CN113130757A - Composite material, preparation method thereof, photovoltaic device and light emitting diode - Google Patents
Composite material, preparation method thereof, photovoltaic device and light emitting diode Download PDFInfo
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- CN113130757A CN113130757A CN201911410463.4A CN201911410463A CN113130757A CN 113130757 A CN113130757 A CN 113130757A CN 201911410463 A CN201911410463 A CN 201911410463A CN 113130757 A CN113130757 A CN 113130757A
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 195
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 119
- 239000002096 quantum dot Substances 0.000 claims abstract description 96
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 93
- 239000002105 nanoparticle Substances 0.000 claims abstract description 68
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 58
- 238000010521 absorption reaction Methods 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
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- 238000004519 manufacturing process Methods 0.000 claims description 16
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- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
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- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
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- QKZFBFSFZILINR-UHFFFAOYSA-N 3-methyl-N-[4-[4-(N-(3-methylphenyl)anilino)phenyl]phenyl]-N-phenylaniline Chemical compound CC=1C=C(C=CC1)N(C1=CC=C(C=C1)C1=CC=C(N(C2=CC=CC=C2)C2=CC(=CC=C2)C)C=C1)C1=CC=CC=C1.CC=1C=C(C=CC1)N(C1=CC=C(C=C1)C1=CC=C(N(C2=CC=CC=C2)C2=CC(=CC=C2)C)C=C1)C1=CC=CC=C1 QKZFBFSFZILINR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a composite material, a preparation method thereof, a photovoltaic device and a light emitting diode. The composite material comprises titanium dioxide nanoparticles and graphene nanosheets, wherein the titanium dioxide nanoparticles are combined on the surfaces of the graphene nanosheets, and titanium dioxide and graphene in the composite material are freely combined into bonds through dangling bonds, so that the obtained composite material can effectively reduce the dangling bonds on the surfaces of the titanium dioxide nanoparticles, passivate the surface defects of the titanium dioxide nanoparticles, and can be used as an electron transmission layer of a quantum dot device to promote the migration rate of carriers in the device, thereby improving the performance of the device.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a composite material, a preparation method thereof, a photovoltaic device and a light emitting diode.
Background
Quantum Dots (QD) have the optical characteristics of wide excitation spectrum, narrow emission spectrum, adjustable light-emitting wavelength, high light-emitting efficiency and the like, and are considered to be novel photoelectric materials with great potential. Researches find that the light conversion efficiency of the solar cell based on the metal halide perovskite quantum dot material can reach 20%, which is not comparable with other materials.
At present, in a high-efficiency quantum dot solar cell, the basic cell structures respectively comprise glass and fluorine-doped tin oxide (SnO)2F, FTO), an electron transport layer, a light absorption sensitizing layer, a hole transport layer and a metal electrode. As the most commonly used material of the electron transport layer, the titanium dioxide film has the characteristics of no toxicity, environmental protection, high transparency, good light stability and the like. Nevertheless, the titanium dioxide film as the electron transport layer of the solar cell still has the disadvantages, such as small particle size of titanium dioxide nanoparticles, and the existence of a large number of defects formed by unsaturated titanium dangling bonds on the particle surface, and these defects act as electron traps, and can capture electrons in the working process of the photoelectric device, and reduce the electron transport efficiency in the device, thereby affecting the photoelectric performance of the device.
Thus, the prior art remains to be improved.
Disclosure of Invention
The invention aims to provide a composite material and a preparation method thereof, and aims to solve the technical problem that the titanium dioxide nano material has surface defects so as to influence the carrier migration rate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a composite material comprises the following steps:
dissolving graphene oxide in a first solvent to obtain a first solution;
dissolving a titanium-containing precursor salt in a second solvent to obtain a second solution;
adding the first solution into the second solution, and standing to obtain a precursor solution;
and calcining the precursor solution to obtain the composite material.
According to the preparation method of the composite material, the graphene oxide and the titanium-containing precursor salt are used as raw materials to prepare the precursor solution of the composite material, in the process, the titanium-containing precursor is hydrolyzed to generate metatitanic acid, and the metatitanic acid is firmly combined with the graphene oxide through the action of hydrogen bonds (a large amount of oxygen-containing functional groups exist in the graphene oxide); and then in the process of calcining the precursor solution, the graphene oxide is pyrolyzed into graphene, nano titanium dioxide is generated on the graphene in situ by metatitanic acid, dangling bonds in the titanium dioxide and the graphene are freely combined into bonds to form the graphene nano titanium dioxide composite material, so that the obtained composite material can effectively reduce the surface dangling bonds of titanium dioxide nanoparticles and passivate the surface defects of the titanium dioxide nanoparticles, and the obtained composite material can be used as an electron transport layer of a quantum dot device, so that the migration rate of current carriers in the device can be promoted, and the performance of the device is improved.
The invention also provides a composite material, which is prepared by the preparation method.
And, a composite material comprising titanium dioxide nanoparticles and graphene nanoplatelets, the titanium dioxide nanoparticles being bound to the surface of the graphene nanoplatelets.
The composite material provided by the invention comprises titanium dioxide nanoparticles and graphene nanosheets, wherein the titanium dioxide nanoparticles are combined on the surfaces of the graphene nanosheets, and the titanium dioxide and the graphene in the composite material are freely combined into bonds through dangling bonds, so that the obtained composite material can effectively reduce the dangling bonds on the surfaces of the titanium dioxide nanoparticles, passivate the surface defects of the titanium dioxide nanoparticles, and can be used as an electron transmission layer of a quantum dot device, so that the migration rate of carriers in the device can be promoted, and the performance of the device can be improved.
The invention also aims to provide a photovoltaic device, aiming at solving the technical problem that the carrier migration rate of the device is influenced by the surface defects of the titanium dioxide material in the existing photovoltaic device. In order to achieve the purpose, the invention adopts the following technical scheme:
a photovoltaic device, comprising:
a cathode and an anode which are oppositely arranged;
a quantum dot photosensitizing absorption layer located between the cathode and the anode;
an electron transport layer disposed between the cathode and the quantum dot photosensitizing absorption layer;
the material for forming the electron transport layer comprises the composite material or the composite material obtained by the preparation method.
The photovoltaic device provided by the invention is a quantum dot photovoltaic device, the material of the electron transmission layer of the photovoltaic device comprises titanium dioxide nano particles and graphene nano sheets, and the titanium dioxide nano particles and dangling bonds in the graphene are freely combined into bonds, so that the defects of the titanium dioxide nano particles are effectively reduced, the transmission rate of carriers in the device is increased, and the photoelectric performance of the quantum dot photovoltaic device is improved.
