CN110923814A - Preparation method of nano vanadium dioxide film - Google Patents
Preparation method of nano vanadium dioxide film Download PDFInfo
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- CN110923814A CN110923814A CN201911164137.XA CN201911164137A CN110923814A CN 110923814 A CN110923814 A CN 110923814A CN 201911164137 A CN201911164137 A CN 201911164137A CN 110923814 A CN110923814 A CN 110923814A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
Abstract
The invention discloses a preparation method of a nano vanadium dioxide film, which solves the problems that in the prior art, the thickness and the uniformity of the film are accurately controlled, doping elements cannot enter the interior of a vanadium dioxide crystal lattice in a doping mode, and a second phase or other impurities exist. Mixing a vanadium source solution and an organic carboxylic acid solution to obtain an element-free doped hydrothermal reaction solution; or mixing the vanadium source solution, the organic carboxylic acid solution and the doped element solution to obtain an element-doped hydrothermal reaction solution; completely immersing the substrate in the hydrothermal reaction solution for hydrothermal reaction; and cleaning, drying and then annealing to obtain the nano vanadium dioxide film. The vanadium dioxide film prepared by the method of the invention presents a regular nano structure, the crystal grain of the nano rod is a single crystal structure, and the minimum diameter of the crystal grain can reach 10 nm; the chemical valence state is stable; the uniformity and the thickness are controllable; has excellent thermotropic phase transition performance and good visible light transmittance.
Description
Technical Field
The invention belongs to the field of inorganic functional materials, and particularly relates to a preparation method of an element-doped or undoped nano vanadium dioxide film.
Background
Vanadium dioxide (VO)2) Is a typical electron strongly-correlated compound, has metal-insulation transition (MIT) at 68 ℃, and has reversible phase transition from a monoclinic phase (M phase) to a tetragonal rutile structure (R phase), and the phase transition response speed is extremely high. The physical properties of the vanadium dioxide material before and after the phase change are obviously changed, and are specifically reflected in abrupt changes of resistivity, light transmittance and reflectivity. The change range of the resistivity of the vanadium dioxide material before and after phase change can reach 4-5 orders of magnitude. Meanwhile, the light transmittance of the vanadium dioxide thin film material in an infrared region is greatly changed, and the low-temperature semiconductor vanadium dioxide thin film is in a high-transmittance and low-reflection state to infrared light; above the phase transition temperature, the vanadium dioxide film is converted into a metal phase, and is in a low-transmission and high-reflection state for infrared light with the wavelength of more than 1.3 mu m. The excellent performances enable the vanadium dioxide to have wide application prospects in the fields of laser protection, intelligent windows, thermal/photoelectric switches, multi-field control electronic devices, optical storage devices and the like.
The preparation and application of film materials are of great importance in industrial production. Potential application values of the vanadium dioxide material based on metal-insulator phase transition, such as laser protection, intelligent windows and the like, require the vanadium dioxide material to be applied in a thin film material mode. Therefore, a film process with excellent preparation performance and stable process can be developed, and the method is a crucial step for the application and development of vanadium dioxide materials. Based on the application characteristics of vanadium dioxide materials, the application form of the vanadium dioxide thin film at present mainly comprises the steps of directly preparing the vanadium dioxide thin film on a hard substrate and compounding the vanadium dioxide thin film nano particles into an organic medium to prepare a flexible composite thin film. Common methods for preparing vanadium dioxide films on hard substrates include magnetron sputtering, molecular beam epitaxy, pulsed laser deposition, chemical vapor deposition and other vapor deposition methods, and such vapor deposition methods are complex in equipment, high in energy consumption, low in yield and difficult to realize practical production. The flexible composite film is limited in application due to complex preparation process, harsh use conditions and storage of the film and the like.
In order to broaden the practical applications of vanadium dioxide materials, chemical element doping has proven to be a feasible way to improve the physicochemical properties of vanadium dioxide materials. By doping single chemical element, the visible light transmittance can be improved, the phase transition temperature point can be adjusted, and the like. By co-doping of a plurality of elements, improved designs of various properties can be more achieved. Moreover, reasonably regulating the surface appearance of the film is regarded as one of important factors influencing the performance of the vanadium dioxide. The size of the nano particles causes the position of the lowest infrared transmittance of the high-temperature vanadium dioxide to change, and the small particles can remarkably adjust the tuning performance of the vanadium dioxide material. Due to the fact that the application scenes of the vanadium dioxide thin film have different requirements on the thickness, the controllable preparation of the thickness is necessary while the performance of the vanadium dioxide thin film can be guaranteed.
