A mutant temperature-sensitive device and a method for manufacturing the same

Abstract

The present application relates to a kind of mutant temperature sensitive components and its preparation method.The basic structure of the mutant temperature sensitive component includes: first transparent electrode layer, and electronic barrier layer, VO2 temperature sensitive layer, electrolyte layer and second transparent electrode layer formed in the surface of first transparent electrode layer in sequence.

Description

TECHNICAL FIELD

[0001] The application relates to a mutant temperature-sensitive component and a preparation method thereof, in particular to a VO2-based mutant temperature-sensitive component and a preparation method thereof, which are mainly used for temperature measurement and overheating temperature alarm of equipment or environment and belong to the field of negative temperature coefficient thermistor temperature sensors. BACKGROUND

[0002] As a detection device, a sensor converts a detected signal into an electrical signal or other output signal according to a certain rule and plays an indispensable role in production and life. Temperature, as one of important measurable information, temperature control and temperature measurement have become the basis of many industries. Therefore, a temperature sensor converts a perceived temperature into a usable output signal and is widely used in modern industry, medical treatment, life, transportation, smart home and other fields.

[0003] According to the category of electronic components, temperature sensors can be roughly divided into thermocouples and thermistor sensors. The thermocouple is the most commonly used temperature sensor in temperature measurement. Its main advantages are wide temperature range, adaptation to various atmospheric environments, ruggedness, low price, no power supply and low price. However, the thermocouple is not suitable for high-precision measurement and application. The thermistor is composed of semiconductor materials and its resistance changes accordingly when the temperature changes. Most thermistors are negative temperature coefficient thermistors, that is, the resistance decreases with the increase of temperature, so the thermistor has the advantage of high sensitivity. However, as a resistive device, the thermistor needs a small current source to ensure that it will not be permanently damaged due to excessive current heating. In addition, the linearity of the thermistor is poor and is greatly related to the production process.

[0004] The negative temperature coefficient thermistor is mainly made of manganese, cobalt, nickel and copper oxides and is manufactured by a ceramic process. The metal oxide material has semiconductor properties. When the temperature is low, the number of carriers (electrons and holes) of the oxide material is small, so the resistance value is high. As the temperature rises, the number of carriers increases, so the resistance value decreases. The resistance value of the negative temperature coefficient thermistor changes in the range of 100-1000000 ohms at room temperature, and the temperature coefficient is-2% to-6.5%. Due to the exponential increase of part of the resistance in the low temperature zone, the accuracy of the measurement is difficult to guarantee. In addition, the semiconductor material often has high requirements for doping conditions and device size, so the production process of this type of temperature sensor is relatively complex. Therefore, it is necessary to seek a semiconductor material with linear relationship between resistance and temperature to realize high sensitivity and high standardization of the negative temperature coefficient thermistor.

[0005] VO2 as a kind of semiconductor-metal phase transition occurs at a certain temperature, with the potential as a negative temperature coefficient thermistor. When below the phase transition temperature, VO2 is a semiconductor phase, its resistance value decreases with temperature rising. According to the relationship between its resistance and temperature, it is not difficult to find that there is a certain linear relationship between resistance and temperature, which is conducive to realize high-precision measurement of temperature. In addition, VO2 thin film can be prepared by magnetron sputtering, and the obtained VO2 thin film is often dense and smooth, the process is simple, the cost is low, and large-area large-size preparation can be realized.

[0006] For example, patent 1 (Chinese patent publication No. CN 109269656 A) discloses a new type of temperature measurement method based on vanadium dioxide gradient film sensor. This new type of temperature measurement method based on vanadium dioxide gradient film sensor not only can utilize the phase transition mechanism of new materials to complete the high-precision measurement of temperature near room temperature, but also can utilize the phase transition characteristics (metal-insulator phase transition) of new materials to directly obtain the digital signal quantity of the corresponding temperature. However, the patent needs to use microprocessing technology to cut the surface of the epitaxial VO2 thin film sample into multiple small film regions with different phase transition temperatures, and then lead out electrodes in each small film region to realize temperature measurement in a certain temperature range. The device preparation is relatively complicated. Patent 2 (Chinese patent publication No. CN 111854998 A) discloses a temperature sensor composed of VO2-based single crystal. This temperature sensor can realize high-precision temperature detection in a larger range. However, the preparation of VO2 single crystal in the patent requires a prerequisite of 950-1150 DEG C for 24-72 hours, and the preparation process is relatively complex and costly. SUMMARY

[0007] In view of the problems existing in the prior art, the purpose of the present application is to provide a preparation method and use of a mutant temperature sensitive device, which is simple in process and can be produced in large area.