The invention also aims to provide a light-emitting diode, aiming at solving the technical problem that the carrier migration rate of a device is influenced by the surface defect of a titanium dioxide material in the conventional light-emitting diode device. In order to achieve the purpose, the invention adopts the following technical scheme:
a light emitting diode comprising:
a cathode and an anode which are oppositely arranged;
a quantum dot light emitting layer positioned between the cathode and the anode;
an electron transport layer disposed between the cathode and the quantum dot light emitting layer;
the material for forming the electron transport layer comprises the composite material or the composite material obtained by the preparation method.
The light-emitting diode provided by the invention is a quantum dot light-emitting diode, the material of the electron transmission layer of the light-emitting diode comprises titanium dioxide nano-particles and graphene nano-sheets, and the titanium dioxide nano-particles and dangling bonds in the graphene are freely combined into bonds, so that the defects of the titanium dioxide nano-particles are effectively reduced, the transmission rate of carriers in the device is increased, and the light-emitting performance of the device is finally improved.
Drawings
FIG. 1 is a schematic flow chart of a method of preparing a composite material according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a quantum dot photovoltaic device according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
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 one aspect, an embodiment of the present invention provides a method for preparing a composite material, as shown in fig. 1, the method includes the following steps:
s01: dissolving graphene oxide in a first solvent to obtain a first solution;
s02: dissolving a titanium-containing precursor salt in a second solvent to obtain a second solution;
s03: adding the first solution into the second solution, and standing to obtain a precursor solution;
s04: and calcining the precursor solution to obtain the composite material.
According to the preparation method of the composite material, the graphene oxide and the titanium-containing precursor salt are used as raw materials to prepare the precursor solution of the composite material, in the process, the titanium-containing precursor is hydrolyzed to generate metatitanic acid, and the metatitanic acid is firmly combined with the graphene oxide through the action of hydrogen bonds (a large amount of oxygen-containing functional groups exist in the graphene oxide); and then in the process of calcining the precursor solution, the graphene oxide is pyrolyzed into graphene, nano titanium dioxide is generated on the graphene in situ by metatitanic acid, dangling bonds in the titanium dioxide and the graphene are freely combined into bonds to form the graphene nano titanium dioxide composite material, so that the obtained composite material can effectively reduce the surface dangling bonds of titanium dioxide nanoparticles and passivate the surface defects of the titanium dioxide nanoparticles, and the obtained composite material can be used as an electron transport layer of a quantum dot device, so that the migration rate of current carriers in the device can be promoted, and the performance of the device is improved.
In a fruitIn an embodiment, the composite material obtained by the preparation method comprises titanium dioxide nanoparticles and graphene nanosheets, the mass ratio of the graphene nanosheets to the titanium dioxide nanoparticles is 1 (20-100), the effect of reducing dangling bonds on the surface of the titanium dioxide nanoparticles is optimal for the composite material obtained within the mass ratio range, and further the specific surface area of the graphene nanosheets obtained after calcination is about 2600m2Per g, graphene nanoplatelets in this range of specific surface area can bind more titanium dioxide nanoparticles. Further, the titanium dioxide nanoparticles are anatase crystal type titanium dioxide nanoparticles.
Step S01, the mass concentration range of the graphene oxide in the first solution is 3-20 mg/ml; the graphene oxide concentration is too low, and after the graphene oxide is mixed with the second solution in the same proportion, the graphene content in the prepared composite material is too low, so that the graphene oxide composite material is used in a device, the improvement on the carrier migration rate is not obvious, the performance optimization space of the device is small, the graphene oxide concentration is too high, the dispersion difficulty is increased, partial graphite oxide is not completely stripped into single-layer graphene oxide, the obtained composite material influences the electronic transmission capability of the composite material, and the improvement on the photoelectric performance of the device is not facilitated.
The first solvent comprises at least one of water and an alcohol solvent, and specifically can be a combination of water and an alcohol solvent, wherein the alcohol solvent can be a solvent such as methanol, ethanol, propanol, and the like, and absolute ethanol is preferred in the embodiment of the invention. Specifically, a certain amount of graphite oxide powder and deionized water are added into a beaker and subjected to ultrasonic dispersion to obtain graphene oxide aqueous dispersion, then a certain amount of alcohol solvent (such as ethanol) is added into the graphene oxide aqueous dispersion, and the mixture is stirred uniformly at room temperature to obtain a first solution. In the above process, the purpose of the ultrasonic treatment is to peel off the multi-layered graphene oxide into a single-layered graphene oxide. The graphene oxide is obtained by oxidizing graphene, and the distance between graphene oxide layers is far larger than that of the graphene, so that the graphene oxide can be peeled into single-layer graphene oxide through simple ultrasonic treatment. The ultrasonic treatment time range is 10-60 min, the ultrasonic time is too short, the single-layer graphene oxide is not completely separated, the performance of the device is improved due to the obtained composite material, the ultrasonic time is too long, the production efficiency is reduced, and the industrial application is not facilitated. In the process, absolute ethyl alcohol is doped into the graphene oxide aqueous dispersion, so that the concentration of deionized water is diluted by the ethyl alcohol, the subsequent hydrolysis reaction rate is reduced, and the uniformity of a precursor solution and the reaction operability are improved. In the first solvent, the volume ratio of deionized water to alcohol solvent (such as absolute ethyl alcohol) is in the range of 1: (3-20), the proportion of the two is too large, the water content in the first solution system is too high, the subsequent hydrolysis reaction of titanium-containing precursor salt such as butyl titanate is too fast, the reaction system is easy to form gel, the fluidity is lost, and the subsequent spin coating film forming is difficult; the proportion of the two is too small, the hydrolysis process is slow, the preparation period of the precursor material is prolonged, and the industrial production is not facilitated.
Step S02, the second solvent includes an alcohol solvent, which may be methanol, ethanol, propanol, etc., the titanium-containing precursor salt is selected from at least one of propyl titanate and isobutyl titanate, such as isobutyl titanate and isopropyl titanate, for example, butyl titanate and ethanol, and the volume ratio of butyl titanate and ethanol is in the range of 1: (10-50), the proportion of the two is too low, the content of butyl titanate in the system is low, if a precursor solution is formed into a film, the film layer is too thin, the migration of current carriers in the device is influenced, the photoelectric property of the device is poor, the proportion of the two is too high, the concentration of butyl titanate is high, gel is easily formed in the hydrolysis process, and the subsequent preparation is influenced.
