Silver-based chalcogenide metal-insulator phase-change flexible semiconductor thermal sensor and its application technology

Abstract

The present invention belongs to the field of energy micro-disturbance detection such as micro-area thermal disturbance, infrared signal, electromagnetic signal, etc., and specifically relates to a silver-based chalcogenide metal insulator phase change flexible semiconductor thermistor and application technology. The present invention uses silver-based chalcogenide compounds as temperature-sensitive materials, designs its thermal resistance coefficient, Seebeck coefficient, and metal-insulator phase change characteristics through material components, and uses precision machining to make it into a flexible self-supporting film, a silk low-dimensional material for further making component-based vertical devices or array devices. Combining the negative resistance temperature coefficient thermistor characteristics of silver-based chalcogenide compounds, metal-insulator phase change, and Seebeck coefficient, temperature sensing, thermal switching, and high-precision thermal disturbance detection applications are realized. The technical method provided by the present invention has considerable application value in intelligent temperature sensing, infrared detection, thermal disturbance detection, thermal switching, and surge current suppression, and can realize the flexibility of devices.

Description

Technical Field

[0001] The present invention belongs to the field of energy micro-disturbance detection such as micro-area thermal disturbance, infrared signal, electromagnetic signal, etc., and specifically relates to a silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor and application technology. Background Art

[0002] The development of accurate detection methods for micro-area thermal disturbances has important application value in both military and civilian detection fields. The technical methods for temperature and thermal disturbance sensing usually include thermistor technology, thermocouple technology, etc. [1-4] Among them, the working principle of thermistor is that the resistivity of its material changes gradually or suddenly with the change of temperature, and according to the degree of change of resistivity, it can be divided into positive resistance temperature coefficient thermistor, negative resistance temperature coefficient thermistor, sudden thermistor, etc. For example, commonly used positive resistance temperature coefficient thermistors include oxides such as doped barium titanate; negative resistance temperature coefficient thermistor material systems mainly include: iron-based spinel oxide, manganese-based spinel oxide and other oxide materials; and sudden thermistors mainly include: vanadium oxide compounds, rare earth nickel-based oxides and other oxide materials [5-7] Compared with the above-mentioned oxide thermistors, although the metal thermistors represented by platinum thermistors have a lower positive temperature coefficient of resistance to temperature change, they are also widely used in industrial temperature measurement due to their good ductility, and play a key role in temperature sensing applications in special environments such as the seabed. In addition, thermistor materials represented by vanadium oxide, amorphous silicon, etc. are prepared into bridge films with self-supporting structures, which have also been widely used in uncooled infrared focal plane imaging, night vision devices, etc. [6-9] . Compared with thermistors, the working principle of thermocouples is mainly to utilize the Seebeck effect of materials such as platinum and platinum-rhodium, and to calibrate the temperature gradient by generating the Seebeck electromotive force at the two joints of the alloy thermocouple under the temperature gradient to achieve temperature measurement. In addition to the two traditional temperature sensing technologies mentioned above, in recent years, people have discovered that rare earth nickel-based oxides can achieve both a higher thermistor coefficient and a larger Seebeck coefficient. They have also proposed a technical method to use rare earth nickel-based oxides as sensitive resistor materials and to synergistically apply the thermistor effect and the Seebeck effect to improve the accuracy of temperature sensing and thermal disturbance detection.

[10] .

[0003] However, the oxide-based thermistor materials used in the prior art are usually hard and brittle, making it difficult to achieve flexibility to adapt to the complex environment in actual applications; and the temperature resistance coefficient of metal thermistor materials is usually low, making it difficult to achieve precise measurement of temperature changes. In addition, due to the difficulty in making sensitive materials flexible, self-supporting and low-dimensional, the existing thermal detection methods are relatively simple. For example, although previous reports have proposed improving the accuracy of thermal disturbance detection and reducing noise by comprehensively utilizing the high thermistor temperature coefficient and high Seebeck coefficient of rare earth nickel-based oxides

[10] However, due to the high hardness and difficulty in achieving flexibility of rare earth nickel-based oxides, it is difficult to achieve flexibility in the collaborative detection method based on thermistor effect and Seebeck effect, which increases the difficulty of promoting this technology in practical applications.

