CN111223997A - Composite material, preparation method thereof and quantum dot light-emitting diode - Google Patents
Composite material, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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- CN111223997A CN111223997A CN201811414728.3A CN201811414728A CN111223997A CN 111223997 A CN111223997 A CN 111223997A CN 201811414728 A CN201811414728 A CN 201811414728A CN 111223997 A CN111223997 A CN 111223997A
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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Abstract
The invention provides a composite material which comprises a metal phthalocyanine compound and a nano carbon material, wherein the mass ratio of the metal phthalocyanine compound to the nano carbon material is 1: 1-1: 10. The composite material provided by the invention comprises a metal phthalocyanine compound and a nano carbon material. The metal phthalocyanine compound has a large pi-bond conjugated system and easily delocalized pi electrons, has a large optical nonlinear coefficient and a short photoelectric response time, and can be used as a hole transport material; but also has good structural stability.
Description
Technical Field
The invention belongs to the technical field of photoelectric display, and particularly relates to a composite material and a preparation method thereof, and a quantum dot light-emitting diode and a preparation method thereof.
Background
In recent years, with the rapid development of display technology, quantum dot light emitting diodes (QLEDs) having semiconductor quantum dot materials as light emitting layers have received much attention. The quantum dot light-emitting diode has the advantages of high color purity, high luminous efficiency, adjustable luminous color, stable device and the like, and has wide application prospect in the fields of flat panel display, solid state lighting and the like.
QLED devices can improve device performance (including device efficiency and lifetime) through material improvements. In a traditional quantum dot light emitting diode device structure [ substrate (glass, flexible material)/transparent anode electrode (such as ITO)/conductive buffer layer (such as PEDOT: PSS)/hole transport layer/quantum dot light emitting layer/electron transport layer/cathode electrode (such as aluminum and silver) ], the hole transport layer mainly has the functions of collecting holes injected by an anode, promoting the transmission of the holes, adjusting the matching of energy levels and improving the light emitting efficiency of the device. Meanwhile, the hole transport layer also needs to have better conductivity, so that the internal resistance of the device can be reduced.
The hole transport layer material currently used in optoelectronic devices is typically TFB, which has a hole mobility of 1 x 10- 2cm2And V is, the transmission efficiency is lower than that of the common electron transmission layer zinc oxide by one order of magnitude. The QLED is an electron-dominated device, the unbalanced injection of electrons and holes can cause the device to generate leakage current, and meanwhile, the quantum dots are charged by excessive electrons, so that nonradiative Auger recombination occurs, and fluorescence quenching is caused. Therefore, it is important to find a hole transport layer material having improved hole transport efficiency.
Disclosure of Invention
The invention aims to provide a composite material and a preparation method thereof, and aims to solve the problem of unbalanced electron and hole injection caused by the fact that the transmission efficiency of a hole transport layer material is lower in the conventional quantum dot light-emitting diode.
Another object of the present invention is to provide a quantum dot light emitting diode containing the above composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite material includes a metal phthalocyanine compound and a nanocarbon material, and a mass ratio of the metal phthalocyanine compound to the nanocarbon material is 1:1 to 1: 10.
Correspondingly, the preparation method of the composite material comprises the following steps: providing a metal phthalocyanine compound and a nano-carbon material, and mixing the metal phthalocyanine compound and the nano-carbon material.
And the quantum dot light-emitting diode comprises an anode and a cathode which are oppositely arranged, and a quantum dot light-emitting layer which is laminated and combined between the anode and the cathode, and the quantum dot light-emitting diode also comprises a hole transport layer which is laminated and combined between the anode and the quantum dot, wherein the material of the hole transport layer is a composite material containing a metal phthalocyanine compound and a nano carbon material, and in the composite material, the mass ratio of the metal phthalocyanine compound to the nano carbon material is 1: 1-1: 10.
The composite material provided by the invention comprises a metal phthalocyanine compound and a nano carbon material. The metal phthalocyanine compound has a large pi-bond conjugated system and easily delocalized pi electrons, has a large optical nonlinear coefficient and a short photoelectric response time, and can be used as a hole transport material; but also has good structural stability. Furthermore, the metal phthalocyanine compound and the nano carbon material are compounded according to the mass ratio of 1:1 to 1:10, and the obtained composite material has a wider band gap (3.5-5.2eV), good conductivity and stability, good hole transport performance and effective balance of electron and hole injection.