[0008] In the first aspect, the present application provides a mutant temperature sensitive device, the basic structure of the mutant temperature sensitive device comprises: a first transparent electrode layer, and an electron blocking layer, a VO2 temperature sensitive layer, an electrolyte layer and a second transparent electrode layer formed in turn on the surface of the first transparent electrode layer.

[0009] In the present application, the phase transition of the temperature sensitive layer VO2 is adjusted by introducing an ultraviolet light curing electrolyte layer (for example, an ultraviolet light curing electrolyte layer, preferably a cationic ultraviolet light curing electrolyte based on resin material) to meet the needs of different temperature alarm points of the temperature sensor in actual use. On the one hand, VO2 will undergo a reversible metal-insulator phase transition near 68℃, and before the phase transition, VO2 belongs to the insulating phase, and its resistance value decreases linearly with the increase of temperature. The linear characteristic of the resistance value and the temperature can be used as a negative temperature coefficient thermistor in a temperature sensor.

[0010] Preferably, the first transparent electrode layer is a transparent conductive oxide, preferably FTO, ITO, ATO, or AZO; the sheet resistance of the first transparent electrode layer is 5-100 Ω / cm 2 The visible light transmittance is ≥70%.

[0011] Preferably, the second transparent electrode layer is a transparent conductive oxide, preferably FTO, ITO, ATO, or AZO; the sheet resistance of the second transparent electrode layer is 5-100 Ω / cm 2 The visible light transmittance is ≥70%.

[0012] Preferably, the electronic barrier layer is composed of at least one of SiO2, SiN X , HfO2, SnO2, and GeO2; the thickness of the electronic barrier layer is 10-100 nm.

[0013] Preferably, the electrolyte layer is composed of a cationic light curing electrolyte based on resin material; wherein the cation is at least one of H + , Li + , K + , Na + , Ca 2+ , Cu 2+ , Al 3+ , Zn 2+ , and Mg 2+ , preferably at least one of H + , Li + , Al 3+ , and Mg 2+ .

[0014] The thickness of the electrolyte layer is 50 nm-300 μm.

[0015] Preferably, the VO2 temperature sensitive layer is composed of monoclinic VO2; the thickness of the VO2 temperature sensitive layer is 20 nm-200 nm.

[0016] Preferably, the mutant temperature sensitive component further comprises an electrically controlled element connected between the first transparent electrode layer and the second transparent electrode layer.

[0017] When a negative voltage is applied through the electrically controlled element, cations in the electrolyte layer are inserted into the VO2 temperature sensitive layer, and the VO2 temperature sensitive layer is converted from the high resistance state to the low resistance state; when a positive voltage is applied through the electrically controlled element again, the cations inserted into the VO2 temperature sensitive layer are removed and enter the electrolyte layer, and the VO2 temperature sensitive layer is converted from the low resistance state to the high resistance state.

[0018] Preferably, the mutant temperature sensitive component further comprises a resistance measuring device and a signal conversion device connected between the first transparent electrode layer and the second transparent electrode layer, and the signal conversion device is provided with a conversion program of the resistance-temperature linear relationship; the mutant temperature sensitive component outputs the resistance through the resistance measuring device and converts the resistance into temperature through the signal conversion device.

[0019] Preferably, the mutant temperature sensitive component further comprises a temperature alarm connected to the signal conversion device, which outputs an alarm signal when the temperature changes sharply. When the temperature reaches the phase transition temperature, the VO2 temperature sensitive layer undergoes phase transition, and the resistance value of the VO2 temperature sensitive layer changes by several orders of magnitude, which can be used as an alarm point to provide a temperature alarm function for the temperature sensor.

