CN113130768A - 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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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 an aluminum element and an indium element which are doped In the titanium dioxide nanoparticles, and the composite material can reduce the HOMO energy level of the titanium dioxide nanoparticles and simultaneously improve the LUMO energy level of the nano titanium dioxide material In a mode of co-doping the titanium dioxide nanoparticles with In and Al.
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 an electron transport layer of a solar cell still has disadvantages, such as that the surface of the titanium dioxide film is rough, the bonding effect between the functional layers of the device is not good, and the mobility of the current carrier in the device is low. In addition, the energy level difference between the nano titanium dioxide material and the quantum dot light-sensitized material in the solar cell is large, and a large energy level barrier needs to be overcome when carriers migrate among different materials, so that the migration rate of the carriers in the quantum dot solar cell is low, the factors are not favorable for the transfer output of photo-generated electrons of a light absorption sensitized layer, and the photoelectric performance of a photovoltaic device is further limited to be improved.
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 of low carrier migration rate of a titanium dioxide material.
In order to achieve the purpose, the invention adopts the following technical scheme:
one aspect of the present invention provides a method for preparing a composite material, comprising:
dissolving an aluminum salt and an indium salt 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.
Adding a first solution prepared from aluminum salt and indium salt into a second solution prepared from titanium-containing precursor salt, standing for reaction to form a precursor solution, and calcining and decomposing the precursor solution to form the In and Al co-doped titanium dioxide nanoparticle composite material; by utilizing the co-doping mode of aluminum and indium, the HOMO energy level of the titanium dioxide nano material can be reduced, and the LUMO energy level of the nano titanium dioxide material is improved, so that the prepared composite material is used for a quantum dot device and can be better matched with a quantum dot energy level structure, and the carrier migration rate in the device can be improved.
The invention also provides a composite material, which is prepared by the preparation method.
And a composite material including titanium dioxide nanoparticles and an aluminum element and an indium element doped in the titanium dioxide nanoparticles.
The composite material provided by the invention comprises titanium dioxide nanoparticles and an aluminum element and an indium element which are doped In the titanium dioxide nanoparticles, and the HOMO energy level of the titanium dioxide nanoparticles can be reduced and the LUMO energy level of the titanium dioxide nanoparticles can be improved In an In and Al co-doped mode of the titanium dioxide nanoparticles.
The invention also aims to provide a photovoltaic device, aiming at solving the technical problem that the energy level of a titanium dioxide material in the existing photovoltaic device cannot be well matched with the energy level of a quantum dot material, so that the carrier transfer rate is slow. 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 aluminum element and indium element doped in the titanium dioxide nano-particles, the HOMO energy level of the titanium dioxide nano-particles is reduced by utilizing a co-doping mode of aluminum and indium, and the LUMO energy level of the nano-titanium dioxide material is improved, so that the energy level structure of the doped titanium dioxide is more matched with the energy level structure of the quantum dot light-sensitized absorption layer, the carrier migration rate in the photoelectric device is improved, and the photoelectric performance of the device is finally improved.
The invention also aims to provide a light-emitting diode, aiming at solving the technical problem that the energy level of a titanium dioxide material in the existing diode device cannot be well matched with the energy level of a quantum dot material, so that the carrier transfer rate is slow. 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 electron transmission layer of the light-emitting diode comprises titanium dioxide nano-particles and aluminum element and indium element doped in the titanium dioxide nano-particles, the HOMO energy level of the titanium dioxide nano-particles is reduced by utilizing a co-doping mode of aluminum and indium, and the LUMO energy level of the nano-titanium dioxide material is improved, so that the doped titanium dioxide energy level structure is more matched with the quantum dot energy level structure of the quantum dot light-emitting layer, the carrier migration rate in the light-emitting diode device is improved, 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 an aluminum salt and an indium salt 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 provided by the embodiment of the invention, a first solution prepared from aluminum salt and indium salt is added into a second solution prepared from a titanium-containing precursor salt, a precursor solution is formed after standing reaction, and the precursor solution is calcined and decomposed, so that the In and Al co-doped titanium dioxide nanoparticle composite material is formed; by utilizing the co-doping mode of aluminum and indium, the HOMO energy level of the titanium dioxide nano material can be reduced, and the LUMO energy level of the nano titanium dioxide material is improved, so that the prepared composite material is used for a quantum dot device and can be better matched with the energy level structure of quantum dot light, and the carrier migration rate in the device can be improved.