The preparation method of the composite material provided by the invention only needs to carry out mixing treatment according to the mass ratio of the two, and has simple process and strong method controllability.
According to the quantum dot light-emitting diode provided by the invention, a material obtained by compounding the metal phthalocyanine compound and the nano carbon material according to the mass ratio of 1:1 to 1:10 is used as a hole transport layer material, so that the hole transport capability of the hole transport layer can be effectively improved, and the injection of electrons and holes can be effectively balanced. In addition, the material obtained by compounding the metal phthalocyanine compound and the nano carbon material has good structural stability, so the quantum dot light-emitting diode has good performance stability.
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.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a composite material, which comprises a metal phthalocyanine compound and a nano carbon material, wherein the mass ratio of the metal phthalocyanine compound to the nano carbon material is 1: 1-1: 10.
The composite material provided by the embodiment of the invention comprises a metal phthalocyanine compound and a nano carbon material. The metal phthalocyanine compound has a large pi-bond conjugated system and easily delocalized pi electrons, has a large optical nonlinear coefficient and a short photoelectric response time, and can be used as a hole transport material; but also has good structural stability. Furthermore, the metal phthalocyanine compound and the nano carbon material are compounded according to the mass ratio of 1:1 to 1:10, and the obtained composite material not only has a wider band gap (3.5-5.2eV), but also has good conductivity, good stability and good hole transport performance.
It is to be noted that in the composite material according to the embodiment of the present invention, the metal phthalocyanine compound and the nanocarbon material are compounded at a mass ratio of 1:1 to 1:10, and the obtained composite material has a good electrical conductivity and can be used as a hole transport material. When the content of the metal phthalocyanine compound is too high or the content of the nano carbon material is too low, and the mass ratio of the metal phthalocyanine compound to the nano carbon material is more than 1:1, on one hand, excessive metal phthalocyanine compound is stacked, and the crystal grains of the composite material are not controlled by a conjugation action to grow up, which is not beneficial to the stability of the electrical material; on the other hand, the conductive performance of the obtained composite material is not improved compared with TFB due to the fact that the content of the nano carbon material is too low, and the hole transmission performance is not improved effectively. When the content of the metal phthalocyanine compound is too low or the content of the nano carbon material is too high, and the mass ratio of the metal phthalocyanine compound to the nano carbon material is less than 1:10, a conduction structure is formed due to the fact that the content of the nano carbon material in the composite material is too high, and the composite material cannot be used as a hole transport material.
Specifically, the phthalocyanine compound system comprises a conjugated network formed by 18 pi electrons, and electrons in the conjugated network are distributed very uniformly, so that four benzene rings in the phthalocyanine compound molecule have strong stability and are extremely difficult to deform, and in addition, the C-N bond length in the phthalocyanine compound system is basically the same, and C, N atoms are arranged on the inner ring in an alternating mode, so that the phthalocyanine compound system has extremely strong structural stability. And because eight N atoms and eight C atoms in the center of the phthalocyanine compound system enclose a cavity with the diameter d of 0.27nm, a plurality of metal elements such as iron, nickel, copper and the like can be accommodated in the cavity, and a series of metal phthalocyanine compounds are correspondingly obtained. The metal phthalocyanine compound has a large pi-bond conjugated system and easily delocalized pi electrons, has a large optical nonlinear coefficient and a short photoelectric response time, and can be used as a hole transport material; but also has good structural stability.
In the embodiment of the present invention, the metal phthalocyanine compound may be a phthalocyanine compound of a common metal. In some embodiments, the metal phthalocyanine compound is selected from one or more of iron phthalocyanine compound, cobalt phthalocyanine compound, nickel phthalocyanine compound, copper phthalocyanine compound, and zinc phthalocyanine compound, but is not limited thereto.
