CN112331555A - Preparation method of vanadium dioxide film with adjustable thermal hysteresis loop - Google Patents

Preparation method of vanadium dioxide film with adjustable thermal hysteresis loop Download PDF

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CN112331555A
CN112331555A CN202011166908.1A CN202011166908A CN112331555A CN 112331555 A CN112331555 A CN 112331555A CN 202011166908 A CN202011166908 A CN 202011166908A CN 112331555 A CN112331555 A CN 112331555A
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temperature
film
vanadium dioxide
hysteresis loop
thermal hysteresis
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储新宏
张小明
郭兵锋
刘健平
余济海
陶海征
梁瑞
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Yichun University
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Abstract

The invention discloses a preparation method of a vanadium dioxide film with an adjustable thermal hysteresis loop, which comprises the steps of firstly preparing a metal vanadium film on a substrate, then placing the film in a vacuum atmosphere furnace for oxidation annealing, and controlling the crystal grain size, the number of crystal boundaries, the number of oxygen vacancies, the number of microcrystals below 15-20nm, the particle size distribution, the interface energy and other performance influencing factors of the vanadium dioxide film by cooperatively controlling annealing air pressure of 10-3000 Pa, annealing temperature of 300-550 ℃, heating rate of 5-20 ℃/min, annealing time of 0-90 min and the like through a method of low-pressure secondary annealing treatment, so as to obtain the vanadium dioxide film with the adjustable thermal hysteresis loop, wherein the width regulation range is 5-35 ℃, the light transmittance height regulation range is 17-54%, and the phase transition temperature regulation range is 34-60 ℃. The simple and reliable preparation method meets the requirements of different fields such as thermosensitive photosensitive elements, laser blinding protection devices, biosensors, gas detectors, intelligent windows and the like on vanadium dioxide films with different thermochromic performances.

Description

Preparation method of vanadium dioxide film with adjustable thermal hysteresis loop
The technical field is as follows:
the invention belongs to the field of preparation of film materials, relates to a preparation method of a vanadium dioxide film, and particularly relates to a preparation method of a vanadium dioxide film with an adjustable thermal hysteresis loop.
Background art:
the vanadium dioxide film is a reversible phase-change material, the phase-change temperature (68 ℃) of a block body of the vanadium dioxide film is close to room temperature, the vanadium dioxide film is one of the best materials applied to an intelligent window, the phase-change reaction speed is very fast in nanosecond level, and the vanadium dioxide film is also one of the first-choice materials for preparing various thermosensitive elements, photoelectric switches, laser blind-leading protection devices, uncooled focal plane detectors, optical data storages, low-temperature nonlinear filters, biosensors, gas detectors, intelligent windows and the like. The vanadium dioxide has high infrared transmittance at low temperature, and has high absorption and reflection in an infrared region at high temperature, so that the transmittance is greatly reduced; the change amplitude of the resistivity before and after the phase change can reach 102 and 104 times. The VO2(M/R) has wide application prospect in the fields of infrared regulation, uncooled focal plane infrared detection, photoelectric switches, laser protection, optical storage, optical modulation and the like due to the sudden change of optical and electrical physical properties before and after phase change. The vanadium dioxide M/R phase transformation is a reversible process, the phase transformation has thermal hysteresis in the heating and cooling processes, and the difference is expressed by the difference of phase transformation temperatures in the heating and cooling processes, and the difference is the width of a thermal hysteresis loop.
Meanwhile, vanadium dioxide below the phase transition temperature is in a monoclinic crystal form (M) and belongs to an insulator or a semiconductor, and vanadium dioxide above the phase transition temperature is in a tetragonal rutile crystal form (R) and belongs to a conductor. VO accompanying phase transition2All have abrupt changes in optical, electrical and magnetic properties. The properties of the vanadium dioxide can be shown by testing a temperature-variable transmission curve or a temperature-variable resistor, and the performance of the vanadium dioxide film can be observed and judged more visually by further drawing a thermal hysteresis loop. The height of the thermal hysteresis loop represents the near-infrared adjusting efficiency or adjusting capacity of the film; the width of the thermal hysteresis loop represents the temperature span of the film in a reversible cycle process or the temperature hysteresis degree of a phase change point in the reverse process; the gradient or gradient of the thermal hysteresis loop represents the speed of the film completing phase change at the phase change temperature point orDegree, or represents the speed or degree of response of the thin film material to the critical temperature; the temperature corresponding to the perpendicular bisector of the thermal hysteresis loop represents the phase transition temperature of the film material, and the more the positions of the perpendicular bisector and the thermal hysteresis loop are close to the positive direction of the temperature of the abscissa axis, the higher the phase transition temperature is. The distance between the perpendicular bisector and the midpoint of the left and right loops is half of the width, which shows that the forward and reverse phase transformation have a certain lag relative to the temperature, and the phase transformation temperature represented by the perpendicular bisector represents the average phase transformation temperature of the film material.