At present, common methods for preparing the M-phase film include physical vapor deposition (magnetron sputtering, pulsed laser deposition, etc.), chemical vapor deposition, etc., but since the vanadium element is a valence-variable element, the vanadium content in the vanadium dioxide is 4+Valence, which is a metastable phase, the above method has difficulty in securing its chemical valence state and causes loss of performance; the hydrothermal method can better control the chemical valence state of the vanadium dioxide and keep the good phase change performance of the vanadium dioxide. However, the current common method for preparing vanadium dioxide materials is often limited to the preparation of vanadium dioxide powder materials, which leads to more complicated use of vanadium dioxide materials. In the prior art, the preparation method is the preparation of the truss-structured vanadium dioxide film, but the growth process of the prepared film is two-dimensional growth due to the truss structure of the film, the thickness and uniformity of the film are difficult to accurately control in the growth process, and the disclosed method is not suitable for some doping elements. At the same time, doping the preparation element with twoThe vanadium oxide film, a common physical vapor deposition method and the like cannot ensure that doping elements enter the interior of vanadium dioxide crystal lattices in a doped form, and a second phase or other impurities often exist.
Therefore, the method for preparing the nano vanadium dioxide film can effectively control and ensure the valence state of the vanadium dioxide, the thickness and the uniformity of the film, and ensure that the doping elements can be well blended into the crystal lattice structure of the vanadium dioxide, which becomes a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The technical problem solved by the invention is as follows: the preparation method of the nano vanadium dioxide film is provided, and the problems that in the prior art, the thickness and the uniformity of the film are accurately controlled, doping elements cannot enter the interior of a vanadium dioxide crystal lattice in a doping mode, and a second phase or other impurities exist are solved.
The technical scheme adopted by the invention is as follows:
the preparation method of the nano vanadium dioxide film comprises the following steps:
Mixing a vanadium source solution, an organic carboxylic acid solution and a doped element solution to obtain an element-doped hydrothermal reaction solution; the organic carboxylic acid solution is a binary organic carboxylic acid solution or a ternary organic carboxylic acid solution;
and step 3, cleaning and drying: after the hydrothermal reaction is finished, taking out the substrate on which the film with the deposit grows, cleaning to remove the deposit on the surface of the film, and drying to obtain the substrate on which the film grows;
and 4, annealing treatment: and (4) annealing the substrate with the film grown in the step (3) to obtain the nano vanadium dioxide film.
In the technical scheme of the invention, the metal ions in the liquid vanadium source solution are only vanadium ions.
In the embodiment of the invention, the concentration of vanadium ions in the hydrothermal reaction solution is 1 mmol/L-20 mmol/L; the molar ratio of the vanadium ions to acid radical ions in the organic carboxylic acid solution is 1: 0.5-8; the pH value of the hydrothermal reaction solution is 1-5; preferably, the concentration of the vanadium ions is 3 mmol/L-10 mmol/L, more preferably 3 mmol/L-6 mmol/L; preferably, the molar ratio of the vanadium ions to acid radical ions in the organic carboxylic acid solution is 1: 3-8; preferably, the pH value of the hydrothermal reaction solution is 2-4.
In the technical scheme of the invention, the addition amount of the doping element solution is determined according to the actual required amount of the doping element.
As an embodiment of the invention, the adding amount of the doping element solution is determined according to the actual required amount of the doping element;
in the technical scheme of the invention, the vanadium source solution is prepared by dissolving a solid vanadium-containing compound with a first solvent;
wherein the solid vanadium-containing compound is selected from one or more of vanadyl sulfate, vanadium pentoxide, vanadyl acetylacetonate, triisopropoxyl vanadium oxide and ammonium metavanadate; preferably at least one of vanadyl sulfate and vanadyl acetylacetonate;
the first solvent is selected from water or ethanol.
The dissolution can be carried out by a conventional stirring method, such as ultrasonic stirring or heating stirring;
preferably, the stirring is carried out by a water bath magnetic stirrer, the stirring temperature is 50-90 ℃, and the stirring time is 15 min-1 h.
In the technical scheme of the invention, the acid in the organic carboxylic acid solution is selected from any one of acetic acid, phthalic acid, citric acid and terephthalic acid; when the acid is liquid, the acid is directly used as an organic carboxylic acid solution; when the acid is solid, adding a second solvent for dissolving to prepare an organic carboxylic acid solution; the second solvent is selected from one of ethanol, water and glycol.
In the step 2, the hydrothermal reaction is carried out at 150-280 ℃ for 15 min-24 h.
As some examples of the invention, the hydrothermal reaction is carried out in a reaction kettle.
In the technical scheme of the invention, the substrate is selected from any one of alumina, titanium oxide or glass; preferably a polished C-axis oriented single crystal alumina.
In the step 3, the cleaning is ultrasonic cleaning.
Specifically, deionized water, alcohol rinse and acetone ultrasonic cleaning were used, respectively.
As some embodiments of the present invention, the drying in step 3 is drying gas blow-drying; preferably, the drying gas is nitrogen, preferably with a purity of 99.99%.
In the technical scheme of the invention, the specific operation of the annealing treatment is to carry out annealing treatment for 30 s-24 h at 250-600 ℃ under the condition that the air pressure is 0.1-100 KPa;
preferably, the air pressure is 0.5KPa to 10KPa, the annealing temperature is 300 ℃ to 500 ℃, and the annealing time is 30s to 30 min.