Step S03, in the step of adding the first solution into the second solution, the first solution is dripped into the second solution at the speed of 1-10 ml/min; the dripping speed is slow, the reaction period is long, and the production is not facilitated. The dropping speed is too fast, a large amount of deionized water is rapidly introduced into a mixed system, the hydrolysis speed of the precursor salt containing the titanium element is very fast, the mixed system is easy to form gel, the fluidity is lost, and the subsequent production cannot be carried out. In the above process, the volume ratio range of the first solution and the second solution is 1: (0.5-10), the proportion of the first solution to the second solution is too small, the water content in the system is too small, the hydrolysis of a precursor salt (such as butyl titanate) of titanium is slow, the system contains a large amount of precursor salt containing titanium, and the butyl titanate is easy to volatilize in the subsequent calcination process, so that the content of titanium dioxide is reduced. The proportion of the titanium element precursor salt and the water content in the mixed system is too large, the hydrolysis rate of the titanium element precursor salt is high, the mixed system is easy to form gel, the fluidity is lost, and the subsequent production cannot be carried out.
Further, the temperature range of the standing treatment is 20-50 ℃; the standing time range is 2-8 h. The standing temperature is that the hydrolysis temperature range of the titanium element precursor salt is 20-50 ℃, the standing treatment temperature is too low, the hydrolysis of the titanium element precursor salt (such as butyl titanate) is incomplete, and the system contains a large amount of titanium element precursor salt which is easy to volatilize in the subsequent calcination process; the temperature of the standing treatment is too high, the reaction system is easy to form gel, the fluidity is lost, and the subsequent process is influenced. The standing time range of the mixed solution is 2-8 h, the standing time is too short, the raw materials cannot be hydrolyzed fully, the hydrolysis time is too long, a reaction system is easy to form gel, and the subsequent process is influenced.
In step S04, the composite material may be obtained by calcining the precursor solution. In order to obtain the composite material film, the precursor solution can be deposited on the substrate and calcined to obtain the composite material film, namely the composite material film can be used as an electron transport layer of a device. The method comprises the following specific steps: and after obtaining the precursor solution, spin-coating the precursor solution on the substrate at the speed of 1000-5000 rpm. If the spin coating speed is too low, the obtained film layer is too thick, and if the spin coating speed is too high, the obtained film layer is too thin, and the film layer with the thickness of 30-50 nm can be obtained within the speed range. The electron transport layer in the device is too thin or too thick, which leads to the imbalance of electron-hole inside the device, and thus leads to the deterioration of the device performance.
Further, the temperature range of the calcining treatment is 400-600 ℃; the time range of the calcination treatment is 30-90 mim. The purpose of calcination is to decompose metatitanic acid by heating to produce titanium dioxide nanocrystals in anatase crystal form, and simultaneously, graphene oxide is reduced to graphene by thermal reduction reaction. In the process, the dangling bond on the surface of the titanium dioxide and the dangling bond of the graphene form a bond freely, so that the surface defect of the nano titanium dioxide can be reduced. The calcining temperature range is 400-600 ℃, metatitanic acid is decomposed into amorphous titanium dioxide, the electron mobility is poor, the performance of the device is poor, the calcining temperature is too high, the crystal form of the titanium dioxide is rutile structure from anatase structure, the electron mobility and the charge diffusion coefficient are both obviously reduced, and the photoelectric performance of the device is poor; the calcining time range is 30-90 min, the calcining time is too short, the anatase purity is low, the photoelectric property of the device is poor, the calcining time is too long, and the preparation period of the device is prolonged. The atmosphere for the calcination treatment may be an inert gas such as nitrogen or argon.
On the other hand, the embodiment of the invention also provides a composite material, and the composite material is prepared by the preparation method. Specifically, the composite material comprises titanium dioxide nanoparticles and graphene nanosheets, wherein the titanium dioxide nanoparticles are bonded to the surface of the graphene nanosheets.
The composite material provided by the embodiment of the invention comprises titanium dioxide nanoparticles and graphene nanosheets, wherein the titanium dioxide nanoparticles are combined on the surfaces of the graphene nanosheets, and the titanium dioxide and the graphene in the composite material are freely combined into bonds through dangling bonds, so that the obtained composite material can effectively reduce the dangling bonds on the surfaces of the titanium dioxide nanoparticles, passivate the surface defects of the titanium dioxide nanoparticles, and can be used as an electron transmission layer of a quantum dot device to promote the migration rate of carriers in the device, thereby improving the performance of the device. More specifically, the composite material is composed of titanium dioxide nanoparticles and graphene nanoplates. Wherein, the titanium dioxide nano-particles are combined on the surface of the graphene nano-sheet.
In one embodiment, in the composite material of the embodiment of the present invention, the mass ratio of the graphene nanoplatelets to the titanium dioxide nanoparticles is 1: (20-100), the composite material in the mass ratio range has the best effect of reducing dangling bonds on the surface of the titanium dioxide nano material, and further, the specific surface area of the graphene nano sheet is about 2600m2Per g, graphene nanoplatelets in this range of specific surface area can bind more titanium dioxide nanoparticles. Further, the titanium dioxide nanoparticlesThe particles are anatase crystal type titanium dioxide nano particles.
On the other hand, an embodiment of the present invention provides a photovoltaic device, which is a quantum dot photovoltaic device, as shown in fig. 2, the quantum dot photovoltaic device includes a cathode, an anode, and a quantum dot light-sensitized absorption layer located between the cathode and the anode, an electron transport layer is disposed between the cathode and the quantum dot light-sensitized absorption layer, and the electron transport layer is composed of the composite material according to the embodiment of the present invention or the composite material obtained by the preparation method according to the embodiment of the present invention. Namely, the material of the electron transport layer comprises titanium dioxide nanoparticles and graphene nanosheets, and the titanium dioxide nanoparticles are bonded to the surfaces of the graphene nanosheets. More specifically, the electron transport layer in the quantum dot photovoltaic device is composed of titanium dioxide nanoparticles and graphene nanosheets. Wherein, the titanium dioxide nano-particles are combined on the surface of the graphene nano-sheet.
In the quantum dot photovoltaic device provided by the embodiment of the invention, the material of the electron transport layer comprises titanium dioxide nanoparticles and graphene nanosheets, and the titanium dioxide nanoparticles and dangling bonds in graphene are freely combined into bonds, so that the defects of the titanium dioxide nanoparticles are effectively reduced, the transmission rate of carriers in the device is increased, and the photoelectric performance of the quantum dot photovoltaic device is improved.