[0020] Preferably, when a negative voltage is applied through the electrically controlled element, cations in the electrolyte layer are inserted into the VO2 temperature sensitive layer, and the phase transition temperature of the VO2 temperature sensitive layer is lowered; when a positive voltage is applied through the electrically controlled element again, the cations inserted into the VO2 temperature sensitive layer are removed and enter the electrolyte layer, and the phase transition temperature of the VO2 temperature sensitive layer gradually recovers to the intrinsic temperature; the phase transition temperature of the VO2 temperature sensitive layer is dynamically adjustable, and the phase transition temperature range is 295K-343K, and the measurement accuracy is ≤0.1K. The electrolyte layer introduced in the present application makes cations enter VO2 under the action of an electric field, and the phase transition temperature of VO2 is lowered. According to the actual alarm point requirement, the amount of cations entering can be controlled to adjust the phase transition temperature of VO2. According to the resistance and temperature phase transition curve of VO2, the temperature range of the phase transition hysteresis can correspond to the safety critical interval in the actual use process.

[0021] In another aspect, the present application also provides a preparation method of a mutant temperature sensitive component, and the VO2 temperature sensitive layer is prepared by magnetron sputtering and post-annealing treatment.

[0022] The parameters of the magnetron sputtering include: V2O3 as the target material; oxygen partial pressure of 0-50vol%; distance between the target material and the substrate of 10-20cm; direct current power applied on the target material of 100-400W;

[0023] The temperature of the post-annealing treatment is 280-550℃, and the time is 2-6 minutes.

[0024] Advantages:

[0025] 1. The temperature-sensitive layer VO2 has a characteristic that the resistance changes several orders of magnitude before and after the phase transition point, which is used as a temperature alarm signal. The electrolyte layer is designed to dynamically control the phase transition temperature of the temperature-sensitive layer VO2, thereby expanding the temperature range that the temperature-sensitive device can adapt to in actual use.

[0026] 2. The linear relationship between temperature and resistance of VO2 before phase transition realizes high-precision measurement of the temperature sensor. The hysteresis width temperature interval corresponds to the safety critical interval in use.

[0027] 3. The structure of the abrupt temperature-sensitive device is simple, and the temperature measurement is highly controllable, which is suitable for mass production and industrialization. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 Fig. 1 is a structural schematic diagram of the abrupt temperature-sensitive device.

[0029] Figure 2 Fig. 2 is a schematic diagram of the relationship between the resistance and temperature of the abrupt temperature-sensitive device when the thickness of the electronic barrier layer SiO2 is different.

[0030] Figure 3 Fig. 3 is a schematic diagram of the relationship between the resistance and temperature of the abrupt temperature-sensitive device when the thickness of VO2 is different.

[0031] Figure 4 Fig. 4 is a schematic diagram of the relationship between the resistance and temperature of the abrupt temperature-sensitive device when different cations are used.

[0032] Figure 5 Fig. 5 is a schematic diagram of the adjustable phase transition point of the abrupt temperature-sensitive device when different voltages are applied. DETAILED DESCRIPTION

[0033] The present application will be further described below by the following embodiments, which should be understood as merely illustrating the present application, but not limiting the present application.

[0034] In the present disclosure, a simple preparation process is used to prepare a VO2 thin film, and an electrolyte layer is added to realize dynamic and continuous adjustment of the phase transition of VO2, thereby meeting the needs of temperature sensors in different temperature alarm points in actual use. Specifically, the basic structure of the abrupt temperature-sensitive device is as shown in Figure 1 Fig. 1, which includes a first transparent electrode layer, an electronic barrier layer, a VO2 temperature-sensitive layer, an electrolyte layer, and a second transparent electrode layer.

[0035] In an embodiment of the present application, by adjusting the thickness of each functional layer and the preparation process of the mutant temperature-sensitive device, adjusting the ion composition of the electrolyte layer and the amount of cations entering by applying voltage and time control, a widely promoted and valuable dynamic mutant temperature-sensitive device can be obtained. The preparation method of the mutant temperature-sensitive device is described below.

[0036] The transparent conductive glass substrate is continuously deposited on the surface to prepare an electron blocking layer and a temperature-sensitive layer.

[0037] In an optional embodiment, the deposition method can be magnetron sputtering deposition. The direct current magnetron sputtering system used in the magnetron sputtering deposition can include a deposition chamber, a sample chamber, a plurality of target heads, a substrate plate, a direct current, a radio frequency power supply, and a series of mechanical pumps and vacuum pumps, wherein the target heads and the substrate plate are at a certain angle and a certain distance apart, and the direct current power supply and the radio frequency power supply are connected to the target heads. The substrate is ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 30 minutes each, and dried with compressed air. A certain part of the conductive substrate is covered with high-temperature adhesive tape as an electrode, and is fixed on the substrate tray and placed in the sample chamber. The mechanical pump is opened to below 5 Pa, and then the baffle valve is opened to send it into the sputtering chamber with a vacuum degree (background vacuum degree) of 10 -4 Pa or below.