Preferably, the annealing treatment is carried out in a quartz inner cavity type rapid annealing furnace.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for preparing an element-doped nano vanadium dioxide film, which utilizes simple hydrothermal reaction, by controlling the types of acid, the alcohol-water ratio and the vanadium ion concentration in the raw materials, freely controlling the doping or non-doping of elements, selecting a proper substrate, strictly controlling the reaction feeding sequence and the heating temperature, providing the optimal stirring time, strictly controlling the annealing treatment conditions, and being capable of controlling the nucleation and growth of vanadium dioxide crystals and the valence state of vanadium in the hydrothermal process, the prepared vanadium dioxide film is an M-phase vanadium dioxide film, compared with the vanadium dioxide film obtained by other preparation methods, the vanadium dioxide film prepared by the method is a film formed by connecting uniform nano particles, and has a regular nano structure, the nano rod crystal grains are of a single crystal structure, and the minimum grain diameter can reach 10 nm; the chemical valence state is stable; the uniformity is higher, and the thickness is controllable; the vanadium dioxide thin film has excellent thermotropic phase change performance and good visible light transmittance (shows excellent thermotropic phase change resistance mutation performance and infrared light modulation performance);
2. the invention provides a preparation method of an element-doped nano vanadium dioxide film, which is suitable for preparing a doped or undoped vanadium dioxide film by single element doping and multi-element co-doping;
3. the invention provides a preparation method of an element-doped nano vanadium dioxide film, which has the advantages of easily available raw materials, simple process, short preparation period, low energy consumption, excellent performance and industrial application value.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the vanadium dioxide thin film obtained in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the vanadium dioxide thin film prepared in example 1.
FIG. 3 is a graph showing the variation of the thermotropic phase-change sheet resistance of the vanadium dioxide thin film prepared in example 1.
FIG. 4 is a graph showing the UV-IR transmittance of the vanadium dioxide film prepared in example 1.
FIG. 5 is a SEM image of a thickness section obtained in example 1.
FIG. 6 is an SEM image of a vanadium dioxide thin film obtained in example 2.
FIG. 7 is a graph showing the UV-IR transmittance of the vanadium dioxide film prepared in example 2.
FIG. 8 is a SEM image of a thickness section obtained in example 2.
FIG. 9 is an SEM image of a vanadium dioxide thin film obtained in example 3.
FIG. 10 is a graph showing the UV-IR transmittance of the vanadium dioxide film obtained in example 3.
FIG. 11 is a SEM image of a thickness section obtained in example 3.
FIG. 12 is a graph showing the UV-IR transmittance of the vanadium dioxide film obtained in example 4.
FIG. 13 is a graph showing the UV-IR transmittance of the vanadium dioxide film obtained in example 5.
FIG. 14 is a graph showing the variation of the thermotropic square resistance of the vanadium dioxide thin film obtained in example 6.
FIG. 15 is an X-ray diffraction (XRD) pattern of the vanadium dioxide thin film obtained in example 6.
FIG. 16 is a graph showing the changes in the thermotropic phase-change sheet resistance of the vanadium dioxide thin film obtained in example 7.
FIG. 17 is an SEM photograph of a sample prepared in example 8.
Detailed Description
The following detailed description of the embodiments of the present invention is provided with reference to the drawings, and the embodiments are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are provided, but the protection scope of the present invention is not limited to the following embodiments.
The vanadium dioxide films prepared in the following examples were examined and analyzed as follows:
(1) x-ray diffraction analysis:
the test was carried out using an X-ray diffractometer model Rigaku-D/max-2550pc from Hitachi, Japan, using Cu-k α as radiation source and a wavelength of
Adopting a Ni filter plate, wherein the pipe flow is 40mA, the pipe pressure is 40KV, the scanning range is 10-90 degrees, the scanning speed is 8 degrees/min, and the step length is 0.02 degrees; placing the vanadium dioxide thin film in the middle of a glass slide, embedding the glass slide in the middle of an instrument experiment groove, and testing; phase identification and crystal structure information were analyzed by the JADE 6.0 software;
(2) observation by a scanning electron microscope:
and carrying out microscopic morphology test on the vanadium dioxide film by adopting a Hitachi S-4800 high-resolution field emission Scanning Electron Microscope (SEM).
(3) Testing the temperature-changing square resistance:
testing the square resistance of the vanadium dioxide film by adopting an Agilent U3606A ammeter, wherein a temperature changing table is self-made; the testing temperature is 30-100 ℃.
(4) Testing the transmittance from variable temperature ultraviolet to near infrared:
the test is carried out by an Agilent Carry Series UV-Vis-NIR spectrometer. The transmittance wavelength test range is 300 nm-3000 nm, and the test temperature is 20 ℃ (low temperature) and 90 ℃ (high temperature).