Step S01, dissolving aluminum salt and indium salt in a first solvent, wherein the molar ratio of aluminum element in the aluminum salt to indium element in the indium salt is 1 (0.6-3.0); the doped titanium dioxide formed in the proportion range enables the carrier transport performance of the composite material to be optimal. The aluminum salt can be water-soluble aluminum salt such as aluminum nitrate, aluminum chloride, aluminum sulfate, etc.; the indium salt may be water-soluble silver salt such as indium nitrate, indium sulfate, indium chloride, and indium acetate. In the finally formed first solution, the concentration range of the aluminum salt is 0.01-0.1 mol/L, the concentration of the aluminum salt is too low, the content of aluminum ions in a target product is low, the doping effect is poor, the concentration of the aluminum salt is too high, and the aluminum salt is difficult to completely dissolve.
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. The first solution system is mixed with an alcohol solvent such as absolute ethyl alcohol in water, so that the concentration of the reaction system is diluted by the ethyl alcohol, the subsequent hydrolysis reaction rate is reduced, and the uniformity of a precursor material and the operability of the reaction are improved. The volume ratio of deionized water to alcohol (e.g., absolute ethanol) may range from 1: (3-20), the proportion of the two is too large, the water content in the system is too high, the subsequent hydrolysis reaction of the titanium-containing precursor is too fast, the reaction system is easy to form gel and lose fluidity, and aluminum ions and indium ions are difficult to uniformly disperse in a gel network, so that the particles are not uniformly dispersed, and the film forming of the solution is difficult; when the ratio of the aluminum salt to the indium salt is too small, the aluminum salt and the indium salt are difficult to dissolve and uniform solutions containing aluminum ions and indium ions are obtained, which is not favorable for production.
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: (10-30), 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 to the second solution, a ratio of molar amounts of aluminum element, indium element in the first solution and titanium element in the second solution is 1: (0.6-3.0): (10-150); within the range, the energy level structure of the doped titanium dioxide and the quantum dot material have the best matching effect. 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 if the dripping speed is too slow, the reaction period is long, which is not beneficial to production; if the dropping speed is too fast, a large amount of deionized water is quickly introduced into the 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 preparation is influenced, so that the effect obtained by the dropping speed is optimal.
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-containing precursor salt such as butyl titanate is 20-50 ℃, the temperature of standing treatment is too low, the hydrolysis of the butyl titanate is incomplete, and the system contains a large amount of titanium-containing precursor salt which is easy to volatilize in the subsequent calcination process and affects the performance of the composite material; 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.
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 a substrate at the speed of 1000-5000 rpm, and then carrying out the calcination treatment. 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. In the device, the electron transport layer is too thin or too thick, which leads to the imbalance of electron-hole inside the device and further leads to the deterioration of the device performance, and the carriers of the electron transport layer in the range are more balanced.
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 titanium hydroxide by heating to produce titanium dioxide nanocrystals in the anatase crystal form, and to uniformly disperse and dope aluminum and indium in the titanium dioxide nanocrystals. The calcining temperature range is 400-600 ℃, the calcining temperature is too low, the titanium hydroxide is decomposed into amorphous titanium dioxide, the electron mobility is poor, the performance of a photoelectric device is poor, the calcining temperature is too high, the crystal form of the titanium dioxide is in a rutile structure from an 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.
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 an aluminum element and an indium element doped in the titanium dioxide nanoparticles. More specifically, the composite material is composed of titanium dioxide nanoparticles and aluminum element and indium element doped in the titanium dioxide nanoparticles.
The composite material provided by the embodiment of the invention comprises titanium dioxide nanoparticles and an aluminum element and an indium element doped In the titanium dioxide nanoparticles, and the HOMO energy level of the titanium dioxide nanoparticles can be reduced and the LUMO energy level of the nano titanium dioxide material can be simultaneously promoted In a mode of In and Al co-doping the titanium dioxide nanoparticles.
Further, the molar weight ratio of the aluminum element, the indium element and the titanium element in the composite material is 1 (0.6-3.0): (10-150); within the above proportion range, the performance improvement effect of the aluminum and indium co-doped titanium dioxide is better. Further, the titanium dioxide nanoparticles are anatase crystal type titanium dioxide nanoparticles.
In a further aspect, an embodiment of the present invention provides a photovoltaic device, where the photovoltaic device is a quantum dot photovoltaic device, as shown in fig. 2, and the cathode and the anode of the quantum dot photovoltaic device are arranged opposite to each other; a quantum dot photosensitizing absorption layer located between the cathode and the anode; and the electron transport layer is arranged between the cathode and the quantum dot light-sensitized absorption layer and consists of the composite material or the composite material prepared by the preparation method. Namely, the material of the electron transport layer comprises titanium dioxide nanoparticles and aluminum element and indium element doped in the titanium dioxide nanoparticles.