[0038] As an example of the SiO2 layer as the electron blocking layer, the preparation method includes: using Si target as the target material, argon and oxygen as the sputtering gas, total pressure of 1.0-2.0 Pa, oxygen partial pressure of 5-30%, distance between the target material and the substrate of 10-20 cm, initial substrate temperature of room temperature, and radio frequency power supply power applied to the target material of 50-150 W. The final deposition obtains an electron blocking layer with a thickness of 10 nm-100 nm. When the thickness of the electron blocking layer is much higher than the above range, although the deposited electron blocking layer can well inhibit the diffusion of the transparent conductive layer to VO2, the thick electron blocking layer completely blocks the movement of electrons under the electric field, so that the device cannot realize phase change adjustment. When the thickness of the electron blocking layer is much lower than the above range, the deposited electron blocking layer has no inhibitory effect on the diffusion of the transparent conductive layer, so that the overall resistance of the device is very low and only changes within the same order of magnitude, which will seriously affect the high-precision feedback of the resistance to temperature, and also cannot realize the phase change point alarm function. In addition, under a larger bias electric field, cations will cross the thin electron blocking layer into the transparent conductive layer, reducing the cycling performance of the device.

[0039] As a preparation example of the temperature sensitive layer, the following conditions are used: V2O3 as the target material, total pressure of 1.0-2.0 Pa, oxygen partial pressure of 0-50%, distance between the target material and the substrate of 10-20 cm, initial substrate temperature of room temperature, and direct current power applied to the target material of 100-400 W. A VO2 thin film with a thickness of 20-200 nm is finally deposited. A monoclinic phase VO2 temperature sensitive layer with a stoichiometric ratio of 1:2 is obtained by post-annealing. The post-annealing temperature can be 280-550°C, and the annealing time can be 2-6 minutes. If the thickness of the VO2 temperature sensitive layer is too high, the interface between the deposited VO2 layer and the substrate and the electron blocking layer is not firm, and the VO2 layer is easily detached. If the thickness of the VO2 temperature sensitive layer is too low, the deposited VO2 layer has poor resistance responsiveness, which reduces the measurement accuracy of the temperature sensitive device in the application.

[0040] The resin precursor is configured according to the prior art, and the resin precursor slurry is filled between the temperature sensitive layer and the second transparent conductive electrode by means of vacuum filling or coating. Finally, an electrolyte layer is prepared by using ultraviolet irradiation curing technology. The electrolyte layer is obtained by light curing treatment of a resin slurry containing cations. The composition of the resin slurry containing cations includes: an organic solvent, a curing resin, an organic precursor, a stabilizer, and an ion source solution. The curing resin is a light curing resin, preferably an ultraviolet light curing resin. The mass ratio of the organic solvent, the curing resin, the organic precursor, the stabilizer, and the ion source solution can be (1-5):(0.5-3):(0.5-2):(0.05-0.5):1. The organic solvent can be at least one of isopropyl alcohol, propylene glycol methyl ether acetate, nylon acid dimethyl ester, dimethyl formamide, and dimethyl sulfoxide. The organic precursor is at least one of ETPTA (ethoxylated trimethylolpropane triacrylate), TMPTA (trimethylolpropane triacrylate), EO-CHA (ethoxylated cyclohexanol acrylate), and IBOA (isobornyl acrylate). The stabilizer is a transition metal organic compound, preferably ferrocene and its derivatives. The solute in the ion source solution can be at least one of lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, zinc perchlorate, and aluminum perchlorate, and the concentration can be 0.5-5 moL / L. The solvent of the ion source solution is at least one of propylene carbonate, acetonitrile, dimethyl sulfoxide, and N,N-dimethyl formamide. The light curing treatment is ultraviolet light irradiation at 50-300 W for 30 seconds-30 minutes.

[0041] The mutant temperature sensitive component designed in the application can set the alarm point according to the actual use condition, and can meet various requirements in actual life. The mutant temperature sensitive component (or VO2-based temperature sensitive component) can realize dynamic and continuous controllable phase change of the VO2 temperature sensitive layer by adjusting the positive and negative and size of the applied bias. Meanwhile, the interface between each layer of the VO2-based temperature sensitive component and the electrolyte is optimized, the ion migration resistance is reduced, the ion trapping defects are reduced, and the continuous phase change performance of VO2 is improved.