Example 1
The embodiment discloses a preparation method of a nano vanadium dioxide film, which specifically comprises the following steps:
1.63g of vanadyl sulfate (VOSO)4) Mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution A;
mixing 4.15g of phthalic acid powder with 250ml of ethylene glycol, and dissolving for 30min by ultrasonic dispersion (at room temperature) to obtain a solution B;
taking 2ml of the solution A and 3ml of the solution B, adding 15ml of deionized water, and uniformly mixing to obtain 20ml of hydrothermal reaction solution, wherein the pH value of the reaction solution is 3.5, the ratio of vanadium ions to acid radical ions is 1:3, and the concentration of the vanadium ions is 0.01 mol/L;
placing the hydrothermal reaction solution in a 20ml p-polyphenyl reaction kettle, and completely immersing a C-axis oriented alumina substrate (the size of the substrate can be selected according to actual requirements) in the hydrothermal reaction solution prepared in the step (1); then sealing the reaction kettle, putting the reaction kettle in a drying oven, preserving heat at 190 ℃ for 4 hours, clarifying upper-layer liquid in the reaction kettle, and finishing hydrothermal reaction;
and step 3, cleaning and drying:
after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform brownish black film on the C-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%.
And 4, annealing treatment:
and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the temperature in the atmosphere of air at 1kpa, annealing at 450 ℃ for 6min to obtain the regular vanadium dioxide film with the nano-particle structure, wherein the film is M-phase vanadium dioxide powder and completely covers the substrate.
The vanadium dioxide film prepared in this example was tested, and the results were as follows:
(1) x-ray diffraction analysis:
the X-ray diffraction analysis result of the regular nano-particle structure vanadium dioxide film is shown in figure 1, and the characteristic peak of the regular nano-particle structure vanadium dioxide film is consistent with the characteristic peak in JCPDS 65-2358, so that the regular nano-particle structure vanadium dioxide film is an M-phase vanadium dioxide nano material, and the M-phase vanadium dioxide film is obtained through annealing treatment. The film has a preferred orientation of crystal planes (020).
(2) Observation by a scanning electron microscope:
the scanning electron microscope image and the film nanoparticle size analysis of the final vanadium dioxide film are shown in fig. 2, and it can be known that the film appearance is a uniform film with a regular nanoparticle structure, the film is formed by continuous uniform nanoparticles, the particles are closely arranged, and the film is macroscopically compact. The particle size distribution of the nano particles is concentrated in 60-70 nm. The thickness of the film was analyzed in cross section, and the thickness of the vanadium dioxide film was 180 nm, as shown in FIG. 5.
(3) Testing the temperature-changing square resistance:
as shown in FIG. 3, it is found from the test results that the sheet resistance was decreased from 6.1 in the low-temperature phase (monoclinic phase vanadium dioxide) to 1.1 in the high-temperature phase (rutile phase vanadium dioxide), the resistivity was changed by 5 orders of magnitude or more, and the temperature-raising phase-change temperature of the thin film was about 68 ℃.
(4) Variable temperature infrared test analysis:
the test result of the final product is shown in fig. 4, and it can be seen from fig. 4 that the temperature-variable infrared modulation rate at 2000nm reaches more than 60%, and the optical modulation performance is excellent.
Example 2
The embodiment discloses a preparation method of a nano vanadium dioxide film, which specifically comprises the following steps:
2.65g of vanadyl (C) acetylacetonate10H14O5V) powder in 100ml ethanol (C)2H5OH), placing the mixture in a water bath magnetic stirrer for aging and dissolving, stirring and dissolving for 30min at 45 ℃ until the mixture is completely dissolved to obtain a dark green solution, and cooling the dark green solution to obtain a brownish red solution, namely a vanadium-containing solution A;
2.04g of dihydrate and citric acid (C) are taken6H8O7·2H2O) mixing the powder with 100ml of distilled water, stirring to dissolve for 30min, and uniformly mixing to obtain a solution B;
0.6ml of the solution A and 0.9ml of the solution B were added with 17.9ml of a mixed solution of deionized water and ethanol (alcohol-water ratio volume: 1) to prepare 20ml of a hydrothermal reaction solution. The concentration of vanadium ions in the hydrothermal reaction solution is 0.003mol/L, and the ratio of the vanadium ions to acid radical ions in the reaction solution is 1:3, pH value is 3.9.
placing the hydrothermal reaction solution in a 20ml p-polyphenyl reaction kettle, and completely immersing a C-axis oriented alumina substrate (the size of the substrate can be selected according to actual requirements) in the hydrothermal reaction solution prepared in the step (1); and sealing the reaction kettle, putting the reaction kettle in a drying oven, preserving the heat at 200 ℃ for 10 hours, clarifying the upper-layer liquid in the reaction kettle, and finishing the hydrothermal reaction.
And step 3, cleaning and drying:
after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform blue-black film on the C-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%.
And 4, annealing treatment:
and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the atmosphere of air at 5kpa, annealing temperature at 600 ℃ and time at 30s to obtain the regular nano-particle structure vanadium dioxide film.
