, the metal oxide nanoparticles are the same as the metal oxide nanoparticles described in the above preparation method, and are not repeated herein for the sake of brevity.
In one embodiment, in the metal oxide nanoparticle having a trifluoromethyl group modified on the surface thereof, the trifluoromethyl group is coordinately bonded to the metal oxide nanoparticle.
In one embodiment, the weight ratio of the metal oxide nanoparticles to the trifluoromethyl groups is (5-10): 1.
In addition, when the electron transport layer is prepared using the above nanocomposite material, the electron transport layer is deposited on the substrate using a magnetron sputtering method, a chemical vapor deposition method, an evaporation method, a spin coating method, an inkjet printing method, or the like. In some embodiments, the nanocomposite is dispersed in a solution to prepare a slurry, and then the slurry is spin-coated on a substrate to form a film by using a spin coating method, wherein the thickness of the light emitting layer is controlled, for example, 20-60nm, by adjusting the concentration of the solution, the spin coating speed (for example, adjusting the spin speed between 2000 and 6000 rpm) and the spin coating time, and then the film is annealed at 200 and 250 ℃. The annealing can be performed in air or in a nitrogen atmosphere, and the annealing atmosphere is selected according to actual needs.
Correspondingly, the light-emitting diode comprises a cathode and an anode which are oppositely arranged, a light-emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the light-emitting layer, wherein the material of the electron transport layer comprises: a nanocomposite material produced by the foregoing production method, or the above nanocomposite material.
According to the light-emitting diode provided by the embodiment of the invention, the material of the electron transport layer comprises the nano composite material prepared by the method, the electron transport efficiency is good, the interface contact is good between the electron transport layer and the light-emitting layer, and the light-emitting performance is excellent. The materials of the electron transport layer described above may also include other known materials.
In some examples, the material of the electron transport layer is formed from a nanocomposite material prepared by the above-described preparation method. The material of the electron transport layer is the nano composite material prepared by the preparation method. The material of the electron transport layer only comprises the nano composite material prepared by the preparation method.
The structure of the light emitting diode can refer to the conventional technology in the field, and in some embodiments, the light emitting diode is in a positive type structure, and the anode is connected with a substrate to serve as a bottom electrode; in other embodiments, the light emitting diode is an inverted structure, and the cathode is connected to the substrate as a bottom electrode. Further, in addition to the above-described basic structural film layers such as the cathode, the anode, the light-emitting layer, and the electron transport layer, a hole functional layer such as a hole transport layer, a hole injection layer, and a hole blocking layer may be provided between the anode and the light-emitting layer, and an electron functional layer such as an electron injection layer and an electron blocking layer may be provided between the cathode and the electron transport layer.
As an embodiment, the basic structure of the light emitting diode includes an anode L01, a hole injection layer L02, a hole transport layer L03, a light emitting layer L04, an electron transport layer L05, and a cathode L06, which are sequentially stacked and disposed as shown in fig. 2. In some embodiments, the electron transport layer has a thickness of 20-60 nm. In some embodiments, the light emitting layer has a thickness of 20-60 nm. In some embodiments, the cathode has a thickness of 15-30 nm.
The materials of the anode, the hole injection layer, the hole transport layer and the cathode can refer to the conventional light emitting diode, and can also be respectively selected to be specific materials. In some embodiments, the anode is connected to a substrate, the substrate is a rigid substrate or a flexible substrate, and the material of the anode is selected from at least one of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), and tin-doped zinc oxide (ZTO). In some embodiments, the cathode is made of Cu or Ag, and has a small resistance so that carriers can be smoothly injected.
When in preparation, an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer and a cathode are sequentially deposited on a substrate by adopting a magnetron sputtering method, a chemical vapor deposition method, an evaporation method, a spin coating method, an ink-jet printing method and the like. In some embodiments, an inversion structure QLED device is prepared, comprising the steps of:
1) dispersing the nano composite material in isopropanol to obtain electron transport layer slurry; depositing the electron transport layer slurry on the ITO substrate to form an electron transport layer;
2) depositing a CdSe/ZnS core-shell green quantum dot light-emitting layer on the electron transport layer;
3) and printing a hole transport layer on the CdSe/ZnS core-shell green quantum dot light-emitting layer, and then evaporating an Al anode on the hole transport layer to obtain the light-emitting diode.