[0042] Specifically, the temperature sensitive component is a VO2 thin film, the characteristics of sharp change of resistance before and after phase change of VO2 and linear relationship between resistance and temperature before phase change of VO2 are utilized, and the corresponding temperature can be accurately obtained according to the measured resistance by combining a resistance measuring device. The electrolyte layer is used to control the phase change temperature of VO2. When the voltage is low, ions enter VO2, and the phase change temperature of VO2 is reduced. When the voltage is high, more ions enter VO2, and the phase change temperature is further reduced. When the voltage is positive, ions are removed from VO2 and return to the electrolyte layer, and the phase change temperature returns to the intrinsic phase change temperature, so as to realize dynamic adjustment of the phase change of VO2. According to the actual use requirement, appropriate ions are used to meet the phase change of VO2 at the required alarm point, the alarm signal is generated by the sharp change of resistance, and the temperature range corresponding to the phase change hysteresis of VO2 corresponds to the safety critical interval. Compared with the previous temperature sensor, the preparation process of the application is simpler, the function is more abundant, and the actual use requirement can be better met.

[0043] The following further examples are used to further illustrate the application. It should also be understood that the following examples are only used to further illustrate the application, and cannot be understood as limiting the protection scope of the application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the application all belong to the protection scope of the application. The specific process parameters in the following examples are only one example in the appropriate range, i.e. those skilled in the art can select within the appropriate range according to the description herein, and are not limited to the specific values in the following examples.

[0044] Example 1

[0045] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, put into the sample chamber, open the mechanical pump to below 5 Pa, open the baffle valve, and send the vacuum degree (background vacuum degree) to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the VO2 film is obtained after 450 ℃ annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uC35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a mass ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The device is uniformly irradiated for 5 min under the 100 W ultraviolet light for light curing. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device. The mutant temperature sensitive element device is obtained, and the structure schematic diagram is as shown in Figure 1 The relationship between the device resistance and the temperature is as shown in Figure 2 The external voltage of-1 to-3 V is applied between the two electrodes, the lithium ions in the electrolyte enter the vanadium oxide under the driving of the electric field, and the phase transition temperature of the vanadium oxide is reduced. The schematic diagram of the phase transition of the vanadium oxide under different voltages is as shown in Figure 5 .

[0046] Example 2

[0047] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then the substrate is fixed on the substrate tray with high temperature tape, put into the sample chamber, open the mechanical pump to below 5 Pa, open the baffle valve, and send the vacuum degree (background vacuum) to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 20 min, and the thickness of the electron barrier layer film is about 30 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the required VO2 film is obtained after 450 °C post-annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is performed by placing the device under the uniform irradiation of a 100 W ultraviolet lamp for 5 min. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device. The mutant temperature sensitive element device is obtained, and the relationship between the resistance and the temperature of the device is shown in Figure 2 In this embodiment, the thin electron barrier layer can drive the cations into VO2 under a smaller electric field, so that the phase transition of VO2 can be realized by a smaller applied bias.

[0048] Example 3

[0049] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, placed in the sample chamber, opened the mechanical pump to 5 Pa or less, opened the baffle valve, and sent into the vacuum degree (background vacuum) to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 30 min, and the thickness of the electron barrier layer film is about 50 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the required VO2 film is obtained after 450°C post-annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is to place the device under the uniform irradiation of a 100 W ultraviolet lamp for 5 min. After the device is cured, the organic matter on the surface of the device is removed by using an organic solvent, and the mutant temperature sensitive element device is obtained. The relationship between the resistance and the temperature of the device is shown in FIG. 1. In this embodiment, the thickness of the electron barrier layer is further increased to improve the overall resistance of the device, inhibit the adverse effects of the transparent conductive electrode on the VO2 layer after annealing, and inhibit the migration of cations to the transparent conductive layer during high voltage and multiple cycles, so as to improve the cycle stability and high-precision measurement in the temperature sensor. Figure 2 The thickness of the electron barrier layer is further increased in this embodiment to improve the overall resistance of the device, inhibit the adverse effects of the transparent conductive electrode on the VO2 layer after annealing, and inhibit the migration of cations to the transparent conductive layer during high voltage and multiple cycles, so as to improve the cycle stability and high-precision measurement in the temperature sensor.