The vanadium dioxide film prepared in this example was tested, and the results were as follows:
(1) observation and analysis by a scanning electron microscope:
the scanning electron microscope image of the final vanadium dioxide film is shown in fig. 6, and it can be known that the film is a uniform film with a regular nanoparticle structure, which is formed by continuous uniform nanoparticles, the particles are closely arranged, and the film is macroscopically compact. The thickness of the film was analyzed in cross section, and the thickness of the vanadium dioxide film was 120 nm, as shown in FIG. 8.
(2) Variable temperature infrared test analysis:
the test result of the final product film is shown in fig. 7, and the film has good visible light transmittance and tuning performance due to the moderate thickness of the film, and as can be seen from the figure, the variable temperature infrared modulation rate above 1500nm reaches more than 50%, and the film has excellent optical modulation performance.
Example 3
The embodiment discloses a preparation method of a nano vanadium dioxide film, which specifically comprises the following steps:
1.63g of VOSO4Mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution A;
mixing 4.15g of phthalic acid powder with 250ml of ethylene glycol, and dissolving for 30min by ultrasonic dispersion (at room temperature) to obtain a solution B;
0.6ml of the solution A and 1.2ml of the solution B are taken, and 16.5ml of deionized water is added and uniformly mixed to obtain 20ml of hydrothermal reaction solution. The concentration of vanadium ions in the hydrothermal reaction solution is 0.003mol/L, and the ratio of the vanadium ions to acid radical ions in the reaction solution is 1: 4, pH 4.0.
placing the hydrothermal reaction solution in a 50ml p-polyphenyl reaction kettle, and completely immersing a C-axis oriented alumina substrate (the size of the substrate can be selected according to actual requirements) in the hydrothermal reaction solution prepared in the step (1); and sealing the reaction kettle, putting the reaction kettle in a drying oven, preserving the heat at 250 ℃ for 2 hours, clarifying the upper-layer liquid in the reaction kettle, and finishing the hydrothermal reaction.
And step 3, cleaning and drying:
after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform blue-black film on the C-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%.
And 4, annealing treatment:
and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the atmosphere of air at 20kpa, annealing at 400 ℃ for 900s to obtain the vanadium dioxide film with the regular nanoparticle structure.
The element-doped vanadium dioxide thin film prepared in the embodiment is tested, and the results are as follows:
(1) observation and analysis by a scanning electron microscope:
as shown in fig. 9, the scanning electron microscope image of the final vanadium dioxide film shows that the film has a uniform regular nanoparticle structure, and is formed by continuous uniform nanoparticles which are arranged closely. The thickness of the film was analyzed in cross section, and the thickness of the vanadium dioxide film was 50nm, as shown in FIG. 11.
(2) Variable temperature infrared test analysis:
the test result of the final product film is shown in fig. 10, because the film has a thin thickness, the film has a good visible light transmittance, and it can be seen from the figure that the film still maintains a good optical tuning performance, and the temperature-variable infrared modulation rate above 1250nm reaches above 40%.
Example 4
The embodiment discloses a preparation method of an element-doped nano vanadium dioxide film, which comprises the following steps:
1.63g of VOSO4Powder is inMixing 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution A;
mixing 4.15g of phthalic acid powder with 250ml of ethylene glycol, and dissolving for 30min by ultrasonic dispersion (at room temperature) to obtain a solution B;
0.8ml of the solution A and 3.2ml of the solution B are taken, and 16.5ml of deionized water is added and uniformly mixed to obtain 20ml of hydrothermal reaction solution. The concentration of vanadium ions in the hydrothermal reaction solution is 0.004mol/L, and the ratio of the vanadium ions to acid radical ions in the reaction solution is 1: 8, pH value is 2.
placing the solution 3 in a 50ml p-polyphenyl reaction kettle for hydrothermal reaction, placing a C-axis oriented alumina substrate in the reaction kettle, sealing the reaction kettle, placing the reaction kettle in a drying oven, keeping the temperature at 230 ℃ for 6 hours, clarifying the upper layer liquid in the reaction kettle, and finishing the hydrothermal reaction
(2) After the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform blue-black film on a C-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%;
(3) and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the atmosphere of air at 100pa, annealing at 450 ℃ for 50s to obtain the regular nano-particle structure vanadium dioxide film.
The vanadium dioxide thin film prepared in the step (3) of this example was tested, and the results were as follows:
(1) variable temperature infrared test analysis:
the test result of the final product film is shown in fig. 12, because the film has a thin thickness, the film has a good visible light transmittance, and it can be seen from the figure that the film still maintains a good optical tuning performance, and the temperature-variable infrared modulation rate above 1250nm reaches 40%.