Graphene (Graphene) is a planar two-dimensional nanomaterial composed of single-layer carbon atoms, and the carbon atoms composed of the Graphene are subjected to orbital hybridization in an sp2 mode, so that the Graphene has the characteristics of high thermal conductivity, high electrical conductivity, high structural strength and the like. By virtue of the excellent physical and chemical properties of the graphene, the graphene has a wide application prospect in the field of photoelectric devices. In the embodiment of the invention, the titanium dioxide nanoparticles and dangling bonds in graphene are freely combined into bonds, so that the defects of the titanium dioxide nanoparticles are effectively reduced, the transmission rate of carriers in the device is increased, and the photoelectric performance of the quantum dot photovoltaic device is improved.
In one embodiment, the mass ratio of the graphene nanoplatelets to the titanium dioxide nanoparticles of the electron transport layer is in a range of 1: (20 to 100); the electron transport layer obtained in the mass ratio range has the best effect of reducing dangling bonds on the surface of the titanium dioxide nano material, and further, the specific surface area of the graphene nanosheet in the electron transport layer is about 2600m2Per gram, graphene in this specific surface area range can bind more titanium dioxide nanoparticles. Further, the titanium dioxide nanoparticles are anatase crystal type titanium dioxide nanoparticles. Furthermore, the thickness range of the electron transmission layer is 30-50 nm. The electron-hole balance in the photovoltaic device can be influenced by the fact that the electron transport layer is too thin and too thick, and the balance of current carriers is optimal within the thickness range.
Further, as shown in fig. 2, a hole transport layer is disposed between the anode and the quantum dot photosensitizing absorption layer. The material of the hole transport layer may be P3H T (poly (3-hexylthiophene-2, 5-diyl)), TFB (poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (4,4' - (N- (4-N-butyl) phenyl) -diphenylamine) ]), PVK (polyvinylcarbazole), poly-TPD (N, N ' -bis (3-methylphenyl) -N, N ' -diphenyl-1, 1 ' -biphenyl-4, 4' -diamine), TCTA (4,4',4 ″ -tris (carbazol-9-yl) triphenylamine), CBP (4,4' -bis (9-carbazole) biphenyl), and other common hole transport layer materials.
In one embodiment, the cathode is disposed on a substrate (e.g., a glass substrate), and the cathode may be ITO glass or FTO glass; the anode is made of metal materials, and the metal materials of the anode can be aluminum simple substance, magnesium simple substance, calcium simple substance, silver simple substance and other materials and alloy materials thereof; the thickness range of the anode is 20-200 nm, the anode is too thin, the electrode is easily damaged, the use of a device is influenced, the metal electrode is too thick, the consumption of raw materials is increased, the evaporation time is prolonged, and the production cost is increased. The quantum dot material in the quantum dot light-sensitized absorption layer can be II-VI family single-component quantum dots, or core-shell structure quantum dots, or alloy structure quantum dot materials; III-V group single-component quantum dots, or core-shell structure quantum dots, or alloy structure quantum dot materials; an organic-inorganic hybrid perovskite quantum dot material; at least one of fully inorganic quantum dot materials. The particle size range of the quantum dot material is 2-10 nm, the particle size is too small, the film forming property of the quantum dot material is poor, the energy resonance transfer effect among quantum dot particles is obvious, the application of the material is not facilitated, the particle size is too large, the quantum effect of the quantum dot material is weakened, and the photoelectric property of the material is reduced.
The embodiment of the invention also provides a preparation method of the quantum dot photovoltaic device, which comprises the following steps: providing a substrate; preparing an electron transport layer on the substrate; wherein the material of the electron transport layer comprises titanium dioxide nanoparticles and graphene nanoplatelets, and the titanium dioxide nanoparticles are combined on the surface of the graphene nanoplatelets.
The substrate may be a cathode substrate, and specifically, may be ITO glass or FTO glass. The step of preparing an electron transport layer on the substrate includes: dissolving graphene oxide in a first solvent to obtain a first solution; dissolving a titanium-containing precursor salt in a second solvent to obtain a second solution; adding the first solution into the second solution, and standing to obtain a precursor solution; depositing the precursor solution on the substrate, and then performing calcination treatment to obtain the electron transport layer; the selection of specific materials and process parameters may be referred to above for the preparation of the composite material. The process can effectively reduce the surface dangling bonds of titanium dioxide nano particles, passivate material defects and promote the migration rate of current carriers in a device, meanwhile, the flatness of a calcined film is good, the calcined film is tightly combined with a substrate and a subsequently prepared quantum dot light-sensitized absorption layer, the interface resistance is small, namely, the interface combination effect is good, thus the transmission of the current carriers is facilitated, the quality of an electronic transmission film is further improved through a specific film forming mode of a photovoltaic device, and the photoelectric performance of the device is improved. The preparation method is simple to operate, low in cost and easy to realize industrialization, and has good application prospects in the field of solar cells.
Finally, after the preparation of the electron transport layer, the subsequent steps include: preparing a quantum dot light-sensitized absorption layer on the electron transport layer, preparing a hole transport layer on the quantum dot light-sensitized absorption layer, and preparing an anode on the hole transport layer.
In a particular embodiment, the method of making the photovoltaic device comprises:
(1) preparation of precursor solution
A: adding a certain amount of graphite oxide powder and deionized water into a beaker, and performing ultrasonic dispersion to obtain the graphene oxide aqueous dispersion. And then, adding a certain amount of ethanol into the graphene oxide aqueous dispersion, and uniformly stirring at room temperature to obtain a dispersion A.
B: adding a certain amount of titanium precursor salt and absolute ethyl alcohol into a beaker, and uniformly stirring at room temperature to obtain a uniform and transparent butyl titanate ethanol solution B
And then, slowly dropwise adding the solution A into the solution B, continuously stirring, standing and reacting the mixed solution for a period of time after dropwise adding is finished, and obtaining an electron transport layer precursor solution. In the process, precursor salt of titanium element is contacted with deionized water, and hydrolysis reaction is slowly carried out to generate metatitanic acid and metatitanic acid sol is formed. Meanwhile, metatitanic acid is uniformly and firmly dispersed in graphene oxide through hydrogen bond interaction, so that nano titanium dioxide is generated on graphene in situ and uniformly in the subsequent spin coating and calcining processes.