[0050] Example 4

[0051] First, two pieces of ITO transparent conductive glass substrate are used, and the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min. Then, the substrate is fixed on the substrate tray with high-temperature tape, placed in the sample chamber, and the mechanical pump is pumped to below 5 Pa. The shutter valve is opened, and the vacuum degree (background vacuum degree) is reached to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 30 nm, and the required VO2 film is obtained after 450 °C annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is to place the device under the 100 W ultraviolet lamp for uniform irradiation for 5 min. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the mutant temperature sensitive element device is obtained. The relationship between the resistance and the temperature of the device is shown in Figure 3 In this embodiment, the thickness of the VO2 layer is reduced, which is beneficial to improve the depth of the cations entering the VO2 under the electric field, and further improve the modulation amplitude of the adjustable phase change of VO2.

[0052] Example 5

[0053] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, put into the sample chamber, open the mechanical pump to 5 Pa or less, open the baffle valve, and send into the vacuum degree (background vacuum) to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 150 nm, and the required VO2 film is obtained after 450 °C annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is to place the device under the 100 W ultraviolet lamp for uniform irradiation for 5 min. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the abrupt temperature sensitive element device is obtained. The relationship between the resistance and the temperature of the device is shown in FIG. 1. In this embodiment, the thickness of VO2 is further increased, which is beneficial to inhibit the influence of substrate strain on VO2 and enhance the interface bonding force between VO2 and the substrate. Figure 3

[0054] Example 6

[0055] First, two pieces of ITO transparent conductive glass substrate are used, and the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, placed in the sample chamber, opened the mechanical pump to 5 Pa or less, opened the baffle valve, and sent into the vacuum degree (background vacuum) to 10 -4 ​The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the required VO2 film is obtained after 450°C post-annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (sodium perchlorate PEO solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The residual methanol in the electrolyte is the proton source. The thickness of the resin layer in the electrolyte is controlled to be 80 μm by the hard template and the surface tension of the resin solution. The light curing is to place the device under the 100 W ultraviolet lamp for uniform irradiation for 5 min. After the device is cured, the organic matter on the surface of the device is removed by using the organic solvent, and the mutant temperature sensitive element device is obtained. The hydrogen ions in the electrolyte enter the VO2 under the action of the electric field when the external voltage of-2 V is applied between the two electrodes. The relationship between the temperature and the resistance of the device is shown in Figure 4 In this embodiment, the hydrogen ion as the smallest ion can enter and exit the VO2 to a large extent under the action of the electric field.

[0056] Example 7

[0057] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, placed in the sample chamber, the mechanical pump is opened to below 5 Pa, the baffle valve is opened, and the vacuum degree (background vacuum degree) is reached to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the electron barrier layer film with a thickness of about 80 nm is obtained. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, and the VO2 film is deposited for 80 nm, and then annealed at 450 ℃ for 5 min to obtain the required VO2 film. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uuc35), the stabilizer (ferrocene) and the ion source (PC solution of aluminum perchlorate, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is to place the device under the uniform irradiation of a 100 W ultraviolet lamp for 5 min. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the mutant temperature sensitive element device is obtained. When a voltage of-2 V is applied between the two electrodes, the aluminum ions in the electrolyte enter the vanadium oxide under the driving of the electric field, and the relationship between the temperature and the resistance of the device is shown in Figure 4 In this embodiment, the aluminum ion has a small ionic radius, a high ion mobility, and three electrons, and the modulation rate is faster and more stable.

[0058] Embodiment 8

[0059] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, placed in the sample chamber, the mechanical pump is opened to below 5 Pa, the baffle valve is opened, and the vacuum degree (background vacuum degree) is reached to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the required VO2 film is obtained after 450 ℃ annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uC35), the stabilizer (ferrocene) and the ion source (PC solution of magnesium perchlorate, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is to place the device under the uniform irradiation of a 100 W ultraviolet lamp for 5 min. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the sudden change type temperature sensitive element device is obtained. When a voltage of-2 V is applied between the two electrodes, the magnesium ions in the electrolyte enter the vanadium oxide under the driving of the electric field, and the relationship between the temperature and the resistance of the device is shown in Figure 4 In this embodiment, the magnesium ion carries two electrons, and can carry more times of electrons when the same ion is injected.