When the metal phthalocyanine compound is used alone as a hole transport material, the hole transport performance of the metal phthalocyanine compound is relatively low, and the problem of unbalanced electron and hole injection is not sufficiently overcome. In the embodiment of the invention, the composite material also contains a nano carbon material. The nano carbon material has better conductivity, and can effectively improve the charge transmission performance of the material on the basis of ensuring the stability of the composite material after being compounded with the metal phthalocyanine compound.
In some embodiments, the nanocarbon material is selected from one or more of graphene oxide, graphene, carbon fiber and carbon nanotube, but is not limited thereto. Wherein the bonding mode of the graphene or the graphene oxide between carbon atoms is SP2In addition to the S orbit which forms a single bond on a plane, the hybrid has an empty P orbit on a vertical plane which is vertical to the plane, and the S orbit and the P orbit can be mutually conjugated to form a large pi bond, so that the whole structure is very stable. The structure of graphene or graphene oxide determines its very good conductivity and carrier mobility (carbon atoms have freely movable p electrons inside them). Therefore, in the preferred embodiment, when graphene oxide or graphene with better conductivity is selected to be compounded with the metal phthalocyanine compound and used as a hole transport material, the hole transport capacity is better, and the current carriers of a device can be balanced and the performance of the device can be improved.
In addition to the above embodiments, it is preferable that the nanocarbon material is subjected to a fluorination treatment, and a part of fluorine atoms are doped in the nanocarbon material (that is, the nanocarbon material is a fluorine-doped nanocarbon material), so that a barrier for hole transport of the composite material is further reduced. Specifically, after the fluorination treatment, F atoms are introduced into the nano carbon material. The electronegativity of the F atom is stronger than that of the carbon atom, the oxygen atom and the hydrogen atom, so that the F atom can attract hole transfer when being used as a hole transfer material, and the potential barrier of carrier transfer is reduced. In addition, F atoms are introduced into the nano carbon material, and fluorine atoms mainly exist in a C-F semiionic bond and a C-F covalent bond, wherein the existence of the C-F semiionic bond can improve the conductivity of the material, and the existence of the C-F covalent bond can provide the stability of the material. The existence of the C-F semi-ionic bond and the C-F covalent bond can endow the composite material with better conductivity and improve the stability of the material.
Further preferably, the molar ratio of fluorine atoms to carbon atoms in the fluorine-doped nanocarbon material is 0.2-0.3: 1. in the fluorine-doped nano carbon material, the molar ratio of fluorine to carbon atoms is 0.2-0.3, C-F semiionic bonds and C-F covalent bonds with proper proportion are formed between the carbon and the fluorine, the conductivity of the material can be improved due to the C-F semiionic bonds, and the stability of the material can be provided due to the C-F covalent bonds, so that the excellent conductivity and stability of the composite material can be simultaneously endowed. And when the molar ratio of the fluorine to the carbon atoms is within the range of 0.2-0.3, the C-F bond is converted from a semi-ionic bond to a C-F covalent bond with the increase of the fluorine to the carbon ratio. When the fluorine doping amount is too low (molar ratio of fluorine atoms to carbon atoms is <0.2), F doped into the nanocarbon material exists mainly as a C — F semiionic bond, and in this case, although the composite material has good conductivity, the stability is insufficient. When the fluorine doping amount is too high (the molar ratio of fluorine atoms to carbon atoms is greater than 0.3), F doped into the nano carbon material exists mainly as a C-F covalent bond, and although the stability of the composite material can be ensured, the conductivity is low, and the hole transport capability is influenced. According to the embodiment of the invention, the fluorine-doped nano carbon material with the fluorine-carbon ratio of 0.2-0.3 is selected, so that the stability of the material can be ensured, and the conductivity of the material is good.