Example 5
The embodiment discloses a preparation method of a tin-doped nano vanadium dioxide film, which comprises the following steps:
0.5ml of 37 at% hydrochloric acid (HCl) solution was added to 49.5ml of distilled water and mixed, and stirred well, and 1.75g of crystalline tin tetrachloride tetrahydrate (SnCl) was added4·4H2O) dissolving the powder in the 50ml solution, and stirring to form a solution A;
1.63g of VOSO4Mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution B;
mixing 4.15g of phthalic acid powder with 250ml of ethylene glycol, and dissolving for 30min by ultrasonic dispersion (at room temperature) to obtain a solution C;
taking 2ml of the solution C, 2.5ml of the solution B and 0.02ml of the solution A, adding 16.3ml of deionized water, and uniformly mixing to obtain 20ml of hydrothermal reaction solution, wherein the concentration of vanadium ions is 0.01mol/L, and the concentration of tin ions is 0.0006 mol/L;
placing 20ml of hydrothermal reaction solution with the pH value adjusted to 3.5 into a 50ml p-polyphenyl reaction kettle for hydrothermal reaction, placing an M-axis oriented alumina substrate into the reaction kettle, sealing the reaction kettle, placing the reaction kettle into a drying oven, preserving heat at 200 ℃ for 10 hours, clarifying upper-layer liquid in the reaction kettle, and finishing the hydrothermal reaction;
and step 3, cleaning and drying:
after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform blue-black film on an M-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%;
and 4, annealing treatment:
and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the atmosphere of air at the air pressure of 1kpa, the annealing temperature of 480 ℃ and the time of 100s to obtain the tin-doped vanadium dioxide film.
The vanadium dioxide film prepared in this example was tested, and the results were as follows:
(1) variable temperature infrared test analysis:
the test results of the final product film are shown in fig. 13, and the film obtained in this example had the same thickness as that of the film of example 1. The film had better visible transmittance than the final product film of example 1.
Example 6
The embodiment discloses a preparation method of a tungsten-doped nano vanadium dioxide film, which comprises the following steps:
2.54g of ammonium tungstate ((NH)4)10W12O41～xH2O) mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, heating and stirring the mixture at the temperature of 75 ℃ for dissolving the mixture for 15min till the mixture is completely dissolved to obtain a colorless ammonium tungstate solution A;
1.63g of VOSO4Mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution B;
mixing 4.15g of phthalic acid powder with 250ml of ethylene glycol, and dissolving for 30min by ultrasonic dispersion (at room temperature) to obtain a solution C;
adding 16.5ml of deionized water into 1.2ml of the solution B, 2.5ml of the solution C and 0.012ml of the solution A, uniformly mixing to obtain 20ml of reaction solution, wherein the concentration of vanadium ions is 0.006mol/L, the concentration of tungsten ions is 0.0006mol/L, the pH value of the hydrothermal reaction solution is 3.0, and the ratio of the vanadium ions to acid ions is 1: 4.
placing 20ml of hydrothermal reaction solution into a 50ml p-polyphenyl reaction kettle for hydrothermal reaction, placing a C-axis oriented alumina substrate (the size of the substrate can be selected according to actual needs) into the reaction kettle, sealing the reaction kettle, placing the reaction kettle into a drying oven, keeping the temperature at 230 ℃ for 6 hours, clarifying the upper layer liquid in the reaction kettle, and completing the hydrothermal reaction;
and step 3, cleaning and drying:
after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform blue-black film on an M-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%;
and 4, annealing treatment:
and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the atmosphere of air at the air pressure of 1kpa, the annealing temperature of 480 ℃ and the time of 100s to obtain the tungsten-doped vanadium dioxide film.
The vanadium dioxide thin film prepared in the step (3) of this example was tested, and the results were as follows:
(1) testing the temperature-changing square resistance:
the test result is shown in fig. 14, and it can be known from the test result that the sheet resistance is reduced from 4.5 in the low-temperature phase (monoclinic phase vanadium dioxide) to 2.2 in the high-temperature phase (rutile phase vanadium dioxide), the resistivity change reaches-2.3 orders of magnitude, and the temperature-rising phase-change temperature of the film is about 43 ℃, which proves that the phase-change temperature point of the vanadium dioxide film can be significantly reduced by doping the tungsten element in the embodiment.
(2) X-ray diffraction analysis:
the X-ray diffraction analysis result of the regular nano-particle structure vanadium dioxide film is shown in fig. 15, the characteristic peak of the regular nano-particle structure vanadium dioxide film is consistent with that of JCPDS 65-2358, so that the regular nano-particle structure vanadium dioxide film is an M-phase vanadium dioxide nano material, the M-phase vanadium dioxide film is obtained through annealing treatment, the film has the crystal face (020) preferred orientation, and other miscellaneous peaks are not found except the peak, so that the doping element can be well fused into the lattice structure of the vanadium dioxide.