(2) Process for making photovoltaic devices
The structural schematic diagram of the quantum dot photoelectric device is shown in fig. 2, and the quantum dot photoelectric device sequentially comprises the following components from bottom to top: a cathode (which may be a glass substrate + ITO); an electron transport layer; a quantum dot photosensitizing absorption layer; a hole transport layer; and an anode.
The preparation method comprises the following specific steps:
a: firstly, spin-coating the precursor solution of the electron transport layer prepared in the step (1) on ITO glass, placing the spin-coated wafer in a muffle furnace, calcining at constant temperature, and forming the electron transport layer of the graphene composite nano titanium dioxide on the ITO glass. The spin coating speed of the electron transmission layer is 1000-5000 rpm; the muffle furnace calcination treatment aims to decompose metatitanic acid in the film by heating to generate titanium dioxide nanocrystals in anatase crystal form, and simultaneously, graphene oxide is heated to generate thermal reduction reaction and reduced into graphene. In the process, the dangling bond on the surface of the titanium dioxide and the dangling bond of the graphene form a bond freely, so that the surface defect of the nano titanium dioxide can be reduced. The calcining temperature ranges from 400 ℃ to 600 ℃, and the calcining time ranges from 30min to 90 min;
b: and (3) spin-coating quantum dots on the electron transport layer to prepare the quantum dot light-sensitized absorption layer. The specific method comprises the following steps: providing a quantum dot material, dissolving the quantum dot material in n-octane to prepare a quantum dot solution with a certain concentration, and spin-coating the solution on the electron transport layer. And the spin-coated wafer is subjected to a heating treatment to remove the remaining solvent.
The quantum dot material can be II-VI family single-component quantum dots, core-shell structure quantum dots or alloy structure quantum dot materials; III-V group single-component quantum dots, or core-shell structure quantum dots, or alloy structure quantum dot materials; an organic-inorganic hybrid perovskite quantum dot material; at least one of fully inorganic quantum dot materials. The particle size range of the quantum dot material is 2-10 nm, the particle size is too small, the film forming property of the quantum dot material is poor, the energy resonance transfer effect among quantum dot particles is obvious, the application of the material is not facilitated, the particle size is too large, the quantum effect of the quantum dot material is weakened, and the photoelectric property of the material is reduced. The quantum dot material is dissolved in n-octane, the concentration range of the quantum dot material is 10-50 mg/ml, the concentration of the quantum dot material is too low, a photosensitization absorption layer in a photovoltaic device is too thin, the light absorption efficiency is low, the concentration of the quantum dot material is too high, the photosensitization absorption layer is too thick, the quantum dot material is easy to agglomerate, the smoothness of the photosensitization absorption layer is influenced, and the combination of functional layers in the photovoltaic device is not facilitated; the spin-coating speed of the quantum dot light-sensitized absorption layer is 1000-5000 rpm, the spin-coating speed is too low, the light-sensitized absorption layer is too thick, the quantum dot material is easy to agglomerate, the smoothness of the light-sensitized absorption layer is affected, the electron movement in a photovoltaic device is not facilitated, the spin-coating speed is too high, the light-sensitized absorption layer in the photovoltaic device is too thin, and the light absorption efficiency is relatively low; the quantum dot light-sensitized absorption layer is prepared, the spin coating time is 30-90 s, the time is too short, the light-sensitized absorption layer contains a large amount of solvent and is not volatilized, the light-sensitized absorption layer is easily damaged in the subsequent drying process, the film forming effect is poor, the spin coating time is too long, and the production efficiency is reduced; the heating treatment is to completely remove solvent molecules in the quantum dot light-sensitized absorption layer and avoid the influence of residual solvent on the film forming effect of the light-sensitized absorption layer. The heating temperature range is 80-150 ℃, the temperature is too low, solvent molecules are difficult to completely remove, the temperature is too high, the film structure of the photosensitization absorption layer is easy to damage, and the photoelectric performance of the device is influenced; the heating time range is 10-60 min, the time is too short, solvent molecules are difficult to completely remove, the time is too long, the preparation period of a device is prolonged, and the production is not facilitated;
c: and (3) spin-coating a high molecular material on the quantum dot light sensitization absorption layer to prepare a hole transport layer. The specific method comprises the following steps: p3HT was dissolved in dichlorobenzene solvent to prepare a P3HT solution at a certain concentration, and the solution was spin coated over the photosensitized absorbing layer. After the completion of spin coating, the wafer is subjected to heat treatment to remove the remaining solvent. Wherein, the P3HT can be replaced by common hole transport layer materials such as TFB, PVK, poly-TPD, TCTA, CBP and the like; the spin coating speed of the hole transport layer is 1000-5000 rpm, the spin coating speed is too low, the hole transport layer is too thick, the spin coating speed is too high, the hole transport layer is too thin, and the hole transport layer is too thin and too thick, so that the internal electron-hole imbalance of the device can be caused, and the performance of the device is further poor. The concentration range of the P3HT dissolved in dichlorobenzene is 10-50 mg/ml, the concentration is too low, a hole transport layer in a photovoltaic device is too thin and too high, the hole transport layer is too thick, and the electron-hole imbalance in the device can be caused by the fact that the hole transport layer is too thin and too thick, so that the performance of the device is poor; the spin coating time range of the prepared hole transport layer is 30-90 s, the time is too short, the hole transport layer contains a large amount of solvent and is not volatilized, the film forming effect of the electron transport layer is poor in the subsequent drying process, the spin coating time is too long, and the production efficiency is reduced; the heat treatment is intended to completely remove solvent molecules in the hole transport layer and prevent residual solvent from affecting the film formation effect. The heating temperature range is 50-150 ℃, the temperature is too low, solvent molecules are difficult to completely remove, the temperature is too high, the functional layer film structure of the photovoltaic device is easy to damage, and the photoelectric performance of the device is influenced; the heating time range is 10-60 min, the time is too short, solvent molecules are difficult to completely remove, the time is too long, the structure of a functional layer film of the device is easy to damage, and the photoelectric performance of the device is influenced;
d: and preparing a metal anode above the hole transport layer in a vacuum thermal evaporation mode. In the process, the metal material is bombarded and heated by electron beams with certain current in a vacuum environment, is evaporated into an atomic state, and then atom steam freely moves in a vacuum cavity and collides with the surface of a substrate with lower temperature to be condensed to form a film. The metal material can be a simple substance of aluminum, a simple substance of magnesium, a simple substance of calcium, a simple substance of silver and other materials and alloy materials thereof; the electron beam bombardment current range is 100-250A, the current is too small, the evaporation of metal materials is difficult, the evaporation is difficult, the current is too high, a large amount of metal atom steam is pure in a vacuum cavity, the evaporation process is fast carried out, the flatness of a metal electrode film is reduced, the contact between the electrode and a hole transmission layer is influenced, and the transmission of current carriers in a device is not facilitated; the thickness range of the metal anode is 20-200 nm, the metal anode is too thin, the electrode is easily damaged, the use of a device is influenced, the metal electrode is too thick, the consumption of raw materials is increased, the evaporation time is prolonged, and the production cost is increased.