[0060] Comparative Example 1

[0061] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, placed in the sample chamber, opened the mechanical pump to 5 Pa or less, opened the baffle valve, and the vacuum degree (background vacuum) was reached to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method on the surfaces of the substrates, respectively. The Si target is used as the target material, argon and oxygen are used as the sputtering gas, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 10 min, and the electron barrier layer film with a thickness of about 5 nm is obtained. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the VO2 film required is obtained after 450°C post-annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The light curing is to uniformly irradiate the device under a 100 W ultraviolet lamp for 5 min. After the device is cured, the organic matter on the surface of the device is removed by using an organic solvent, and the mutant temperature sensitive element device is obtained. Compared with examples 1, 2 and 3, the thickness of the electron barrier layer is much lower than the preferred value, and the deposited electron barrier layer has no inhibitory effect on the diffusion of the transparent conductive layer, so that the overall resistance of the device is very low and only changes in the same order of magnitude, which will seriously affect the high-precision feedback of the resistance to temperature, and the phase change point alarm function cannot be realized. In addition, under a larger bias electric field, cations can cross the thin electron barrier layer into the transparent conductive layer, reducing the cycle performance of the device.

[0062] Comparative example 2

[0063] First, two pieces of ITO transparent conductive glass substrate are used, and the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, put into the sample chamber, open the mechanical pump to below 5 Pa, open the baffle valve, and send the vacuum degree (background vacuum) to 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the argon and oxygen are used as the sputtering gas, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 90 min, and the electron barrier layer film with a thickness of about 150 nm is obtained. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 80 nm, and the VO2 film required is obtained after 450 °C post-annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uC35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The device is uniformly irradiated for 5 min under the 100 W ultraviolet light for light curing. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the mutant temperature sensitive element device is obtained. Compared with examples 1, 2 and 3, the thickness of the electron barrier layer is much higher than the preferred value. At this time, although the deposited electron barrier layer can well inhibit the diffusion of the transparent conductive layer to the VO2, the thick electron barrier layer completely blocks the movement of the electrons under the electric field, so that the device cannot realize the phase change adjustment.

[0064] Comparative example 3

[0065] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, put into the sample chamber, open the mechanical pump to pump to 5 Pa or less, open the baffle valve, send into the vacuum (background vacuum) to reach 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 10 nm, and the required VO2 film is obtained after 450 °C annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The device is uniformly irradiated for 5 min under a 100 W ultraviolet lamp for light curing. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the mutant temperature sensitive component device is obtained. Compared with examples 4 and 5, the thickness of VO2 is much lower than the preferred value, the deposited VO2 layer has poor resistance response, and the measurement accuracy of the temperature sensitive component device in the application is reduced.

[0066] Comparative example 4

[0067] First, two pieces of ITO transparent conductive glass substrate are used, the substrate is ultrasonically cleaned with acetone, ethanol and deionized water for 30 min, then fixed on the substrate tray with high temperature tape, put into the sample chamber, open the mechanical pump to below 5 Pa, open the baffle valve, send into the vacuum degree (background vacuum degree) to reach 10 -4The electron barrier layer and the temperature sensitive layer are prepared by magnetron sputtering method. The Si target is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, the deposition time is 45 min, and the thickness of the electron barrier layer film is about 80 nm. The V2O3 target is used as the target material, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the direct current power applied to the target material is 200 W, the deposition time is 300 nm, and the required VO2 film is obtained after 450℃ annealing for 5 min. According to the prior art, the resin slurry prepared by mixing the organic solvent (PMA), the organic precursor (ETPTA), the curing resin (fresh beauty uc35), the stabilizer (ferrocene) and the ion source (lithium perchlorate PC solution, 1 mol / L) in a ratio of 2:1:1:0.1:1 is filled between the vanadium oxide film and the second layer of transparent conductive electrode by vacuum filling. The complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 80 μm by the surface tension of the hard template and the resin solution. The device is uniformly irradiated for 5 min under the 100 W ultraviolet light for light curing. After the device is cured, the organic solvent is used to remove the excess organic matter on the surface of the device, and the mutant temperature sensitive component device is obtained. Compared with examples 4 and 5, the thickness of the VO2 layer is much higher than the preferred value, and the interface between the deposited VO2 layer and the substrate and the electron barrier layer is not firm, and is easy to fall off.