In a particularly preferred embodiment, the composite material is a composite material formed by a metal phthalocyanine compound and graphene; or the composite material is formed by a metal phthalocyanine compound and graphene oxide. In the composite material, the mass ratio of the metal phthalocyanine compound to the graphene or the graphene oxide is 1:1 to 1:10, so that the composite material can be used as a hole transport material and has a good hole transport effect. When the mass ratio of the metal phthalocyanine compound to the graphene or the graphene oxide exceeds the range of 1:1 to 1:10, the obtained composite material is insufficient in conductivity and stability and is not sufficient to effectively improve the hole transport property. Specifically, when the content of the metal phthalocyanine compound is too low, the stability of the composite material is reduced, and a good stabilizing effect is difficult to achieve, so that the obtained composite material cannot be used as a hole transport material; when the content of the metal phthalocyanine compound is too high, the metal phthalocyanine compound is easily exposed on the film forming surface of the composite film when the composite material is used for forming a film and preparing a hole transport layer, and free radicals of the metal phthalocyanine compound are easily reacted with the material of the next light emitting layer to form a defect recombination center, so that the light emitting efficiency of a device is reduced.
Particularly preferably, the mass ratio of the metal phthalocyanine compound to the graphene or the graphene oxide is 1:1, in which case the structure of the composite material is regular. When the content of the metal phthalocyanine compound is increased, interlayer accumulation occurs under the action of the excessive metal phthalocyanine compound and the graphene oxide or graphene, and meanwhile, the increase of the content of the metal phthalocyanine compound is easier to ensure that crystal grains of the material grow up without being controlled by a conjugation effect, so that the stability of the electrical material is not facilitated.
In a particularly preferred embodiment, the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene; or the composite material is formed by a metal phthalocyanine compound and fluorine-doped graphene oxide, and the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene or the fluorine-doped graphene oxide is 1:1 to 1:10, so that the composite material can be used as a hole transport material and has a good hole transport effect. When the mass ratio of the metal phthalocyanine compound to the graphene or the graphene oxide exceeds the range of 1:1 to 1:10, the obtained composite material is insufficient in conductivity and stability and is not sufficient to effectively improve the hole transport property. Specifically, when the content of the metal phthalocyanine compound is too low, the stability of the composite material is reduced, and a good stabilizing effect is difficult to achieve, so that the obtained composite material cannot be used as a hole transport material; when the content of the metal phthalocyanine compound is too high, the metal phthalocyanine compound is easily exposed on the film forming surface of the composite film when the composite material is used for forming a film and preparing a hole transport layer, and free radicals of the metal phthalocyanine compound are easily reacted with the material of the next light emitting layer to form a defect recombination center, so that the light emitting efficiency of a device is reduced.
Particularly preferably, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene or the fluorine-doped graphene oxide is 1:1, in which case the structure of the composite material is regular. When the content of the metal phthalocyanine compound is increased, interlayer accumulation occurs under the action of the excessive metal phthalocyanine compound and the fluorine-doped graphene oxide or the fluorine-doped graphene, and meanwhile, the increase of the content of the metal phthalocyanine compound is easier to ensure that crystal grains of the material grow up without being controlled by a conjugation effect, which is not favorable for the stability of the electrical material.
The composite material provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention provides a preparation method of a composite material, which comprises the following steps: providing a metal phthalocyanine compound and a nano carbon material, and mixing the metal phthalocyanine compound and the nano carbon material according to the mass ratio of 1:1 to 1: 10.
The preparation method of the composite material provided by the embodiment of the invention only needs to carry out mixing treatment according to the mass ratio of the two materials, and has simple process and strong method controllability.
In the embodiment of the present invention, the selection and preferred cases of the metal phthalocyanine compound and the nanocarbon material can be added to the above.
Preferably, the nano carbon material is selected from one or more of graphene oxide, graphene, carbon fiber and carbon nanotube.
Preferably, the metal phthalocyanine compound is selected from one or more of iron phthalocyanine compounds, cobalt phthalocyanine compounds, nickel phthalocyanine compounds, copper phthalocyanine compounds and zinc phthalocyanine compounds.
Preferably, the nano carbon material is a fluorine-doped nano carbon material.
Preferably, the molar ratio of fluorine atoms to carbon atoms of the fluorine-doped nanocarbon material is 0.2-0.3: 1.
particularly preferably, the composite material is a composite material formed by a metal phthalocyanine compound and graphene.
Further preferably, the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene.
More preferably, when the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene is 1: 1.
Particularly preferably, the composite material is a composite material formed by a metal phthalocyanine compound and graphene oxide.
Further preferably, the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene oxide.
More preferably, when the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene oxide, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene oxide is 1: 1.