In the quantum dot photovoltaic device provided by the embodiment of the invention, the material of the electron transmission layer comprises titanium dioxide nano-particles and aluminum element and indium element doped in the titanium dioxide nano-particles, the HOMO energy level of the titanium dioxide nano-particles is reduced by utilizing a co-doping mode of aluminum and indium, and the LUMO energy level of the nano titanium dioxide material is simultaneously improved, so that the energy level structure of the doped titanium dioxide is more matched with the energy level structure of the quantum dot light-sensitized absorption layer, the carrier migration rate in the photoelectric device is improved, and the photoelectric performance of the device is finally improved. More specifically, the electron transport layer in the quantum dot photovoltaic device is composed of titanium dioxide nanoparticles and aluminum element and indium element doped in the titanium dioxide nanoparticles.
The energy level of the titanium dioxide nano material is greatly influenced by the purity of the material, and the energy level structure of the titanium dioxide nano material can be changed through atom doping. In one embodiment, the molar weight ratio of the aluminum element, the indium element and the titanium element in the composite material is 1 (0.6-3.0): (10-150); within the range, the energy level structure of the doped titanium dioxide and the quantum dot material have the best matching effect, so that the carrier transmission performance of the device is the best. The titanium dioxide nano-particles are anatase crystal type titanium dioxide nano-particles. 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 P3HT (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 aluminum element and indium element doped in the titanium dioxide nanoparticles.
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 an aluminum salt and an indium salt 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. In the process, the precursor solution is deposited on the substrate, and an electron transmission layer is formed In a calcining mode, namely, the In and Al co-doped titanium dioxide nano material film (namely, the electron transmission layer) is In situ on the conductive substrate, so that the film has good flatness, is tightly combined with the substrate and a subsequently prepared quantum dot light-sensitized absorption layer, has small interface resistance, namely, has good interface combination effect, is more favorable for the transmission of current carriers, and improves the quality of the electron transmission film and the photoelectric performance of a device through a special film forming mode of a photovoltaic device; and the In and Al co-doped titanium dioxide nano material can also accelerate the carrier migration rate In the device, so that the photoelectric property of the device is further improved under the combined action. The quantum dot photovoltaic device prepared in the way can improve the migration rate of carriers, so that the photoelectric property is improved. The preparation method is simple to operate, easy to realize industrialization and wide in application prospect 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: and adding a certain amount of aluminum salt, indium salt, deionized water and absolute ethyl alcohol into a beaker in sequence, stirring at room temperature and dissolving to obtain a uniform solution A containing aluminum and indium ions.
B: adding a certain amount of precursor salt of the titanium element and absolute ethyl alcohol into a beaker, and uniformly stirring at room temperature to obtain a uniform and transparent solution B.
And then, slowly dripping the solution A containing aluminum and indium ions into the solution B, continuously stirring, standing and reacting the mixed solution for a period of time after finishing dripping, and obtaining the precursor solution of the electron transport layer. In the process, precursor salt of titanium element is contacted with deionized water and slowly undergoes hydrolysis reaction to generate titanium hydroxide and form titanium hydroxide sol, and aluminum ions and indium ions are uniformly dispersed in the sol network.
(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 aluminum-indium-doped titanium dioxide composite material 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 titanium hydroxide in the film by heating to generate titanium dioxide nano-crystals in anatase crystal form, and uniformly disperse aluminum and indium in the titanium dioxide nano-crystals. 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 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 aluminum element and indium element doped in the titanium dioxide nano-particles, the HOMO energy level of the titanium dioxide nano-particles is reduced by utilizing a co-doping mode of aluminum and indium, and the LUMO energy level of the nano-titanium dioxide material is improved, so that the doped titanium dioxide energy level structure is more matched with the quantum dot energy level structure of the quantum dot light-emitting layer, the carrier migration rate in the light-emitting diode device is improved, 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 aluminum element and indium element doped in the titanium dioxide nanoparticles.
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: sequentially adding 1mmol of aluminum nitrate, 1mmol of indium nitrate, 10ml of deionized water and 40ml of absolute ethyl alcohol into a 100ml beaker, stirring at room temperature and dissolving to obtain a uniform solution A containing aluminum and indium ions;
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) Preparation of 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 wafer after the spin-coating in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃, and forming the electron transport layer (the material is titanium dioxide nano-particles doped with aluminum and indium, wherein the molar ratio of aluminum, indium and titanium is 1:1:28) 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, and removing the residual solvent to obtain 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 obtaining a hole transport layer.
D: and transferring the wafer into an evaporation machine, bombarding the 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: sequentially adding 1mmol of aluminum chloride, 2mmol of indium chloride, 10ml of deionized water and 40ml of absolute ethyl alcohol into a 100ml beaker, stirring at room temperature and dissolving to obtain a uniform solution A containing aluminum and indium ions;
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) Preparation of 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 wafer after the spin-coating in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃, and forming the electron transport layer (the material is titanium dioxide nano-particles doped with aluminum and indium, wherein the molar ratio of aluminum, indium and titanium is 1: 2: 28) 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, and removing the residual solvent to obtain 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 obtaining a hole transport layer.