[0068] Table 1 is the composition parameters and performance comparison of the mutant temperature sensitive component devices prepared in each example and the comparative example:

[0069]

Claims

1. A mutant temperature-sensitive device, characterized in that, The basic structure of the mutant temperature sensitive component comprises a first transparent electrode layer, and an electron barrier layer, a VO2 temperature sensitive layer, an electrolyte layer and a second transparent electrode layer formed in sequence on the surface of the first transparent electrode layer. The composition of the electron barrier layer is at least one of SiO2, SiN X , HfO2, SnO2, GeO2; the thickness of the electron barrier layer is 10-100 nm; The VO2 temperature sensitive layer is composed of monoclinic VO2, and the thickness of the VO2 temperature sensitive layer is 20 nm to 200 nm.

2. The mutant temperature-sensitive device of claim 1, wherein The first transparent electrode layer is a transparent conductive oxide; the sheet resistance of the first transparent electrode layer is 5-100 Ω / cm 2 The visible light transmittance is ≥70%.

3. The mutant temperature-sensitive device of claim 2, wherein The transparent conductive oxide is FTO, ITO, ATO or AZO.

4. The mutant temperature-sensitive device of claim 1, wherein The second transparent electrode layer is a transparent conductive oxide; the square resistance of the second transparent electrode layer is 5-100 Ω / cm 2 The visible light transmittance is ≥70%.

5. The abrupt temperature-sensitive component according to claim 4, characterized in that, The transparent conductive oxide is FTO, ITO, ATO or AZO.

6. The mutant temperature-sensitive device of claim 1, wherein The electrolyte layer is composed of a cation photo-curing electrolyte based on a resin material; wherein the cation is at least one of H + , Li + , K + , Na + , Ca 2+ , Cu 2+ , Al 3+ , Zn 2+ , Mg 2+ . The thickness of the electrolyte layer is 50 nm to 300 microns.

7. The mutant temperature-sensitive device of claim 1, wherein The mutant temperature sensitive component further comprises an electrically controlled element connected between the first transparent electrode layer and the second transparent electrode layer. When a negative voltage is applied through the electrically controlled element, cations in the electrolyte layer are inserted into the VO2 temperature sensitive layer, and the VO2 temperature sensitive layer is converted from a high resistance state to a low resistance state; when a positive voltage is applied through the electrically controlled element again, the cations inserted into the VO2 temperature sensitive layer are removed and enter the electrolyte layer, and the VO2 temperature sensitive layer is converted from the low resistance state to the high resistance state.

8. The abrupt temperature-sensitive component according to claim 7, characterized in that, The mutant temperature sensitive component further comprises a resistance measuring device and a signal conversion device connected between the first transparent electrode layer and the second transparent electrode layer, and the signal conversion device is provided with a conversion program of the resistance-temperature linear relationship; the mutant temperature sensitive component outputs resistance through the resistance measuring device and converts the resistance into temperature through the signal conversion device.

9. The abrupt temperature-sensitive component according to claim 8, characterized in that, The mutant temperature sensitive component further comprises a temperature alarm connected to the signal conversion device, which outputs an alarm signal when the temperature changes sharply.

10. The mutant temperature-sensitive device of claim 7, wherein When a negative voltage is applied through the electrically controlled element, cations in the electrolyte layer are inserted into the VO2 temperature sensitive layer, and the phase transition temperature of the VO2 temperature sensitive layer is reduced; When a positive voltage is applied through the electrically controlled element again, the cations inserted into the VO2 temperature sensitive layer are removed and enter the electrolyte layer, and the phase transition temperature of the VO2 temperature sensitive layer gradually recovers to the intrinsic temperature; The phase transition temperature of the VO2 temperature sensitive layer is dynamically adjustable, and the phase transition temperature range is 295 K to 343 K, and the measurement accuracy is ≤0.1 K.

11. A method of producing a mutant temperature-sensitive device according to any one of claims 1 to 10, characterized by, The VO2 temperature sensitive layer is prepared by magnetron sputtering and post annealing treatment. The parameters of the magnetron sputtering include: V2O3 as the target material, oxygen partial pressure of 0-50 vol%, distance between the target material and the substrate of 10-20 cm, and direct current power applied on the target material of 100-400 W. The temperature of the post annealing treatment is 280℃-550℃, and the time is 2-6 minutes.

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