Finally, an embodiment of the present invention further provides a light emitting diode, where the light emitting diode is a quantum dot light emitting diode, as shown in fig. 3, the quantum dot light emitting diode includes: a cathode and an anode which are oppositely arranged; a quantum dot light emitting layer positioned between the cathode and the anode; and the electron transport layer is arranged between the cathode and the quantum dot light-emitting layer and consists of the composite material or the composite material prepared by the preparation method.
The light-emitting diode provided by the embodiment of the invention is a quantum dot light-emitting diode, the material of the electron transmission layer of the light-emitting diode comprises titanium dioxide nano-particles and graphene nano-sheets, and the titanium dioxide nano-particles and dangling bonds in the graphene are freely combined into bonds, so that the defects of the titanium dioxide nano-particles are effectively reduced, the transmission rate of carriers in the device is increased, and the light-emitting performance of the device is finally improved. More specifically, the electron transport layer in the light emitting diode is composed of titanium dioxide nanoparticles and graphene nanosheets. Wherein, the titanium dioxide nano-particles are combined on the surface of the graphene nano-sheet.
Furthermore, the thickness range of the electron transmission layer is 30-50 nm. Further, as shown in fig. 3, a hole transport layer is disposed between the anode and the quantum dot light emitting layer. For the quantum dot light emitting diode, the cathode, the anode, the hole transport layer and the electron transport layer of the quantum dot light emitting diode and the preparation method thereof can refer to the description of the photovoltaic device.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A photovoltaic device comprising, in order from bottom to top: comprises ITO glass, an electron transport layer, a quantum dot light sensitization absorption layer, a hole transport layer and an anode; the preparation method comprises the following steps:
(1) preparation of precursor solution for forming electron transport layer
A: and sequentially adding 10ml of deionized water and 50mg of graphite oxide powder into a 100ml beaker, and carrying out ultrasonic treatment for 30min to obtain a light yellow graphene oxide aqueous dispersion. Then, 40ml of absolute ethyl alcohol is added into the dispersion liquid, and the mixture is stirred uniformly at room temperature to obtain uniform solution A;
b: sequentially adding 5ml of butyl titanate and 50ml of absolute ethyl alcohol into a 100ml beaker, and uniformly stirring at room temperature to obtain a uniform and transparent butyl titanate ethanol solution B;
and then, slowly dropwise adding 25ml of the solution A into 55ml of the solution B, continuously stirring, transferring the mixed solution into a 35 ℃ oven after dropwise adding is finished, standing for reacting for 2 hours, and taking out to obtain a precursor solution.
(2) Process for preparing photovoltaic devices
A: firstly, providing ITO glass, fixing the ITO glass in a spin coater, then, taking 0.2ml of the prepared precursor solution of the electron transport layer, dropwise adding the precursor solution to an ITO glass substrate, spin-coating for 30s at the rotating speed of 3000rpm, placing the spin-coated wafer in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃ under the protection of argon atmosphere, and forming the electron transport layer (the material is a graphene nano titanium dioxide composite material, wherein the mass ratio of graphene to titanium dioxide is 2.2: 100) on the ITO glass.
B: and then, re-fixing the wafer on a spin coater, dropwise adding 0.2ml of CdSe/CdS quantum dot n-octane solution with the concentration of 30mg/ml above the electron transport layer, spin-coating at 3000rpm for 40s, heating the spin-coated wafer to 80 ℃, carrying out heat treatment for 30min, removing the residual solvent, and completing the preparation of the quantum dot light-sensitized absorption layer.
C: then, the wafer was fixed again on a spin coater, 0.2ml of a 10mg/ml P3HT dichlorobenzene solution was added dropwise over the quantum dot photosensitized absorption layer and spin-coated at 3000rpm for 30s, and the spin-coated wafer was heated to 80 ℃ and heat-treated for 30min to remove the remaining solvent, thereby completing the preparation of the hole transport layer.
D: and finally, transferring the wafer into an evaporation machine, bombarding a silver simple substance by an electron beam with the current of 100A, evaporating the silver simple substance into atomic steam, forming a silver electrode with the thickness of 100nm, namely an anode, above the hole transport layer, and packaging to obtain the final photovoltaic device.
Example 2
A photovoltaic device comprising, in order from bottom to top: comprises ITO glass, an electron transport layer, a quantum dot light sensitization absorption layer, a hole transport layer and an anode; the preparation method comprises the following steps:
(1) preparation of precursor solution for forming electron transport layer
A: and sequentially adding 10ml of deionized water and 50mg of graphite oxide powder into a 100ml beaker, and carrying out ultrasonic treatment for 30min to obtain a light yellow graphene oxide aqueous dispersion. Then, 40ml of absolute ethyl alcohol is added into the dispersion liquid, and the mixture is stirred uniformly at room temperature to obtain uniform solution A;
b: sequentially adding 5ml of isopropyl titanate and 50ml of absolute ethyl alcohol into a 100ml beaker, and uniformly stirring at room temperature to obtain a uniform and transparent butyl titanate ethanol solution B;
and then, slowly dropwise adding 25ml of the solution A into 55ml of the solution B, continuously stirring, transferring the mixed solution into a 35 ℃ oven after dropwise adding is finished, standing for reacting for 2 hours, and taking out to obtain a precursor solution.
(2) Process for preparing photovoltaic devices
A: firstly, providing ITO glass, fixing the ITO glass in a spin coater, then, taking 0.2ml of the prepared precursor solution of the electron transport layer, dropwise adding the precursor solution to an ITO glass substrate, spin-coating for 30s at the rotating speed of 3000rpm, placing the spin-coated wafer in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃ under the protection of argon atmosphere, and forming the electron transport layer (the material is a graphene nano titanium dioxide composite material, wherein the mass ratio of graphene to titanium dioxide is 2.7: 100) on the ITO glass.