Further, in order to obtain a high-quality QLED device, the ITO substrate needs to be subjected to a pretreatment process. The basic specific processing steps include: cleaning the whole piece of ITO conductive glass with a cleaning agent, preliminarily removing stains on the surface, then sequentially carrying out ultrasonic cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min respectively to remove impurities on the surface, and finally blowing dry with high-purity nitrogen to obtain the ITO substrate.
Further, the obtained QLED is subjected to a packaging process, and the packaging process may be performed by a common machine or by a manual method. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 0.1ppm so as to ensure the stability of the device.
In order that the above-described details and operation of the present invention will be clearly understood by those skilled in the art, and the advanced performance of the nanocomposite preparation method, the light-emitting film and the light-emitting diode according to the embodiments of the present invention will be apparent, the embodiments of the present invention will be illustrated below by way of examples.
Example 1
The embodiment provides a light emitting diode, and the preparation method specifically comprises the following steps:
1. preparation of nanocomposite A
Dispersing zinc oxide nano particles in 10mL of butanol, heating to 40 ℃ in an argon atmosphere, and stirring until the zinc oxide nano particles are dissolved to form a zinc oxide solution with the concentration of 1.0M; adding 0.5mL of n-octanoic acid into the zinc oxide solution, stirring for 10 minutes, adding 0.1mmol of 2-chloro-4- (trifluoromethoxy) aniline, and reacting for 30 minutes; after the reaction is finished, precipitating and cleaning by using ethyl acetate, ethanol and acetone to obtain a nano composite material A: zinc oxide nano-particles with trifluoromethyl modified on the surface;
2. preparation of light-emitting diode A
1) Dispersing the nano composite material A in butanol to obtain electron transport layer slurry A; depositing the electron transport layer slurry A on an ITO substrate to form an electron transport layer A;
2) depositing a CdSe/ZnS core-shell green quantum dot light-emitting layer on the electron transport layer A;
3) and printing a hole transport layer A on the CdSe/ZnS core-shell green quantum dot light-emitting layer, and then evaporating an Al anode on the hole transport layer to obtain the light-emitting diode A.
Example 2
The embodiment provides a light emitting diode, and the preparation method specifically comprises the following steps:
1. preparation of nanocomposite B
Dispersing titanium oxide nano particles in 10mL of isopropanol, heating to 40 ℃ under the atmosphere of argon, and stirring until the titanium oxide nano particles are dissolved to form a titanium oxide solution with the concentration of 1.0M; adding 0.5mL of acetic acid into the titanium oxide solution, stirring for 10 minutes, adding 0.1mmol of sodium trifluoromethanesulfonate, and reacting for 30 minutes; after the reaction is finished, precipitating and cleaning by using ethyl acetate, ethanol and acetone to obtain a nano composite material B: titanium oxide nanoparticles modified with trifluoromethyl on the surface;
2. preparation of Metal oxide nanoparticle light emitting diode B
The specific process is basically the same as that of embodiment 1, and is not described in detail here.
Example 3
The embodiment provides a light emitting diode, and the preparation method specifically comprises the following steps:
1. preparation of nanocomposite C
Dispersing titanium oxide nano particles in 10mL of isopropanol, heating to 40 ℃ under the atmosphere of argon, and stirring until the titanium oxide nano particles are dissolved to form a titanium oxide solution with the concentration of 1.0M; adding 0.5mL of n-octanoic acid into the titanium oxide solution, stirring for 10 minutes, adding 0.1mmol of trifluoromethyl diazomethane, and reacting for 30 minutes; after the reaction is finished, precipitating and cleaning by using ethyl acetate, ethanol and acetone to obtain a nano composite material C: titanium oxide nanoparticles modified with trifluoromethyl on the surface;
2. preparation of Metal oxide nanoparticle light emitting diode C
The specific process is basically the same as that of embodiment 1, and is not described in detail here.
Comparative example 1
In the light emitting diode provided by the comparative example, the electron transport layer material is zinc oxide nanoparticles.
The performance tests were performed on the light emitting diodes provided in examples 1 to 3 and comparative example 1, and the test indexes and test methods were as follows:
(1) electron mobility: testing the current density (J) -voltage (V) of the led, plotting a graph, fitting the Space Charge Limited Current (SCLC) region in the graph, and then calculating the electron mobility according to the well-known Child's law formula:
J＝(9/8)εrε0μeV2/d3
wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seDenotes the electron mobility in cm2V-1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: and measuring the resistivity of the electron transport layer in the light-emitting diode by using the same resistivity test instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
The test results are shown in table 1 below:
TABLE 1
As can be seen from table 1 above, the light emitting diodes provided in examples 1 to 3 of the present invention have a significantly lower resistivity than comparative example 1, and the EQE and electron mobility are significantly higher than comparative example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. A method of preparing a nanocomposite, comprising: under the atmosphere of inert gas, the metal oxide nano-particles and a precursor containing trifluoromethyl react in a solution under an acidic condition to prepare the metal oxide nano-particles with the surface modified with at least one trifluoromethyl.