Chinese patent publication No. CN101792182A, discloses a tungsten-doped vanadium dioxide powder material and a preparation method thereof,
the tungsten-doped vanadium dioxide powder material comprises the following components in percentage by mass: reducing agent: 2.97% -3.19%, industrial pure tungsten trioxide: 0 to 6.89 percent of vanadium pentoxide, and the balance of industrial pure vanadium pentoxide, wherein the sum of the mass percentages of the components is 100 percent. The preparation method of the tungsten-doped vanadium dioxide powder material comprises the steps of weighing the raw materials according to the mass percentage, mixing for 4-6 hours, carrying out high-temperature reduction on the uniformly mixed powder under the protection of inert gas, and finally dispersing to obtain the tungsten-doped vanadium dioxide powder material. The tungsten-doped vanadium dioxide powder material and the preparation method thereof have the advantages that the tungsten-doped vanadium dioxide powder material is high-purity vanadium dioxide and has a single crystal form, and the phase transition temperature Tc can be controlled within the range of-2.9-67.04 ℃ according to the quantity of doped metal ions W6+, so that the optical, electrical, magnetic and other properties of the tungsten-doped vanadium dioxide powder material are mutated within the range of-2.9-67.04 ℃, and the requirements of special functional materials are met. For example, Chinese publication No. CN101481142, a method for preparing doped vanadium dioxide powder material, relates to W, Mo or W/Mo co-doped vanadium dioxide powder preparation. The method comprises the steps of uniformly mixing and grinding a vanadium source, a doping raw material and an auxiliary agent, pouring the mixture into cold water for rapid water quenching after high-temperature melting and heat preservation for a certain time, drying and heat treating the formed gel to form dry gel, carrying out thermal reduction on the ground dry gel in a reducing atmosphere, and carrying out annealing treatment in a protective atmosphere to realize constant-temperature crystalline phase conversion so as to obtain the M-phase VO2 with the phase change property. The phase transition temperature of the doped VO2 powder can be effectively controlled by modulating the doping amount of W, Mo atoms. For example, the method for adjusting the phase transition temperature of a vanadium dioxide film is disclosed in Chinese patent publication No. CN 104261873A. And (3) carrying out oxygen annealing on the metal vanadium or low-valence vanadium oxide film under the vacuum condition, and adjusting the phase transition temperature of the generated vanadium dioxide film by changing the oxygen partial pressure in the annealing process. The phase change adjusting method does not depend on a substrate, can be realized on a crystal substrate or an amorphous substrate, and is a very simple and effective phase change temperature adjusting method for the vanadium dioxide film. As can be seen from the above-mentioned disclosed preparation method for preparing a vanadium dioxide thin film, it is generally realized by changing the chemical composition of the material for preparing the vanadium dioxide thin film, and changing the oxidation atmosphere, etc. The invention discloses a method for adjusting the width of a thermal hysteresis loop, which is characterized in that a specified amount of doping element M is doped in the process of preparing vanadium dioxide powder by a hydrothermal method so that the width of the thermal hysteresis loop of the obtained vanadium dioxide powder with the chemical composition of V1-xMxO2 is continuously adjustable between 1 and 30 ℃, wherein x is more than 0 and less than or equal to 0.3, and the doping element M is indium, tellurium, tin, gallium and/or germanium. From the above disclosure, it can be seen that they are also achieved by changing the composition of the raw materials for preparing the vanadium dioxide film, i.e. by chemical methods.
Because the vanadium metal oxide system is complex, the valence of V element is more, and the preparation of vanadium dioxide with intermediate valence state is very difficult. At present, different experts and scholars adopt different methods or processes to prepare vanadium dioxide films, the prepared vanadium dioxide films are different in structure and performance, the drawn thermal hysteresis loops are different in shape and position, the success rate is low, and the repeatability is poor. The preparation of VO by post-oxidation has been reported2The film obtains better repeatability, but the phase change performance of the vanadium dioxide film is mainly the shape and the position of a thermal hysteresis loop, the film is not controllable and adjustable, and the requirements of different device devices and different fields can not be met, for example, the film is applied to laser protection devices, thermosensitive elements, filters, biosensors, intelligent windows and the like, some device devices need to be wide,High, steep hysteresis loops, and some require narrow, low, sloping or gentle hysteresis loops.
Therefore, how to utilize the preparation process parameter conditions of the vanadium dioxide film in the process of preparing the vanadium dioxide film to prepare the vanadium dioxide film with adjustable thermal hysteresis loop, stability and reliability.
The invention content is as follows:
the invention discloses a preparation method of a vanadium dioxide film with an adjustable thermal hysteresis loop, which comprises the steps of taking glass as a substrate, preparing a metal vanadium film on the substrate, then placing the substrate in a vacuum atmosphere furnace for oxidation annealing, and controlling the crystal grain size, the number of crystal boundaries, the number of oxygen vacancies, the number of microcrystals, the particle size distribution, the stoichiometry, the interfacial energy and other performance influencing factors of the vanadium dioxide film by cooperatively controlling the annealing pressure, the annealing temperature, the heating rate, the annealing time and other parameters and implementing a low-pressure secondary annealing treatment method to obtain the vanadium dioxide film with the adjustable thermal hysteresis loop, wherein the width regulation range comprises a height regulation range and a phase-change temperature regulation range. The preparation method of the vanadium dioxide film with different thermochromic performances in different fields such as thermosensitive photosensitive elements, laser blinding protection devices, biosensors, gas detectors, intelligent windows and the like can be met.
The invention discloses a preparation method of a vanadium dioxide film with an adjustable thermal hysteresis loop, which takes glass as a substrate and comprises the following process steps:
1) preparing a metal vanadium film on a glass substrate;
2) preparing a vanadium dioxide film with an adjustable thermal hysteresis loop, placing the vanadium metal film prepared in the step 1) in an annealing device for annealing treatment, and cooperatively adjusting and controlling annealing parameters to prepare the vanadium dioxide film with the adjustable thermal hysteresis loop, the phase change performance of which can be continuously adjusted;
3) testing a variable-temperature transmission curve, testing the variable-temperature transmission curve of the vanadium dioxide film in the step 1) by using an ultraviolet-visible-infrared spectrophotometer, controlling the testing wavelength range to be 250-500nm, controlling the testing temperature range to be from room temperature to the point of finishing phase transition temperature, controlling the variable-temperature interval to be a transmission curve tested once when the temperature rise process and the temperature drop process change by 5-10 ℃, and preserving the temperature for at least 5min before each test;
4) drawing a thermal hysteresis loop of the vanadium dioxide film sample, taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample.
The preparation method of the vanadium dioxide film with the controllable thermal hysteresis loop comprises the step 1) of preparing the metal vanadium film on a glass substrate by adopting a direct current magnetron sputtering method.