Both the metal phthalocyanine compound and the nanocarbon material can be prepared by a conventional method. The invention is not limited.
As an embodiment, when the metal phthalocyanine compound is a copper phthalocyanine compound, it can be prepared in the following manner: 3.24g of phthalocyanin compound, 0.27g of cuprous chloride and 120ml of N, N-Dimethylacetamide (DMAC) are taken to be put into a 500ml flask, condensed and refluxed for reaction for 20 hours at the temperature of 160 ℃, and then the copper phthalocyanine compound powder is obtained after the copper phthalocyanine compound powder is washed by suction and dried.
As an embodiment, when the nanocarbon material is graphene oxide, it may be prepared in the following manner: preparing graphene oxide by a simplified version of Hummers method; sequentially weighing 1.5g of flake graphite, 180ml of concentrated sulfuric acid, 20ml of phosphoric acid and 9g of potassium permanganate, and adding the materials in sequence; carrying out water bath reaction for 12h at the temperature of 48 ℃, then slowly draining the graphene oxide solution into a beaker, dropwise adding hydrogen peroxide until the solution turns to be golden yellow, carrying out ultrasonic dispersion, and sampling and drying to obtain the graphene oxide.
In addition to the above embodiments, it is preferable that the mixing process further includes a fluorination process of the nanocarbon material. F atoms are introduced into the nano carbon material after the fluorination treatment. The electronegativity of the F atom is stronger than that of the carbon atom, the oxygen atom and the hydrogen atom, so that the F atom can attract hole transfer when being used as a hole transfer material, and the potential barrier of carrier transfer is reduced. In addition, F atoms are introduced into the nano carbon material, and fluorine atoms mainly exist in a C-F semiionic bond and a C-F covalent bond, wherein the existence of the C-F semiionic bond can improve the conductivity of the material, and the existence of the C-F covalent bond can provide the stability of the material. The existence of the C-F semi-ionic bond and the C-F covalent bond can endow the composite material with better conductivity and improve the stability of the material.
As a specific example, the method of fluorinating the nanocarbon material by using a plasma method comprises: and placing the nano carbon material in a plasma cavity, introducing inert gas and fluorine source gas, and carrying out plasma treatment for 1-5h at the temperature of 120-150 ℃. The method comprises the steps of fluorinating a nano-carbon material by a plasma method, particularly fluorinating graphene or graphene oxide by the plasma method, and adsorbing fluorine radicals generated by a plasma technology to the nano-carbon material, particularly the graphene or the graphene oxide, and forming different C-F bonds (C-F semi-ionic bonds and C-F covalent bonds) in the plasma fluorination process. Specifically, the embodiment of the invention controls the proportion of the C-F semi-ionic bond and the C-F covalent bond within a proper range by controlling the fluorination temperature within the range of 120-150 ℃, so that the obtained composite material has excellent conductivity and stability.
In this embodiment, the fluorine source may be a gaseous organic alkane containing fluorine, such as tetrafluoromethane, but is not limited thereto. The doping concentration of fluorine atoms in the nano carbon material is controlled by changing the flow of inert gas and fluorine source. Preferably, the gas flow rates of the inert gas and the fluorine source are 1:1-5:1, so that the doping of fluorine atoms in the nano carbon material is ensured to have proper concentration, and the conductivity and the stability of the composite material are considered. Wherein the inert gas includes, but is not limited to, argon.
The quantum dot light-emitting diode further comprises a hole transport layer which is combined between the anode and the quantum dot in a laminating mode, the hole transport layer is made of a composite material containing a metal phthalocyanine compound and a nano carbon material, and the mass ratio of the metal phthalocyanine compound to the nano carbon material in the composite material is 1: 1-1: 10.
According to the quantum dot light-emitting diode provided by the embodiment of the invention, a material obtained by compounding the metal phthalocyanine compound and the nano carbon material according to the mass ratio of 1:1 to 1:10 is used as a hole transport layer material, so that the hole transport capability of the hole transport layer can be effectively improved. In addition, the material obtained by compounding the metal phthalocyanine compound and the nano carbon material has good structural stability, so the quantum dot light-emitting diode has good performance stability.