D: and transferring the wafer into an evaporation machine, bombarding the 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: sequentially adding 1mmol of aluminum nitrate, 3mmol of indium nitrate, 10ml of deionized water and 40ml of absolute ethyl alcohol into a 100ml beaker, stirring at room temperature and dissolving to obtain a uniform solution A containing aluminum and indium ions;
b: sequentially adding 20ml of butyl titanate and 200ml 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 220ml 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 wafer after the spin-coating in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃, and forming the electron transport layer (the material is titanium dioxide nano-particles doped with aluminum and indium, wherein the molar ratio of aluminum, indium and titanium is 1: 3: 112) 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 obtain 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 obtaining a hole transport layer.
D: and transferring the wafer into an evaporation machine, bombarding the 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: sequentially adding 1mmol of aluminum nitrate, 0.6mmol of indium nitrate, 10ml of deionized water and 40ml of absolute ethyl alcohol into a 100ml beaker, stirring at room temperature and dissolving to obtain a uniform solution A containing aluminum and indium ions;
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 wafer after the spin-coating in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃, and forming the electron transport layer (the material is titanium dioxide nano-particles doped with aluminum and indium, wherein the molar ratio of aluminum, indium and titanium is 1: 0.6: 28) 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, and removing the residual solvent to obtain the quantum dot light-sensitized absorption layer.
C: and then, re-fixing the wafer on a spin coater, taking 0.2ml of TFB dichlorobenzene solution with the concentration of 10mg/ml, dropwise adding the solution above the quantum dot light-sensitized absorption layer, carrying out spin coating at the rotating speed of 3000rpm for 30s, heating the spin-coated wafer to 80 ℃, carrying out heat treatment for 30min, and removing the residual solvent to obtain the hole transport layer.
D: and transferring the wafer into an evaporation machine, bombarding the 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: sequentially adding 1mmol of aluminum nitrate, 1mmol of indium nitrate, 10ml of deionized water and 40ml of absolute ethyl alcohol into a 100ml beaker, stirring at room temperature and dissolving to obtain a uniform solution A containing aluminum and indium ions;
b: sequentially adding 2.5ml of butyl titanate and 25ml 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 27.5ml 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, fixing ITO glass in a spin coater, then, taking 0.2ml of the prepared precursor solution of the electron transport layer, dripping the precursor solution on an ITO glass substrate, spin-coating for 30s at the rotating speed of 3000rpm, placing the wafer after the spin-coating in a muffle furnace, calcining for 60min at the constant temperature of 500 ℃, and forming the electron transport layer (the material is titanium dioxide nano-particles doped with aluminum and indium, wherein the molar ratio of aluminum, indium and titanium is 1:1: 14) 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, and removing the residual solvent to obtain 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 obtaining a hole transport layer.
D: and transferring the wafer into an evaporation machine, bombarding the aluminum simple substance by an electron beam with the current of 100A, evaporating the aluminum simple substance into atomic steam, forming an aluminum 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 (10)
1. A method of making a composite material, comprising:
dissolving an aluminum salt and an indium salt 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 of producing a composite material according to claim 1, wherein in the step of dissolving an aluminum salt and an indium salt in a first solvent, a molar ratio of an aluminum element in the aluminum salt to an indium element in the indium salt is 1: (0.6-3.0); and/or the presence of a gas in the gas,
in the step of adding the first solution to the second solution, a ratio of molar amounts of an aluminum element, an indium element in the first solution and a titanium element in the second solution is 1: (0.6-3.0): (10-150); 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 added dropwise into the second solution at a rate of 1-10 ml/min.
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 preparing a composite material according to any one of claims 1 to 4, wherein the aluminum salt is at least one selected from the group consisting of aluminum nitrate, aluminum chloride and aluminum sulfate; and/or the presence of a gas in the gas,
the indium salt is selected from at least one of indium nitrate, indium sulfate, indium chloride and indium acetate; and/or the presence of a gas in the gas,
the titanium-containing precursor salt is selected from at least one of propyl titanate and isobutyl titanate; and/or the presence of a gas in the gas,
the first solvent is selected from at least one of water and 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, characterized in that it comprises titanium dioxide nanoparticles and an element of aluminium and an element of indium doped in said titanium dioxide nanoparticles.
8. The composite material according to claim 7, wherein the molar weight ratio of the aluminum element, the indium element and the titanium element in the composite material is 1: (0.6-3.0): (10-150); 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;
an electron transport layer disposed between the cathode and the quantum dot photosensitizing 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. 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.
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