Example 7
The embodiment discloses a preparation method of a tungsten and magnesium doped nano vanadium dioxide film, which comprises the following steps:
magnesium sulfate (MgSO 1.2 g)4) Mixing the powder in 100ml of distilled water, placing the mixture into a water bath magnetic stirrer to be stirred and dissolved, and stirring the mixture for 15min at room temperature until the mixture is completely dissolved to obtain colorless magnesium sulfate solution, namely solution A;
2.54g of ammonium tungstate ((NH)4)10W12O41～xH2O) mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, heating and stirring the mixture at the temperature of 75 ℃ for 15min until the mixture is completely dissolved to obtain a colorless ammonium tungstate solution B;
1.63g of VOSO4Mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution C;
mixing 4.15g of phthalic acid powder with 250ml of ethylene glycol, and dissolving for 30min by ultrasonic dispersion (at room temperature) to obtain a solution D;
adding 16.5ml of deionized water into 1.2ml of the solution D, 2.5ml of the solution C, 0.012ml of the solution A and 0.012ml of the solution B, and uniformly mixing to obtain 20ml of hydrothermal reaction solution, wherein the concentration of vanadium ions in the hydrothermal reaction solution is 0.006mol/L, the concentration of tungsten ions is 0.0006mol/L, and the concentration of magnesium ions is 0.0006 mol/L; the pH value of the hydrothermal reaction solution is 2.4, the ratio of vanadium ions to acid radical ions of the hydrothermal reaction solution is 1: 4;
placing 20ml of hydrothermal reaction solution into a 50ml p-polyphenyl reaction kettle for hydrothermal reaction, placing a C-axis oriented alumina substrate into the reaction kettle, sealing the reaction kettle, placing the reaction kettle into a drying oven, preserving heat at 230 ℃ for 6 hours, clarifying upper-layer liquid in the reaction kettle, and finishing the hydrothermal reaction;
and step 3, cleaning and drying:
after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, obtaining a uniform blue-black film on a C-axis oriented alumina substrate, washing the film with deionized water and absolute ethyl alcohol respectively to remove surface sediments, and drying the surface of the film by using nitrogen with the purity of 99.99%;
and 4, annealing treatment:
and (3) placing the blown film in a quartz cavity type rapid annealing furnace for annealing treatment: keeping the atmosphere of air at the air pressure of 1kpa, the annealing temperature of 480 ℃ and the annealing time of 100s to obtain the tungsten-magnesium co-doped vanadium dioxide film.
The vanadium dioxide film prepared in this example was tested, and the results were as follows:
(1) testing the temperature-changing square resistance:
the test results are shown in fig. 16, and it can be seen from the test results that the sheet resistance is reduced from 5 in the low-temperature phase (monoclinic phase vanadium dioxide) to 2.1 in the high-temperature phase (rutile phase vanadium dioxide), the resistivity change reaches-3 orders of magnitude, and the temperature-rising phase-change temperature of the thin film is about 58 ℃.
Example 8
This embodiment is a comparative example, and discloses a method for preparing a nano vanadium dioxide film by using an inorganic acid instead of an organic carboxylic acid, specifically comprising:
1.63g of VOSO4Mixing the powder in 100ml of distilled water, placing the mixture in a water bath magnetic stirrer, and stirring and dissolving the mixture for 15min at room temperature until the mixture is completely dissolved to obtain a dark blue vanadyl sulfate solution A;
taking 1.2ml of the solution A, adding 18.8ml of deionized water, uniformly mixing, and then adding 0.02ml of concentrated sulfuric acid to prepare a hydrothermal reaction solution, wherein the pH value of the hydrothermal reaction solution is 2.4;
placing 20ml of hydrothermal reaction solution into a 50ml p-polyphenyl reaction kettle for hydrothermal reaction, placing a C-axis oriented alumina substrate into the reaction kettle, sealing the reaction kettle, placing the reaction kettle into a drying oven, preserving heat at 230 ℃ for 6 hours, clarifying upper-layer liquid in the reaction kettle, and finishing the hydrothermal reaction;
and step 3, cleaning and drying:
and after the hydrothermal reaction is finished, pouring out supernatant liquor in the reaction kettle, and obtaining no uniform blue-black film on the C-axis oriented alumina substrate.
The samples prepared in this example were tested and the results were as follows:
(1) observation by a scanning electron microscope:
the SEM image of the finally obtained sample is shown in fig. 17, and it can be seen from fig. 17 that only a few hydrothermal powder products appear on the substrate, and no thin film is formed.
Example 9
This example is a comparative example, and compared with example 8, a hydrothermal reaction solution was prepared by replacing 0.02ml of concentrated sulfuric acid with 0.03ml of hydrochloric acid solution, and the pH value of the hydrothermal reaction solution was 3.0; the other conditions were the same.
The results show that no uniform blue-black film was obtained on the C-axis oriented alumina substrate, with only a few hydrothermal powder products appearing on the substrate.
Example 10
This example is a comparative example, and compared with example 1, the amount of vanadyl sulfate in step 1 was changed to 0.326g, and the other conditions were the same, so that the concentration of vanadium ions in the hydrothermal reaction solution was 0.0020 mol/L;
steps 2-4 are the same as in example 1.
The results show that the continuity between the resulting films on the C-axis oriented alumina substrate is poor.
Example 11
This example is a comparative example, and compared with example 1, the amount of vanadyl sulfate in step 1 was changed to 3.26g, and the other conditions were the same, so that the concentration of vanadium ions in the hydrothermal reaction solution was 0.02 mol/L;
steps 2-4 are the same as in example 1.