Preferably, in the preparation method of the vanadium dioxide thin film with the adjustable thermal hysteresis loop, the step 2) is to cooperatively adjust and control annealing parameters: the annealing pressure is controlled to be 10Pa-3000Pa, the annealing temperature is controlled to be 300-550 ℃, the heating rate is controlled to be 5-20 ℃/min, the annealing heat preservation time is 1-90min, and the natural cooling is finished after the heat preservation, so that the vanadium dioxide film with the adjustable thermal hysteresis loop and different phase change performance requirements is obtained.
Further, the annealing treatment in the step 2) comprises low-pressure secondary annealing treatment, wherein the annealing temperature of the low-pressure secondary annealing treatment is controlled to be 250-350 ℃, and the air pressure is controlled to be 0.1-15 Pa.
According to the preparation method of the vanadium dioxide film with the adjustable thermal hysteresis loop, the annealing treatment is carried out in the annealing device, namely the oxidation annealing treatment is carried out in a vacuum atmosphere furnace, and the oxidation annealing treatment is carried out in the vacuum atmosphere furnace under the condition of air or oxygen atmosphere.
The preparation method of the vanadium dioxide film with the controllable thermal hysteresis loop comprises the steps of cleaning the surface of a quartz glass substrate, carrying out ultrasonic treatment in absolute ethyl alcohol for 25-35 minutes, then placing the quartz glass substrate in an acetone solution for ultrasonic treatment for 25-35 minutes, and drying for later use.
Preferably, the vanadium dioxide film with the adjustable thermal hysteresis loop is obtained by controlling the grain size, the number of crystal boundaries, the number of oxygen vacancies, the number of microcrystals below 15-20nm, the particle size distribution and the interfacial energy of the vanadium dioxide film through the coordinated regulation and control of annealing parameters and the low-pressure secondary annealing treatment.
Further, the direct current magnetron sputtering is carried out under the condition that the magnetron sputtering power is controlled to be 70-85W, the working air pressure is 0.5-1.5Pa, the time is 1-25min, a substrate table of the direct current magnetron sputtering is carried out at room temperature, and the thickness of the prepared metal vanadium film is controlled to be 6-150 nm.
Further, in the preparation method of the vanadium dioxide film with the adjustable thermal hysteresis loop, the width of the vanadium dioxide film with the adjustable thermal hysteresis loop is adjusted and controlled within the range of 5-35 ℃, the height of the vanadium dioxide film with the adjustable thermal hysteresis loop is adjusted and controlled within the range of 17-54%, and the phase change temperature is adjusted and controlled within the range of 34-60 ℃.
The preparation method of the vanadium dioxide film with the controllable thermal hysteresis loop has the beneficial effects that: the method controls the grain size, the number of crystal boundaries, the number of oxygen vacancies, the number of microcrystals below 15-20nm, the grain size distribution and the interfacial energy of the vanadium dioxide film by regulating and controlling technological characteristic parameters in the process of preparing the vanadium dioxide film, such as by cooperatively regulating and controlling annealing parameters and low-pressure secondary annealing treatment, so as to obtain the vanadium dioxide film with the controllable thermal hysteresis loop. Meanwhile, by using the simple and reliable preparation method of the vanadium dioxide film with controllable thermal hysteresis loop, the prepared vanadium dioxide film can meet the requirements of different devices, products or fields on different phase change performances of the vanadium dioxide film, and the purpose of preparing the vanadium dioxide film with specific performance according to individual requirements is realized; in addition, the invention provides a reliable, simple and easy method for studying and judging the microstructure of the prepared vanadium dioxide film according to the information of the shape, the position and the like of the thermal hysteresis loop, such as the information of the grain size, the number of crystal boundaries, the grain size distribution, the stoichiometry, the oxygen vacancy defect, the flatness, the interface energy and the like.
Description of the drawings:
FIG. 1 shows example 1: oxidizing 30nm metal vanadium film by 400-1 h-1500Pa-5 ℃/min technology to obtain VO2A thermal hysteresis line of the film;
FIG. 2 shows example 2: oxidizing 30nm metal vanadium film by the process of 550-1 h-1500Pa-5 ℃/min to obtain VO2A thermal hysteresis line of the film; andexample 3 in comparison, the thermal hysteresis loop becomes wider, higher and steeper, and the phase transition temperature increases;
FIG. 3 is example 3: oxidizing 30nm metal vanadium film at the speed of 350-1 h-1500Pa-5 ℃/min to obtain VO2A thermal hysteresis line of the film; compared with the example 2, the thermal hysteresis loop becomes narrow, short and gentle, and the phase transition temperature is reduced;
FIG. 4 shows example 4: VO is obtained by oxidizing 30nm of metal vanadium film by the process of 400-1 h-2000Pa-5 ℃/min2A thermal hysteresis line of the film; compared with example 5, the thermal hysteresis loop becomes narrower, higher and steeper, and the phase transition temperature increases;
FIG. 5 shows example 5: VO is obtained by oxidizing 30nm of metal vanadium film by the process of 400-1 h-10Pa-5 ℃/min2A thermal hysteresis line of the film; compared with the example 4, the thermal hysteresis loop becomes wider, shorter and sloping (gentle), and the phase transition temperature is reduced;
FIG. 6 shows example 6: VO is obtained by oxidizing 30nm of metal vanadium film by the process of 400-1.5 h-1500Pa-5 ℃/min2A thermal hysteresis line of the film; compared with example 1, the thermal hysteresis line becomes wider and shorter, and the phase transition temperature increases;
FIG. 7 shows example 7: oxidizing 30nm metal vanadium film by 400-1 h-1500Pa-10 ℃/min technology to obtain VO2A thermal hysteresis line of the film; compared with the example 1, the thermal hysteresis loop becomes wider, shorter and sloping (gentle), and the phase transition temperature rises;
FIG. 8 shows example 8: VO is obtained by oxidizing 30nm of metal vanadium film by the process of 400-1 h-1700Pa-10 ℃/min2A thermal hysteresis line of the film;
FIG. 9 shows example 9: VO is obtained by oxidizing 30nm of metal vanadium film by the process of 400-1 h-1700Pa-10 ℃/min2Performing low-pressure secondary annealing treatment on the film for 5 hours to obtain a thermal hysteresis loop; compared with example 8, the height of the thermal hysteresis loop is increased, and the phase transition temperature is reduced;
FIG. 10 is a diagram: scanning Electron Microscope (SEM) pictures of film samples of example 1;
FIG. 11 is a diagram of: the X-ray diffraction pattern for the film sample of example 1;
FIG. 12 is a diagram: example 2 SEM photograph of film sample;
FIG. 13 is a graph of: example 6 SEM pictures of film samples.