Specifically, the quantum dot light emitting diode further comprises a substrate, and the material of the substrate can be a conventional substrate material, such as a hard glass substrate, or a flexible substrate. The substrate can be arranged at one end close to the anode and can also be arranged at one end close to the cathode. When the substrate is arranged at one end of the anode, the quantum dot light-emitting diode is an upright quantum dot light-emitting diode; when the substrate is arranged at one end of the cathode, the quantum dot light-emitting diode is an inverted quantum dot light-emitting diode.
The anode may be of conventional anode material such as ITO anode. Preferably, the ITO may be prepared by a magnetron sputtering method. The cathode may be made of conventional cathode materials, such as metal cathode, specifically, silver cathode, and aluminum cathode. Preferably, the ITO can be prepared by an evaporation method, and the evaporation speed is preferably 0.1-0.3 nm/s. In some embodiments, the cathode has a thickness of 50-100 nm.
In the embodiment of the invention, the quantum dot light-emitting layer is laminated and combined between the cathode and the anode, and the quantum dot light-emitting layer can adopt conventional quantum dot materials with conventional colors, including but not limited to core-shell quantum dots such as CdSe/ZnS, CdS/ZnSe, CdZnS/ZnSe and the like or quantum dot materials based on a gradient shell. In some embodiments, the quantum dot light emitting layer has a thickness of 30-60 nm.
In an embodiment of the invention, the quantum dot light emitting diode further includes a hole transport layer laminated and combined between the anode and the quantum dot, and a material of the hole transport layer is a composite material containing a metal phthalocyanine compound and a nanocarbon material, and a mass ratio of the metal phthalocyanine compound to the nanocarbon material in the composite material is 1:1 to 1: 10.
The selection and preferred cases of the metal phthalocyanine compound and the nanocarbon material can be referred to above. Preferably, the nano carbon material is selected from one or more of graphene oxide, graphene, carbon fiber and carbon nanotube. Preferably, the metal phthalocyanine compound is selected from one or more of iron phthalocyanine compounds, cobalt phthalocyanine compounds, nickel phthalocyanine compounds, copper phthalocyanine compounds and zinc phthalocyanine compounds.
Preferably, the nano carbon material is a fluorine-doped nano carbon material. More preferably, the fluorine-doped nano carbon material has a molar ratio of fluorine atoms to carbon atoms of 0.2-0.3: 1.
particularly preferably, the composite material is a composite material formed by a metal phthalocyanine compound and graphene. Further preferably, the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene. By using the metal phthalocyanine compound/graphene composite material as the hole transport layer, the injection and transport capacity of holes are improved, and the hole transport efficiency is increased; meanwhile, the graphene is compounded with the metal phthalocyanine compound after the fluorination treatment, so that the stability of the film is improved, the corrosion of the film to an electrode is reduced, and the stability and the service life of the luminescent device are improved. More preferably, when the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene is 1: 1.
Particularly preferably, the composite material is a composite material formed by a metal phthalocyanine compound and graphene oxide. Further preferably, the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene oxide. By using the metal phthalocyanine compound/graphene oxide composite material as the hole transport layer, the injection and transport capacity of holes are improved, and the hole transport efficiency is increased; meanwhile, the graphene oxide is compounded with the metal phthalocyanine compound after the fluorination treatment, so that the stability of the film is improved, the corrosion of the film to an electrode is reduced, and the stability and the service life of the luminescent device are improved. More preferably, when the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene oxide, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene oxide is 1: 1.
According to the invention, the metal phthalocyanine compound/graphene oxide or the metal phthalocyanine compound/graphene is adopted as the hole transport layer, so that the hole transport capacity can be effectively adjusted and the stability of the device can be improved.
Preferably, the hole transport material is formed into an ink by a solution processing method, and then deposited into a film by a solution processing method. The method of printing is preferably used to prepare a hole transport layer with a metal phthalocyanine compound/graphene oxide or a metal phthalocyanine compound/graphene as a hole transport material. The hole transport layer prepared by the method can improve the hole transport capability, and meanwhile, the stability and the service life of the device are improved because the material with a very stable overall structure is adopted as the hole transport layer.