The results show that the film obtained on the C-axis oriented alumina substrate was easily peeled off and the film could not be used.
Example 12
This example is a comparative example, and compared to example 1, the amounts of the dihydrate and citric acid used in step 1 were changed to 0.022ml formic acid, and the other conditions were the same.
Steps 2-4 are the same as in example 1.
The results show that no uniform blue-black film was obtained on the C-axis oriented alumina substrate.
Example 13
This example is a comparative example, and compared with example 1, the dihydrate and citric acid in step 1 were changed to ascorbic acid, and 1.76g of ascorbic acid (C) was taken6H8O6) Mixing the powder with 100ml of distilled water, stirring to dissolve for 30min, and uniformly mixing to obtain a solution B; the other conditions were the same.
Steps 2-4 are the same as in example 1.
The results show that no uniform blue-black film was obtained on the C-axis oriented alumina substrate.
The foregoing is merely a preferred embodiment of this invention, which is intended to be illustrative, not limiting; those skilled in the art will appreciate that many variations, modifications, and even equivalent variations are possible within the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the nano vanadium dioxide film is characterized by comprising the following steps:
step 1, preparing a hydrothermal reaction solution: mixing the vanadium source solution and the organic carboxylic acid solution to obtain an element-free doped hydrothermal reaction solution; or
Mixing a vanadium source solution, an organic carboxylic acid solution and a doped element solution to obtain an element-doped hydrothermal reaction solution; the organic carboxylic acid solution is a binary organic carboxylic acid solution or a ternary organic carboxylic acid solution;
step 2, hydrothermal reaction: completely immersing the substrate in the hydrothermal reaction solution prepared in the step 1 to carry out hydrothermal reaction;
and step 3, cleaning and drying: after the hydrothermal reaction is finished, taking out the substrate on which the film with the deposit grows, cleaning to remove the deposit on the surface of the film, and drying to obtain the substrate on which the film grows;
and 4, annealing treatment: and (4) annealing the substrate with the film grown in the step (3) to obtain the nano vanadium dioxide film.
2. The method for preparing a nano vanadium dioxide film according to claim 1, wherein the metal ions in the liquid vanadium source solution are only vanadium ions.
3. The method for preparing a nano vanadium dioxide film according to claim 2, wherein the concentration of vanadium ions in the hydrothermal reaction solution is 1mmol/L to 20 mmol/L; the molar ratio of the vanadium ions to acid radical ions in the organic carboxylic acid is 1: 0.5-8; the pH value of the hydrothermal reaction solution is 1-5; preferably, the concentration of the vanadium ions is 3 mmol/L-10 mmol/L, more preferably 3 mmol/L-6 mmol/L; preferably, the molar ratio of the vanadium ions to the acid radical ions in the organic carboxylic acid solution is 1: 3-8; preferably, the pH value of the hydrothermal reaction solution is 2-4.
4. The method for preparing a nano vanadium dioxide film according to claim 1 or 2, wherein the vanadium source solution is prepared by dissolving a solid vanadium-containing compound with a first solvent;
wherein the solid vanadium-containing compound is selected from one or more of vanadyl sulfate, vanadium pentoxide, vanadyl acetylacetonate, triisopropoxyl vanadium oxide and ammonium metavanadate; preferably at least one of vanadyl sulfate and vanadyl acetylacetonate;
the first solvent is selected from water or ethanol.
5. The method for preparing nano vanadium dioxide film according to claim 1 or 2, wherein the acid in the organic carboxylic acid solution is selected from any one of acetic acid, phthalic acid, citric acid and terephthalic acid; when the acid is liquid, the acid is directly used as an organic carboxylic acid solution; when the acid is solid, adding a second solvent for dissolving to prepare an organic carboxylic acid solution; the second solvent is selected from one of ethanol, water and glycol.
6. The method for preparing a nano vanadium dioxide film according to claim 1 or 2, wherein in the step 2, the hydrothermal reaction is carried out at 180-280 ℃ for 15 min-24 h.
7. The method for preparing the nano vanadium dioxide film according to claim 1 or 2, wherein the substrate is selected from any one of alumina, titania or glass; preferably a polished C-axis oriented single crystal alumina.
8. The method for preparing a nano vanadium dioxide film according to claim 1 or 2, wherein in the step 3, the cleaning is ultrasonic cleaning.
9. The method for preparing a nano vanadium dioxide film according to claim 1 or 2, wherein the drying in the step 3 is drying by blowing dry gas; preferably, the drying gas is nitrogen, preferably with a purity of 99.99%.
10. The method for preparing a nano vanadium dioxide film according to claim 1 or 2, wherein the annealing treatment is specifically performed by annealing treatment at 250-600 ℃ for 30 s-24 h under the condition that the air pressure is 0.1-100 KPa;
preferably, the air pressure is 0.5KPa to 10KPa, the annealing temperature is 300 ℃ to 500 ℃, and the annealing time is 30s to 30 min.
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