The specific implementation mode is as follows:
the invention is further described in detail with reference to the drawings and the detailed description; the vanadium dioxide films or films described below have the same meaning;
as shown in fig. 1-13, the method for preparing a vanadium dioxide thin film with an adjustable thermal hysteresis loop, disclosed by the invention, takes glass as a substrate, and comprises the following process steps:
1) preparing a metal vanadium film, namely preparing the metal vanadium film on the pretreated quartz glass substrate; the pretreatment of the quartz glass substrate comprises the steps of cleaning the surface of the quartz glass substrate, carrying out ultrasonic treatment in absolute ethyl alcohol for 25-35 minutes, then placing the quartz glass substrate in an acetone solution for ultrasonic treatment for 25-35 minutes, and drying; or cleaning the surface of a quartz glass substrate, then placing the quartz glass substrate into an acetone solution for ultrasonic treatment for 25-35 minutes, then performing ultrasonic treatment for 25-35 minutes in absolute ethyl alcohol, drying, then preparing the metal vanadium film by adopting a direct current magnetron sputtering method, controlling the magnetron sputtering power to be 70-85W, the working air pressure to be 0.5-1.5Pa and the time to be 1-25 minutes, preparing the metal vanadium film by a substrate table subjected to direct current magnetron sputtering under the room temperature condition, and simultaneously controlling the thickness of the prepared metal vanadium film to be 6-150 nm;
preparing a vanadium dioxide film with an adjustable thermal hysteresis loop or a vanadium dioxide film capable of being continuously adjusted, placing the vanadium dioxide film prepared in the step 1) in an annealing device, namely a vacuum atmosphere furnace for oxidation annealing treatment, cooperatively adjusting and controlling annealing parameters, controlling the annealing pressure to be 10-3000 Pa, the annealing temperature to be 300-550 ℃, the heating rate to be 5-20 ℃/min and the annealing time to be 1-90min, preserving heat, and naturally cooling to obtain the vanadium dioxide film with the adjustable thermal hysteresis loop and different phase change performance requirements;
2) further, the annealing treatment comprises low-pressure secondary annealing treatment, wherein the annealing temperature of the low-pressure secondary annealing treatment is controlled to be 250-350 ℃, and the air pressure is controlled to be 0.1-15 Pa; carrying out oxidation annealing treatment in a vacuum atmosphere furnace, wherein the oxidation annealing treatment in the vacuum atmosphere furnace is carried out under the condition of air or oxygen atmosphere; preparing a vanadium dioxide film with continuously adjustable phase change performance, namely a vanadium dioxide film with adjustable thermal hysteresis line;
3) testing a variable-temperature transmission curve, testing the variable-temperature transmission curve of the film by using an ultraviolet-visible-infrared spectrophotometer with a heating device, controlling the testing wavelength range to be 250-500nm, controlling the testing temperature range to be the temperature from room temperature to the point of finishing phase transition, namely the temperature when the transmission curve does not change any more, controlling the variable-temperature interval to be the temperature rise process and the temperature drop process, testing the transmission curve once at the temperature of 5-10 ℃ each time, and preserving the temperature for at least 5min before each test;
4) preparing a thermal hysteresis loop of the vanadium dioxide film sample, taking a transmittance value at 2000nm from a temperature-changing transmission curve as a vertical coordinate, taking a test temperature of the temperature-changing transmission curve as a horizontal coordinate, and drawing the thermal hysteresis loop of the VO2 film sample; the crystal grain size of the vanadium dioxide film is below 15-20nm, the vanadium dioxide film with the controllable thermal hysteresis loop is obtained, the width control range is 5-35 ℃, the height control light transmittance range is 17-54%, and the phase change temperature control range is 34-60 ℃.
Description of specific parameters:
the ultraviolet-visible-infrared spectrophotometer is an ultraviolet-visible-infrared spectrophotometer with a heating device, the variable temperature transmittance curve of the vanadium dioxide film is tested, the test wavelength range is 250-2500 nm, the test temperature range is from room temperature to the temperature point of finishing phase transition, namely the temperature when the transmittance curve does not change any more, the variable temperature interval is 5 ℃, namely the transmittance curve is tested once when the temperature changes by 5 ℃ in the temperature rising process and the temperature reducing process, and the temperature is kept for at least 5min before each test. And taking the transmittance value at the 2000nm position from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing a thermal hysteresis loop of the vanadium dioxide film sample.