In some embodiments, the thickness of the empty transport layers is 30-150 nm.
In some embodiments, the quantum dot light emitting diode further comprises an electron transport layer laminated between the cathode and the quantum dot. The electron transport layer may be made of conventional materials, such as zinc oxide thin film, among others. The thickness of the electron transport layer is 50-150 nm.
The following description will be given with reference to specific examples.
Example 1
A quantum dot light emitting diode device includes a substrate, a quantum dot light emitting diode electronic component bonded on the substrate, and an encapsulation film for encapsulating the quantum dot light emitting diode electronic component. The structure of the quantum dot light-emitting diode comprises an ITO substrate and a silver electrode which are oppositely arranged, and a laminated structure arranged between the ITO substrate and the silver electrode, wherein the laminated structure is a phthalocyancopper compound/doped graphene oxide composite film (50 nm)/a quantum dot light-emitting layer (20 nm)/zinc oxide (30nm) which are sequentially laminated and combined, the phthalocyancopper compound/doped graphene oxide composite film is combined on the surface of the ITO electrode, and the zinc oxide is combined on the surface of the silver electrode.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
depositing an anode with the thickness of 30nm on the surface of the bottom by adopting magnetron sputtering;
the mass ratio of the prepared phthalocyancopper compound to the fluorine-doped graphene oxide (F: C atom mol ratio is 0.2) is 1:1, dispersing the composite material in a solvent (water), adding a surfactant, an adhesive and the like to prepare ink, controlling the thickness of a corresponding film layer by printing the number of drops, and preparing a phthalocyancopper compound/fluorine-doped graphene oxide composite film with the thickness of 50nm on an anode;
preparing a quantum dot light-emitting layer on the phthalo-cyano-copper compound/fluorine-doped graphene oxide composite film, wherein the thickness of the quantum dot light-emitting layer is 20 nm.
Preparing an electron transmission layer zinc oxide film on the quantum dot light-emitting layer, wherein the thickness of the electron transmission layer is about 30nm,
and evaporating a top electrode Ag with the thickness of 70 nm.
The method comprises the steps of carrying out performance test on a phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film provided by the embodiment of the invention, specifically, the thickness of the phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film is d, applying a deflection voltage V to two sides of the phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film to ensure that a current carrier moves directionally under the action of an electric field, recording drift current and the time t for the current carrier to pass through the film d by an oscilloscope, and carrying out performance test on the phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film through the carrier mobility d2V, calculated carrier mobility of 5 × 10-2cm2V.s. By the same method, the carrier mobility of the hole transport material TFB of the common QLED device is tested to be 1 multiplied by 10-2cm2V.s. Therefore, the conductivity of the phthalocyanic copper compound/fluorine-doped graphene oxide composite film provided by the embodiment 1 of the invention is obviously improved.
Example 2
A quantum dot light emitting diode device includes a substrate, a quantum dot light emitting diode electronic component bonded on the substrate, and an encapsulation film for encapsulating the quantum dot light emitting diode electronic component. The structure of the quantum dot light-emitting diode comprises an ITO substrate and a silver electrode which are oppositely arranged, and a laminated structure arranged between the ITO substrate and the silver electrode, wherein the laminated structure is a zinc oxide (30 nm)/quantum dot light-emitting layer (20 nm)/phthalocyanic copper compound/doped graphene oxide composite film (30nm) which are sequentially laminated and combined, the phthalocyanic copper compound/doped graphene oxide composite film is combined on the surface of the silver electrode, and the zinc oxide is combined on the surface of the ITO.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
depositing a cathode with the thickness of 30nm on the surface of the bottom by adopting magnetron sputtering;
preparing a zinc oxide film of an electron transmission layer by a printing method, wherein the thickness of the electron transmission layer is about 30 nm;
preparing a quantum dot light-emitting layer on the electron transport layer, wherein the light-emitting thickness of the quantum dot layer is 20 nm;
the mass ratio of the prepared phthalocyancopper compound to the fluorine-doped graphene oxide (F: C atom mol ratio is 0.3) is 1: 5, dispersing the composite material in a solvent (water), adding a surfactant, an adhesive and the like to prepare ink, controlling the thickness of a corresponding film layer by printing the number of drops, and preparing a phthalocyancopper compound/fluorine-fluorine doped graphene oxide composite film with the thickness of 30nm on the quantum dot light-emitting layer;
and evaporating a top electrode Ag on the phthalocyancopper compound/doped graphene oxide composite film, wherein the thickness is 70 nm.