B: and then, re-fixing the wafer on a spin coater, dropwise adding 0.2ml of CdSe/CdS quantum dot n-octane solution with the concentration of 30mg/ml above the electron transport layer, spin-coating at 3000rpm for 40s, heating the spin-coated wafer to 80 ℃, carrying out heat treatment for 30min, removing the residual solvent, and finishing the preparation of the quantum dot light-sensitized absorption layer.
C: then, the wafer was fixed again on a spin coater, 0.2ml of a 10mg/ml P3HT dichlorobenzene solution was added dropwise over the quantum dot photosensitized absorption layer and spin-coated at 3000rpm for 30s, and the spin-coated wafer was heated to 80 ℃ and heat-treated for 30min to remove the remaining solvent, thereby completing the preparation of the hole transport layer.
D: and finally, transferring the wafer into an evaporation machine, bombarding a silver simple substance by an electron beam with the current of 100A, evaporating the silver simple substance into atomic steam, forming a silver electrode with the thickness of 100nm, namely an anode, above the hole transport layer, and packaging to obtain the final photovoltaic device.
Example 3
A photovoltaic device comprising, in order from bottom to top: comprises ITO glass, an electron transport layer, a quantum dot light sensitization absorption layer, a hole transport layer and an anode; the preparation method comprises the following steps:
(1) preparation of precursor solution for forming electron transport layer
A: and sequentially adding 10ml of deionized water and 50mg of graphite oxide powder into a 100ml beaker, and carrying out ultrasonic treatment for 30min to obtain a light yellow graphene oxide aqueous dispersion. Then, 40ml of absolute ethyl alcohol is added into the dispersion liquid, and the mixture is stirred uniformly at room temperature to obtain uniform solution A;
b: sequentially adding 10ml of butyl titanate and 100ml of absolute ethyl alcohol into a 100ml beaker, and uniformly stirring at room temperature to obtain a uniform and transparent butyl titanate ethanol solution B;
and then, slowly dropwise adding 25ml of the solution A into 110ml of the solution B, continuously stirring, transferring the mixed solution into a 35 ℃ oven after dropwise adding is finished, standing for reacting for 2 hours, and taking out to obtain a precursor solution.
(2) Process for preparing photovoltaic devices
A: firstly, providing ITO glass, fixing the ITO glass in a spin coater, then, taking 0.2ml of the prepared precursor solution of the electron transport layer, dropwise adding the precursor solution to an ITO glass substrate, spin-coating for 30s at the rotating speed of 3000rpm, placing the spin-coated sheet in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃ under the protection of argon atmosphere, and forming the electron transport layer (the material is a graphene nano titanium dioxide composite material, wherein the mass ratio of graphene to titanium dioxide is 1.1: 100) on the ITO glass.
B: subsequently, the wafer was again fixed on a spin coater, and 0.2ml of CsPbBr with a concentration of 30mg/ml was taken3And (3) dropwise adding a quantum dot n-octane solution above the electron transport layer, carrying out spin coating at the rotating speed of 3000rpm for 40s, heating the spin-coated wafer to 80 ℃, carrying out heat treatment for 30min, and removing the residual solvent to complete the preparation of the quantum dot light-sensitized absorption layer.
And C, re-fixing the wafer on a spin coater, dropwise adding 0.2ml of 10mg/ml P3HT dichlorobenzene solution above the quantum dot light-sensitized absorption layer, carrying out spin coating at 3000rpm for 30s, heating the spin-coated wafer to 80 ℃, carrying out heat treatment for 30min, removing residual solvent, and finishing the preparation of the hole transport layer.
D: and finally, transferring the wafer into an evaporation machine, bombarding a silver simple substance by an electron beam with the current of 100A, evaporating the silver simple substance into atomic steam, forming a silver electrode with the thickness of 100nm, namely an anode, above the hole transport layer, and packaging to obtain the final photovoltaic device.
Example 4
A photovoltaic device comprising, in order from bottom to top: comprises ITO glass, an electron transport layer, a quantum dot light sensitization absorption layer, a hole transport layer and an anode; the preparation method comprises the following steps:
(1) preparation of precursor solution for forming electron transport layer
A: and sequentially adding 10ml of deionized water and 50mg of graphite oxide powder into a 100ml beaker, and carrying out ultrasonic treatment for 30min to obtain a light yellow graphene oxide aqueous dispersion. Then, 40ml of absolute ethyl alcohol is added into the dispersion liquid, and the mixture is stirred uniformly at room temperature to obtain uniform solution A;
b: sequentially adding 2ml of butyl titanate and 20ml of absolute ethyl alcohol into a 100ml beaker, and uniformly stirring at room temperature to obtain a uniform and transparent butyl titanate ethanol solution B;
and then, slowly dropwise adding 25ml of the solution A into 22ml of the solution B, continuously stirring, transferring the mixed solution into a 35 ℃ oven after dropwise adding is finished, standing for reacting for 2 hours, and taking out to obtain a precursor solution.
(2) Process for preparing photovoltaic devices
A: firstly, providing ITO glass, fixing the ITO glass in a spin coater, then, taking 0.2ml of the prepared precursor solution of the electron transport layer, dropwise adding the precursor solution to an ITO glass substrate, spin-coating for 30s at the rotating speed of 3000rpm, placing the spin-coated wafer in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃ under the protection of argon atmosphere, and forming the electron transport layer (the material is a graphene nano titanium dioxide composite material, wherein the mass ratio of graphene to titanium dioxide is 1.1: 20) on the ITO glass.
B: and then, re-fixing the sheet on a spin coater, dropwise adding 0.2ml of 30mg/ml PbS quantum dot n-octane solution above the electron transport layer, spin-coating at 3000rpm for 40s, heating the spin-coated sheet to 80 ℃, carrying out heat treatment for 30min, removing the residual solvent, and completing the preparation of the quantum dot light-sensitized absorption layer.
C: then, the sheet was fixed again on a spin coater, 0.2ml of a 10mg/ml P3HT dichlorobenzene solution was dropped on the photosensitive absorbing layer and spin-coated at 3000rpm for 30 seconds, and the spin-coated sheet was heated to 80 ℃ and heat-treated for 30min to remove the remaining solvent, thereby completing the preparation of the hole transporting layer.
D: and finally, transferring the wafer into an evaporation machine, bombarding a silver simple substance by an electron beam with the current of 100A, evaporating the silver simple substance into atomic steam, forming a silver electrode with the thickness of 100nm, namely an anode, above the hole transport layer, and packaging to obtain the final photovoltaic device.