The invention relates to a preparation method of a vanadium dioxide film with an adjustable thermal hysteresis loop, which is characterized in that the method and the principle of the method for cooperatively adjusting and controlling annealing parameters are as follows: the influence of different parameter change annealing temperature, annealing pressure, annealing time, heating rate and low-pressure secondary annealing treatment on the adjustment thermal hysteresis loop of the vanadium dioxide film is illustrated as follows: namely, the preparation of the vanadium dioxide film with adjustable thermal hysteresis loop under different conditions is explained;
under the condition that other process parameters correspond to each other, the annealing temperature is raised to 550 ℃ for example to obtain the vanadium dioxide film with the phase transition temperature higher by 54 ℃, the thermal hysteresis loop wider by 35 ℃, and the thermal hysteresis loop steeper and higher by 54 percent. The large-grain vanadium dioxide film can be prepared at a high annealing temperature, the number of grain boundaries of the large-grain film is small, the potential barrier to be overcome when phase change occurs is high, phase change can occur at a high temperature, reverse phase change can occur only after lagging to a low temperature, and therefore the prepared film is high in phase change temperature and wide in thermal hysteresis loop. The vanadium dioxide film has no microcrystal with the grain size of below 15-20nm, the grain size distribution is uniform, potential barriers overcome by phase change are approximately equal, phase change basically occurs synchronously, and therefore the thermal hysteresis loop is steep. Annealing at high temperature to obtain crystal VO2The content is high, and the near infrared adjusting efficiency is high, so that the thermal hysteresis loop height is high; under the condition that other process parameters are proper, the annealing temperature is reduced, for example 350 ℃, so that the vanadium dioxide film with lower phase transition temperature of 34 ℃, narrower thermal hysteresis loop, for example, 7 ℃ wider, more sloping, gentle and shorter, for example, 17% higher light transmittance is obtained. The low annealing temperature leads to the generation of a vanadium dioxide film with small crystal grains, the crystal boundary number of the film with the small crystal grains is more, the potential barrier to be overcome when the phase change occurs is lower, the phase change occurs at a lower temperature, and the reverse phase change can occur at a temperature with less hysteresis, so that the prepared film has lower phase change temperature and narrower thermal hysteresis loop. The film has more microcrystals below 15-20nm, the particle size distribution is not uniform, the potential barriers overcome by phase change are different in size, and the phase change occurs asynchronously, so that the thermal hysteresis loop is relatively sloping (gentle). Annealing at low temperature to obtain VO2Microcrystalline or amorphous, crystalline VO2The content is low, and the near infrared adjusting efficiency is low, so the thermal hysteresis loop height is low;
under the condition that other process parameters are proper, the annealing pressure is increased, for example 2000Pa, and the vanadium dioxide film with higher phase transition temperature of 60 ℃, narrower thermal hysteresis loop, wider loop width of 5 ℃, steeper and higher loop, for example 50 percent higher light transmittance is obtained at a proper temperature, for example 400 ℃. The high annealing pressure has sufficient oxygen content, no oxygen vacancy or few oxygen vacancies in the film, the Fermi level moves to a conduction band, and the forbidden bandwidth is increasedAnd phase change is difficult to realize, so that the phase change temperature is increased, the surface of the film obtained by annealing under the condition is relatively flat, the interface energy is relatively small, and the reverse phase change needs to overcome relatively small potential barrier, so that the thermal hysteresis width is relatively narrow. The film does not basically have microcrystals below 15-20nm, so the thermal hysteresis loop is steeper. Annealing at the pressure and temperature to obtain crystal VO2The content is high, and the near infrared adjusting efficiency is high, so that the thermal hysteresis loop height is high; under the condition that other process parameters are proper, the annealing pressure (for example, 10 Pa) is reduced, and the vanadium dioxide film with lower phase transition temperature (for example, 41 ℃), wider thermal hysteresis loop, more sloping, gentle and shorter thermal hysteresis loop and 46% higher thermal transmittance is obtained at a proper temperature (for example, 400 ℃). The low annealing pressure has insufficient oxygen content, more oxygen vacancies exist in the film, the Fermi level moves to a valence band, the forbidden bandwidth is reduced, the phase change is easy, and the phase change temperature is reduced. The film has microcrystals with the diameter of 15-20nm or less, so that the thermal hysteresis loop is relatively sloping. Annealing at the pressure and temperature to obtain crystal VO in stoichiometric ratio2The content is low, and the near infrared adjusting efficiency is low, so the thermal hysteresis loop height is low;
under the condition of proper other process parameters and proper annealing time, such as 60min, the vanadium dioxide film with lower phase transition temperature, 46 ℃, narrower thermal hysteresis loop, 14 ℃ of loop width, higher loop height of 50 percent, light transmittance and the like is obtained. The vanadium dioxide film with a relatively flat surface can be obtained in proper annealing time, the interface energy is relatively small, the phase change needs to overcome a relatively small potential barrier, and therefore the phase change temperature of the film is relatively low, and the thermal hysteresis loop is relatively narrow. Crystal VO obtained by proper annealing time2The content is high, and the near infrared adjusting efficiency is high, so that the thermal hysteresis loop height is high; under the condition of proper other process parameters, overlong annealing time (for example 90 min) can obtain the vanadium dioxide film with higher phase transition temperature, 52 ℃, wider thermal hysteresis loop, 19 ℃ wider loop, shorter loop and 47% higher loop and light transmittance. Too long an annealing time may result in long sheets V2O5The crystal is generated, obliquely inserted and distributed in the film, and the surface becomesThe unevenness causes the increase of the interfacial energy of the film, and the potential barrier which needs to be overcome when the phase change occurs is increased, so the phase change temperature of the film is higher, and the thermal hysteresis loop is wider. Too long annealing time leads to partial VO2Generating V2O5，VO2The crystal content is reduced, and the near infrared adjustment efficiency is reduced, so that the thermal hysteresis loop height is shorter.