2. The method according to claim 1, wherein in the step of reacting the metal oxide nanoparticles with the precursor in a solution under acidic conditions, the weight ratio of the metal oxide nanoparticles to the precursor is (5-10): 1; and/or
In the step of reacting metal oxide nanoparticles with a precursor in a solution under an acidic condition, the metal oxide nanoparticles and the trifluoromethyl group-containing precursor are reacted in the solution under the acidic condition, and the molar concentration of the metal oxide nanoparticles dispersed in the solution is 0.5 to 5 mol/L.
3. The production method according to claim 1, wherein the precursor is at least one selected from the group consisting of 2-chloro-4- (trifluoromethoxy) aniline, sodium trifluoromethanesulfonate, trifluoromethyl diazomethane, silver fluorosulfonyl difluoroacetate and copper fluorosulfonyl difluoroacetate.
4. The method of claim 1, wherein the step of reacting the metal oxide nanoparticles and the precursor in a solution under acidic conditions comprises: dissolving the metal oxide nanoparticles in a non-coordinating solvent, then adding an acid reagent and the precursor, and reacting under a heating condition.
5. The method according to claim 4, wherein the reaction is carried out under heating at a temperature of 35 ℃ to 100 ℃ for a time of 30 to 60 minutes.
6. The production method according to any one of claims 1 to 5, wherein the metal oxide nanoparticles are selected from at least one of zinc oxide, zirconium oxide, titanium oxide; and/or
After the step of reacting the metal oxide nanoparticles and the precursor in a solution under acidic conditions, the method further comprises: separating the prepared metal oxide nano particles with the surfaces modified with trifluoromethyl from the solution.
7. A solution composition, comprising: the metal oxide nanoparticle comprises a solvent and metal oxide nanoparticles dispersed in the solvent, wherein the surfaces of the metal oxide nanoparticles are modified with trifluoromethyl.
8. A nanocomposite, comprising: metal oxide nanoparticles and trifluoromethyl groups modified on the surface of the metal oxide nanoparticles.
9. Nanocomposite according to claim 8, wherein the metal oxide nanoparticles are selected from at least one of zinc oxide, zirconium oxide, titanium oxide; and/or
The particle size of the metal oxide nano-particles is 3-12 nm; and/or
The weight ratio of the metal oxide nanoparticles to the trifluoromethyl groups is (5-10): 1.
10. A light-emitting diode comprising a cathode and an anode disposed opposite to each other, a light-emitting layer disposed between the cathode and the anode, and an electron transport layer disposed between the cathode and the light-emitting layer, wherein the electron transport layer is made of a material comprising: a nanocomposite material produced by the production method described in any one of claims 1 to 6, or a nanocomposite material described in any one of claims 8 to 9.
11. The led of claim 10, wherein the electron transport layer is made of: a nanocomposite material produced by the production method described in any one of claims 1 to 6, or a nanocomposite material described in any one of claims 8 to 9.
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| CN101275285A (en) * | 2007-12-28 | 2008-10-01 | 中国人民解放军国防科学技术大学 | Functional cladding layer tetraacicular zinc oxide whisker and preparation method thereof |
| US20150337135A1 (en) * | 2012-11-29 | 2015-11-26 | Ube Industries, Ltd. | Pentafluorosulfanyl phthalocyanine derivatives and intermediates thereof |
| CN109148695A (en) * | 2017-06-28 | 2019-01-04 | Tcl集团股份有限公司 | A kind of preparation method and electricity device of metal oxide nanoparticles film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101275285A (en) * | 2007-12-28 | 2008-10-01 | 中国人民解放军国防科学技术大学 | Functional cladding layer tetraacicular zinc oxide whisker and preparation method thereof |
| US20150337135A1 (en) * | 2012-11-29 | 2015-11-26 | Ube Industries, Ltd. | Pentafluorosulfanyl phthalocyanine derivatives and intermediates thereof |
| CN109148695A (en) * | 2017-06-28 | 2019-01-04 | Tcl集团股份有限公司 | A kind of preparation method and electricity device of metal oxide nanoparticles film |
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