Example 5
A photovoltaic device comprising, in order from bottom to top: comprises ITO glass, an electron transport layer, a quantum dot light sensitization absorption layer, a hole transport layer and an anode; the preparation method comprises the following steps:
(1) preparation of precursor solution for forming electron transport layer
A: and sequentially adding 10ml of deionized water and 50mg of graphite oxide powder into a 100ml beaker, and carrying out ultrasonic treatment for 30min to obtain a light yellow graphene oxide aqueous dispersion. Then, 40ml of absolute ethyl alcohol is added into the dispersion liquid, and the mixture is stirred uniformly at room temperature to obtain uniform solution A;
b: respectively adding 5ml of butyl titanate and 50ml of absolute ethyl alcohol into a 100ml beaker, and uniformly stirring at room temperature to obtain a uniform and transparent butyl titanate ethanol solution B;
and then, slowly dropwise adding 25ml of the solution A into 55ml of the solution B, continuously stirring, transferring the mixed solution into a 35 ℃ oven after dropwise adding is finished, standing for reacting for 2 hours, and taking out to obtain a precursor solution.
(2) Process for preparing photovoltaic devices
A: firstly, providing ITO glass, fixing the ITO glass in a spin coater, then, taking 0.2ml of the prepared precursor solution of the electron transport layer, dropwise adding the precursor solution to an ITO glass substrate, spin-coating for 30s at the rotating speed of 3000rpm, placing the spin-coated wafer in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃ under the protection of argon atmosphere, and forming the electron transport layer (the material is a graphene nano titanium dioxide composite material, wherein the mass ratio of graphene to titanium dioxide is 2.2: 100) on the ITO glass.
B: and then, re-fixing the wafer on a spin coater, dropwise adding 0.2ml of CdSe/CdS quantum dot n-octane solution with the concentration of 30mg/ml above the electron transport layer, spin-coating at 3000rpm for 40s, heating the spin-coated wafer to 80 ℃, carrying out heat treatment for 30min, removing the residual solvent, and finishing the preparation of the quantum dot light-sensitized absorption layer.
C: then, the wafer was fixed again on a spin coater, 0.2ml of a 10mg/ml TFB dichlorobenzene solution was dropped on the photosensitized absorbing layer and spin-coated at 3000rpm for 30 seconds, and the spin-coated wafer was heated to 80 ℃, heat-treated for 30min, and the residual solvent was removed to complete the preparation of the hole transporting layer.
D: and finally, transferring the wafer into an evaporation machine, bombarding a silver simple substance by an electron beam with the current of 100A, evaporating the silver simple substance into atomic steam, forming a silver electrode with the thickness of 100nm, namely an anode, above the hole transport layer, and packaging to obtain the final photovoltaic device.
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. The preparation method of the composite material is characterized by comprising the following steps:
dissolving graphene oxide in a first solvent to obtain a first solution;
dissolving a titanium-containing precursor salt in a second solvent to obtain a second solution;
adding the first solution into the second solution, and standing to obtain a precursor solution;
and calcining the precursor solution to obtain the composite material.
2. The method for preparing the composite material according to claim 1, wherein the mass concentration of the graphene oxide in the first solution is 3-20 mg/ml; and/or the presence of a gas in the gas,
in the step of adding the first solution into the second solution, the first solution is dripped into the second solution at the speed of 1-10 ml/min; and/or the presence of a gas in the gas,
the obtained composite material comprises titanium dioxide nanoparticles and graphene nanosheets, and the mass ratio of the graphene nanosheets to the titanium dioxide nanoparticles is 1 (20-100).
3. The method for preparing the composite material according to claim 1, wherein the temperature of the standing treatment is 20-50 ℃; and/or the presence of a gas in the gas,
the standing treatment time is 2-8 h; and/or the presence of a gas in the gas,
the temperature of the calcination treatment is 400-600 ℃; and/or the presence of a gas in the gas,
the time of the calcination treatment is 30-90 mim.
4. The method for preparing the composite material according to claim 1, wherein after the precursor solution is obtained, the precursor solution is spin-coated on a substrate at a speed of 1000 to 5000rpm, and then the calcination treatment is performed.
5. The method for producing a composite material according to any one of claims 1 to 4, wherein the titanium-containing precursor salt is at least one selected from the group consisting of propyl titanate and isobutyl titanate; and/or the presence of a gas in the gas,
the first solvent comprises at least one of water and an alcohol solvent; and/or the presence of a gas in the gas,
the second solvent comprises an alcohol solvent.
6. A composite material prepared by the method according to any one of claims 1 to 5.
7. A composite material comprising titanium dioxide nanoparticles and graphene nanoplatelets, the titanium dioxide nanoparticles being bound to the surface of the graphene nanoplatelets.
8. The composite material of claim 7, wherein the mass ratio of the graphene nanoplatelets to the titanium dioxide nanoparticles is 1 (20-100); and/or the presence of a gas in the gas,
the titanium dioxide nano-particles are anatase crystal type titanium dioxide nano-particles.
9. A photovoltaic device, comprising:
a cathode and an anode which are oppositely arranged;
a quantum dot photosensitizing absorption layer located between the cathode and the anode;
the electron transport layer is arranged between the cathode and the quantum dot light-sensitized absorption layer;
wherein the material for forming the electron transport layer comprises the composite material obtained by the preparation method of any one of claims 1 to 5 or the composite material of claim 7 or 8.
10. The photovoltaic device according to claim 9, wherein the electron transport layer is comprised of titanium dioxide nanoparticles and graphene nanoplatelets.
11. A light emitting diode, comprising:
a cathode and an anode which are oppositely arranged;
a quantum dot light emitting layer positioned between the cathode and the anode;
an electron transport layer disposed between the cathode and the quantum dot light emitting layer;
wherein the material for forming the electron transport layer comprises the composite material obtained by the preparation method of any one of claims 1 to 5 or the composite material of claim 7 or 8.
12. The light-emitting diode according to claim 11, wherein the electron transport layer is composed of titanium dioxide nanoparticles and graphene nanoplatelets.
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| CN102492313A (en) * | 2011-11-21 | 2012-06-13 | 四川大学 | Titanium dioxide and graphene oxide composite nano-grade sheet material and preparation method thereof |
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| CN102492313A (en) * | 2011-11-21 | 2012-06-13 | 四川大学 | Titanium dioxide and graphene oxide composite nano-grade sheet material and preparation method thereof |
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