Under the condition of proper other process parameters, the vanadium dioxide film with lower phase-change temperature of 46 ℃, narrower thermal hysteresis loop, 14 ℃ wider loop, steeper return and higher return height of 50 percent and light transmittance is obtained at lower temperature rise rate (for example, 5 ℃/min). The flat small-grain film is obtained at a low temperature rise rate, the interface energy is small, the number of crystal boundaries is large, and the potential barrier to be overcome when phase change occurs is small, so that the phase change temperature of the film is low, and the thermal hysteresis loop is narrow. The film does not basically have microcrystals below 15-20nm, the particle size distribution is uniform, the interface energy is uniform, the potential barriers overcome by phase change are approximately equal, the phase change basically occurs synchronously, and therefore the thermal hysteresis loop is steep. Crystal VO in accordance with stoichiometric ratio obtained by lower temperature rising rate2The content is high, and the near infrared adjusting efficiency is high, so that the thermal hysteresis loop height is high; under the condition of proper other process parameters, the vanadium dioxide film with higher phase transition temperature of 52 ℃, wider thermal hysteresis loop back width of 27 ℃, gentler slope and shorter back height of 36 percent and light transmittance is obtained by higher temperature rising rate such as 10 ℃/min. The higher temperature rise rate can promote large-grain VO2And a long sheet V2O5The growth of (2), the number of large grain boundaries is less, the activation energy is higher, and long flaky V2O5The film is obliquely dispersed in the film, so that the interfacial energy of the film is increased, the potential barrier which needs to be overcome by phase change is increased, and the phase change temperature and the thermal hysteresis loop of the film are higher. The film does not basically have microcrystalline VO below 15-20nm2The particle size distribution is uniform, but the long sheet shape V is distributed obliquely2O5The existence of the thermal hysteresis loop causes uneven interface energy, unequal potential barriers for overcoming the phase change and asynchronous phase change, so that the thermal hysteresis loop is relatively sloping (gentle). Higher heating rate makes partial VO easy2Generating V2O5VO crystal2Reduced content and near infrared regulation effectThe rate decreases, so the thermal hysteresis loop height is short.
The method and the principle of adopting the low-pressure secondary annealing treatment are as follows: the prepared VO2And putting the film into a vacuum annealing furnace, annealing for the second time for a period of time, such as 5 hours, at a lower annealing temperature, such as 300 ℃, and under a lower air pressure, such as below 10Pa, naturally cooling, and taking out to obtain the vanadium dioxide film with a reduced phase transition temperature and an increased thermal hysteresis loop height. The secondary annealing at low temperature and low pressure can produce oxygen vacancy under the condition of unchanged grain size, the increase of the oxygen vacancy enables the Fermi level of the film material to move to the valence band, the forbidden bandwidth is reduced, the phase change is easy, and the phase change temperature is reduced. Heating at low pressure to partially raise valence V2O5Oxygen evolution to VO2VO crystal2The content is increased, the near infrared adjusting efficiency is enhanced, and therefore the height of the thermal hysteresis loop is increased.
Example 1:
in this embodiment, quartz glass is used as a substrate, a vanadium metal thin film is first plated on the surface of the substrate, then the substrate is placed in a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide thin film, the temperature-variable transmittance of a test thin film sample is taken out, and a thermal hysteresis loop is drawn as shown in fig. 10-11. The specific implementation steps are as follows:
(1) pretreatment or cleaning of the glass substrate: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: plating a metal vanadium film on a clean quartz glass substrate by using direct current magnetron sputtering (DC), wherein the target material is a metal vanadium target, the diameter of the metal vanadium target is 56mm, the purity of the metal vanadium target is 99.9%, and the working gas is argon with the purity of 99.99%; controlling the sputtering power of 77W, the working pressure of 1Pa and the degree of vacuum of the back bottom of 3.0 multiplied by 10-3Pa and sputtering for 5 minutes to obtain a metal vanadium film with the thickness of 30 nm;
(3) post oxidation annealing and testing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1500Pa, raising the temperature to 400 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1h, naturally cooling to the temperature below 100 ℃, and taking out a sample; testing a temperature-changing transmission curve: testing an ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing phase transition temperature (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once when the temperature is changed by 5 ℃ in the heating process and the cooling process, and the temperature is kept for at least 5 minutes before each test;
(4) drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of the film sample; as shown in fig. 1, 10-11. The parts which are not described in the following examples are the same as in example 1.
Example 2:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The difference from example 1 is that the change in annealing temperature is an increase; the specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: plating a metal vanadium film on a clean quartz glass substrate by using direct current magnetron sputtering (DC), wherein a target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and a working gas is argon with the purity of 99.99 percent; controlling the sputtering power of 77W, the working pressure of 1Pa and the degree of vacuum of the back bottom of 3.0 multiplied by 10-3Pa and sputtering time of 5 minutes to obtain a metal vanadium film with the thickness of 30 nm.
(3) Post oxidation annealing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1500Pa, raising the temperature to 550 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1h, naturally cooling to the temperature below 100 ℃, and taking out a sample;
testing a temperature-changing transmission curve: testing an ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing phase transition temperature (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once when the temperature is changed by 5 ℃ in the heating process and the cooling process, and the temperature is kept for at least 5 minutes before each test;
(4) drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 2 and 12.
Example 3:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The difference from comparative example 2 is that the change in annealing temperature is reduced. The specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of the quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use.
(2) Performing magnetron sputtering plating on a metal vanadium film: a metal vanadium film is plated on a clean quartz glass substrate by using direct current magnetron sputtering (DC), the target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and the working gas is argon with the purity of 99.99 percent. Controlling the sputtering power of 77W, the working pressure of 1Pa and the degree of vacuum of the back bottom of 3.0 multiplied by 10-3Pa and sputtering time of 5 minutes to obtain a metal vanadium film with the thickness of 30 nm.
(3) Post oxidation annealing: and (3) placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1500Pa, heating to 350 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1h, naturally cooling to the temperature below 100 ℃, and taking out the sample.
(4) Testing a temperature-changing transmission curve: and testing the ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing the phase transition (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once every 5 ℃ in the temperature rising process and the temperature reducing process, and the temperature is kept for at least 5 minutes before each test.
(5) Drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 3.