The method comprises the steps of carrying out performance test on a phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film provided by the embodiment of the invention, specifically, the thickness of the phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film is d, applying a deflection voltage V to two sides of the phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film to ensure that a current carrier moves directionally under the action of an electric field, recording drift current and the time t for the current carrier to pass through the film d by an oscilloscope, and carrying out performance test on the phthalocyaninatocopper compound/fluorine-doped graphene oxide composite film through the carrier mobility d2V, calculated carrier mobility of 5.6 × 10-2cm2V.s; by the same method, the carrier mobility of the hole transport material TFB of the common QLED device is tested to be 1 multiplied by 10-2cm2V.s. Therefore, the conductivity of the phthalocyanic copper compound/fluorine-doped graphene oxide composite film provided by the embodiment 2 of the invention is obviously improved.
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 (12)
1. A composite material is characterized by comprising a metal phthalocyanine compound and a nanocarbon material, wherein the mass ratio of the metal phthalocyanine compound to the nanocarbon material is 1:1 to 1: 10.
2. The composite material of claim 1, wherein the nanocarbon material is a fluorine-doped nanocarbon material.
3. The composite material according to claim 2, wherein the fluorine-doped nanocarbon material has a molar ratio of fluorine atoms to carbon atoms of 0.2 to 0.3: 1.
4. the composite material according to any one of claims 1 to 3, wherein the nanocarbon material is selected from one or more of graphene oxide, graphene, carbon fiber and carbon nanotube; the metal phthalocyanine compound is selected from one or more of iron phthalocyanine compounds, cobalt phthalocyanine compounds, nickel phthalocyanine compounds, copper phthalocyanine compounds and zinc phthalocyanine compounds.
5. The composite material of claim 1, wherein the composite material is a composite material formed of a metal phthalocyanine compound and graphene; or
The composite material is formed by a metal phthalocyanine compound and graphene oxide.
6. The composite material of claim 5, wherein the composite material is a composite material formed from a metal phthalocyanine compound and fluorine-doped graphene; or
The composite material is formed by a metal phthalocyanine compound and fluorine-doped graphene oxide.
7. The composite material according to claim 6, wherein when the composite material is a composite material formed by a metal phthalocyanine compound and fluorine-doped graphene, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene is 1: 1; or
When the composite material is formed by a metal phthalocyanine compound and fluorine-doped graphene oxide, the mass ratio of the metal phthalocyanine compound to the fluorine-doped graphene oxide is 1: 1.
8. A preparation method of a composite material is characterized by comprising the following steps:
providing a metal phthalocyanine compound and a nano carbon material, and mixing the metal phthalocyanine compound and the nano carbon material according to the mass ratio of 1:1 to 1: 10.
9. The method of claim 8, wherein the mixing step further comprises fluorinating the nanocarbon material.
10. The method for preparing a composite material according to claim 9, wherein the nanocarbon material is subjected to fluorination treatment by a plasma method, and the method for subjecting the nanocarbon material to fluorination treatment comprises: and placing the nano carbon material in a plasma cavity, introducing inert gas and fluorine source gas, and carrying out plasma treatment for 1-5h at the temperature of 120-150 ℃.
11. A quantum dot light-emitting diode comprising an anode and a cathode which are oppositely arranged, and a quantum dot light-emitting layer which is laminated and combined between the anode and the cathode, wherein the quantum dot light-emitting diode further comprises a hole transport layer which is laminated and combined between the anode and the quantum dot, and the material of the hole transport layer is a composite material containing the composite material as defined in any one of claims 1 to 7 or the composite material prepared by the preparation method as defined in any one of claims 8 to 10.
12. The quantum dot light emitting diode of claim 11, further comprising an electron transport layer laminated between the cathode and the quantum dot.
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