Example 4:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The difference from example 1 is that the annealing gas pressure is increased. The specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: a metal vanadium film is plated on a clean quartz glass substrate by using direct current magnetron sputtering (DC), the target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and the working gas is argon with the purity of 99.99 percent. Controlling the sputtering power of 85W, the working pressure of 1.5Pa and the vacuum degree of the back bottom of 3.0 multiplied by 10-3Pa and sputtering for 5-10 minutes to obtain a metal vanadium film with the thickness of 30 nm;
(3) post oxidation annealing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to 2000Pa, heating to 400 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, naturally cooling to below 100 ℃, and taking out a sample;
testing a temperature-changing transmission curve: testing an ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing phase transition temperature (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once when the temperature is changed by 5 ℃ in the heating process and the cooling process, and the temperature is kept for at least 5 minutes before each test;
(4) drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 4.
Example 5:
in the embodiment, quartz glass is taken as a substrate, a vanadium metal film is plated on the surface of the substrate, then the substrate is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the vanadium dioxide film is taken out to test the variable temperature transmittance of a vanadium dioxide film sample, and a thermal hysteresis loop is drawn, as shown in fig. 5; mainly, the change of the annealing gas pressure is reduced compared with the example 4; the specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: a metal vanadium film is plated on a clean quartz glass substrate by using direct current magnetron sputtering (DC), the target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and the working gas is argon (the purity is 99.99 percent). Controlling the sputtering power of 77W, the working pressure of 1Pa and the degree of vacuum of the back bottom of 3.0 multiplied by 10-3Pa and sputtering for 5 minutes to obtain a metal vanadium film with the thickness of 30 nm;
(3) post oxidation annealing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to 10Pa, heating to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 0.5h, naturally cooling to below 100 ℃, and taking out a sample;
testing a temperature-changing transmission curve: testing an ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing phase transition temperature (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once when the temperature is changed by 5 ℃ in the heating process and the cooling process, and the temperature is kept for at least 5 minutes before each test;
(4) drawing a thermal hysteresis loop: the transmittance value at 2000nm is taken from the temperature-changing transmission curve as the ordinateTaking the test temperature of the temperature-variable transmission curve as an abscissa and drawing VO2Thermal hysteresis loop of film sample.
Example 6:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The annealing soak time is extended compared to example 1 above. The specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: plating a metal vanadium film on a clean quartz glass substrate by using direct current magnetron sputtering (DC), wherein a target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and a working gas is air; controlling the sputtering power of 77W, the working pressure of 1Pa and the degree of vacuum of the back bottom of 3.0 multiplied by 10-3Pa and sputtering for 5 minutes to obtain a metal vanadium film with the thickness of 30 nm;
(3) post oxidation annealing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1500Pa, raising the temperature to 400 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1.5h, naturally cooling to the temperature below 100 ℃, and taking out a sample;
testing a temperature-changing transmission curve: testing an ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing phase transition temperature (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once when the temperature is changed by 5 ℃ in the heating process and the cooling process, and the temperature is kept for at least 5 minutes before each test;
(4) drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 6.
Example 7:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The rate of temperature rise is increased as in example 1 above. The specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: a metal vanadium film is plated on a clean quartz glass substrate by using direct current magnetron sputtering (DC), the target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and the working gas is argon (the purity is 99.99 percent). Controlling the sputtering power of 77W, the working pressure of 1Pa and the degree of vacuum of the back bottom of 3.0 multiplied by 10-3Pa and sputtering for 5 minutes to obtain a metal vanadium film with the thickness of 30 nm;
(3) post oxidation annealing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1500Pa, raising the temperature to 400 ℃ at the heating rate of 10 ℃/min, preserving the heat for 1h, naturally cooling to the temperature below 100 ℃, and taking out a sample;
testing a temperature-changing transmission curve: testing an ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing phase transition temperature (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once when the temperature is changed by 5 ℃ in the heating process and the cooling process, and the temperature is kept for at least 5 minutes before each test;
(4) drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 7.
Example 8:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of the quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use.
(2) Performing magnetron sputtering plating on a metal vanadium film: a metal vanadium film is plated on a clean quartz glass substrate by using direct current magnetron sputtering (DC), the target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and the working gas is argon (the purity is 99.99 percent). Controlling the sputtering power of 80W, the working pressure of 1Pa and the vacuum degree of the back bottom of 3.0 multiplied by 10-3Pa and sputtering time of 5 minutes to obtain a metal vanadium film with the thickness of 30 nm.
(3) Post oxidation annealing: and (3) placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1700Pa, raising the temperature to 400 ℃ at the heating rate of 10 ℃/min, preserving the heat for 1h, naturally cooling to the temperature below 100 ℃, and taking out the sample.
Testing a temperature-changing transmission curve: and testing the ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing the phase transition (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once every 5 ℃ in the temperature rising process and the temperature reducing process, and the temperature is kept for at least 5 minutes before each test.
(4) Drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 8.
Example 9:
in the embodiment, quartz glass is used as a substrate, a vanadium metal film is plated on the surface of the quartz glass, then the quartz glass is put into a vacuum tube furnace for oxidation annealing to generate a vanadium dioxide film, the variable temperature transmittance of a test film sample is taken out, and a thermal hysteresis loop is drawn. The difference from example 8 is that a low-pressure secondary annealing treatment was further performed. The specific implementation steps are as follows:
(1) cleaning the base lining: cleaning the surface of a quartz glass substrate with a detergent, then putting the quartz glass substrate into acetone for ultrasonic treatment for 30 minutes, finally putting the quartz glass substrate into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, and drying the quartz glass substrate for later use;
(2) performing magnetron sputtering plating on a metal vanadium film: a metal vanadium film is plated on a clean quartz glass substrate by using direct current magnetron sputtering (DC), the target material is a metal vanadium target (the diameter is 56mm, the purity is 99.9 percent), and the working gas is argon (the purity is 99.99 percent). Controlling the sputtering power of 80W, the working pressure of 1Pa and the vacuum degree of the back bottom of 3.0 multiplied by 10-3Pa and sputtering for 5 minutes to obtain a metal vanadium film with the thickness of 30 nm;
(3) post oxidation annealing: placing the metal vanadium film in a vacuum tube furnace, vacuumizing to the air pressure of 1700Pa, heating to 400 ℃ at the heating rate of 10 ℃/min, preserving the heat for 1h, naturally cooling to the temperature below 100 ℃, and taking out a sample;
(4) low-pressure secondary annealing treatment: putting the sample taken out in the step (3) into a vacuum annealing furnace again, vacuumizing to the air pressure below 10Pa, preserving the heat for 5 hours at the temperature of 300 ℃, naturally cooling to the temperature below 100 ℃, and taking out;
(5) testing a temperature-changing transmission curve: and testing the ultraviolet-visible-infrared variable-temperature transmittance curve of the film by using an ultraviolet-visible-infrared spectrophotometer, wherein the testing wavelength range is 250 nm-2500 nm, the testing temperature range is from room temperature to a point of finishing the phase transition (namely the temperature when the transmittance curve does not change any more), the variable-temperature interval is 5 ℃, namely, the transmittance curve is tested once every 5 ℃ in the temperature rising process and the temperature reducing process, and the temperature is kept for at least 5 minutes before each test.
(6) Drawing a thermal hysteresis loop: taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample. As shown in fig. 9.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents. Are within the scope of the patent protection.

Claims (9)

1. A preparation method of a vanadium dioxide film with an adjustable thermal hysteresis loop takes glass as a substrate and is characterized by comprising the following process steps:
(1) preparing a metal vanadium film on a glass substrate;
(2) preparing a vanadium dioxide film with an adjustable thermal hysteresis loop, placing the vanadium metal film prepared in the step 1) in an annealing device for annealing treatment, and cooperatively adjusting and controlling annealing parameters to prepare the vanadium dioxide film with the adjustable thermal hysteresis loop, the phase change performance of which can be continuously adjusted;
(3) testing a variable-temperature transmission curve, testing the variable-temperature transmission curve of the vanadium dioxide film in the step 1) by using an ultraviolet-visible-infrared spectrophotometer, controlling the testing wavelength range to be 250-500nm, controlling the testing temperature range to be from room temperature to the point of finishing phase transition temperature, controlling the variable-temperature interval to be a transmission curve tested once when the temperature rise process and the temperature drop process change by 5-10 ℃, and preserving the temperature for at least 5min before each test;
(4) drawing a thermal hysteresis loop of the vanadium dioxide film sample, taking the transmittance value at 2000nm from the temperature-variable transmission curve as a vertical coordinate, taking the test temperature of the temperature-variable transmission curve as a horizontal coordinate, and drawing VO2Thermal hysteresis loop of film sample.
2. The method for preparing the vanadium dioxide film with the controllable thermal hysteresis loop according to claim 1, wherein the vanadium metal film prepared in the step 1) is prepared on a glass substrate by a direct current magnetron sputtering method.
3. The method for preparing the vanadium dioxide film with the controllable thermal hysteresis loop of claim 1, wherein the annealing parameters are cooperatively controlled in the step 2): the annealing pressure is controlled to be 10Pa-3000Pa, the annealing temperature is controlled to be 300-550 ℃, the heating rate is controlled to be 5-20 ℃/min, the annealing heat preservation time is 1-90min, and the natural cooling is finished after the heat preservation, so that the vanadium dioxide film with the adjustable thermal hysteresis loop and different phase change performance requirements is obtained.
4. The method for preparing a vanadium dioxide thin film with a controllable thermal hysteresis loop as claimed in claim 1, wherein the annealing treatment of step 2) comprises a low-pressure secondary annealing treatment, wherein the annealing temperature of the low-pressure secondary annealing treatment is controlled to be 250-350 ℃, and the air pressure is controlled to be 0.1-15 Pa.
5. The method for preparing a vanadium dioxide thin film with a controllable thermal hysteresis loop according to claim 1, wherein the annealing treatment in the annealing device is an oxidation annealing treatment in a vacuum atmosphere furnace, and the oxidation annealing treatment in the vacuum atmosphere furnace is performed under the air or oxygen atmosphere condition.
6. The method for preparing the vanadium dioxide film with the controllable thermal hysteresis loop according to claim 1 or 2, wherein the glass substrate is a pretreated quartz glass substrate, and the pretreatment comprises the steps of cleaning the surface of the quartz glass substrate, performing ultrasonic treatment in absolute ethyl alcohol for 25-35 minutes, placing the substrate in an acetone solution for ultrasonic treatment for 25-35 minutes, and drying for later use.
7. The method for preparing the vanadium dioxide film with the controllable thermal hysteresis loop as claimed in claim 1, wherein the vanadium dioxide film with the controllable thermal hysteresis loop is prepared by controlling the grain size, the number of crystal boundaries, the number of oxygen vacancies, the number of microcrystals below 15-20nm, the particle size distribution and the interfacial energy of the vanadium dioxide film through the coordinated regulation of annealing parameters and the low-pressure secondary annealing treatment.
8. The method for preparing the vanadium dioxide film with the controllable thermal hysteresis loop according to claim 2, wherein the direct current magnetron sputtering is performed under the condition that the magnetron sputtering power is controlled to be 70-85W, the working air pressure is 0.5-1.5Pa, the time is 1-25min, a substrate stage of the direct current magnetron sputtering is at room temperature, and the thickness of the prepared vanadium dioxide film is controlled to be 6-150 nm.
9. The method for preparing the vanadium dioxide film with the controllable thermal hysteresis loop according to claim 1 or 7, wherein the vanadium dioxide film with the controllable thermal hysteresis loop has a width control range of 5-35 ℃, a height control light transmittance range of 17-54% and a phase transition temperature control range of 34-60 ℃.
CN202011166908.1A 2020-10-27 2020-10-27 Preparation method of vanadium dioxide film with adjustable thermal hysteresis loop Pending CN112331555A (en)

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