[0004] In summary, the existing thermistor material technology still lacks a material system that can simultaneously have high thermistor resistance temperature coefficient and Seebeck coefficient, and has good ductility and processability and can achieve flexibility. In response to the above problems, it is urgent to conduct comprehensive exploration from the aspects of new sensitive resistor material systems, material micro-processing technology methods, and new device structures. Recent studies have shown that Ag2S has good ductility and deformation ability like metals. Mechanical property tests show that the compression deformation of Ag2S can reach more than 50%, the bending deformation can exceed 20%, and the tensile deformation can reach 4.2%.

[11] These deformations far exceed those of known ceramics and semiconductor materials, and their mechanical properties are comparable to those of some metals. Furthermore, they possess high thermal resistivity and a high Seebeck coefficient near room temperature, making them promising new materials for temperature sensing and thermal disturbance detection.

[0005] References:

[0006] 【1】Wu Cheng, Su Junhong, Pan Shunchen, et al., Review of Uncooled Infrared Focal Plane Electron Microscope Technology (Volume 1), Infrared Technology, 1999, 21(1): 6-9

[0007] 【2】Wu Cheng, Su Junhong, Pan Shunchen, et al., Review of Uncooled Infrared Focal Plane Electron Microscope Technology (Part 2), Infrared Technology, 1999, 21(2): 1-3

[0008] 【3】Yang Yasheng, Infrared Focal Plane Array of Bolometers, Semiconductor Technology, 1999, 24(2): 5-8

[0009] 【4】Shao Shiping, Progress of Uncooled Infrared Focal Plane Array, Infrared Technology, 1999, 18(2): 1-6

[0010] 【5】Liu Xiding, Jiang Meiling, Development of an uncooled infrared microbolometer, Journal of Infrared and Millimeter Waves, 1997, 16(6): 459-462

[0011] 【6】Chen, Changhong, Yi, Xinjian, Zhang, Jing, et al., Linear uncooledmicrobolometer array based on VOx thin films, Infrared Physics and Technology, 2001, 42(2): 87-90

[0012] 【7】Wang Yangyuan, Polysilicon Thin Films and Their Role in Integrated Circuits, Beijing: Science Press, 1988: 71-93

[0013] 【8】Tanaka, A., Matsumoto, S., Tsukamoto, N., et al., Infrared Focal PlaneArray Incorporating Silicon IC Process Compatible Bolometer, IEEE Transactionon Electron Devices, 1996, 43(11): 1844-1850

[0014] 【9】Zhou Jin, Ru Guoping, Li Bingzong, et al., Preparation and properties of vanadium oxide thermosensitive films, Journal of Infrared and Millimeter Waves, 2001, 20(4): 291-295

[0015]

[10] Chen, Jikun, Hu, Haiyang, Wang, Jiaou et al. A d-Band Electron Correlated Thermoelectric Thermistor Established in Metastable PerovskiteFamily of Rare-Earth Nickelates, ACS applied materials&interfaces, 2019, 11(37): 34128-34134

[0016]

[11] Shi, Xun, Chen, Hongyi, Hao, Feng et al. Room-temperature ductileinorganic semiconductor, Nature materials, 2018, 17(5): 421-426 Summary of the Invention

[0017] The present invention provides a silver-based chalcogenide metal insulator phase-change flexible semiconductor thermal sensor and application technology.

[0018] A silver-based chalcogenide metal-insulator phase-change flexible semiconductor thermistor sensor, involving sensitive resistor materials and devices for semiconductor thermoelectric composite sensors, is characterized by utilizing silver-based chalcogenides as temperature and thermal disturbance sensitive materials, leveraging their advantages near room temperature: high thermal resistivity, high Seebeck coefficient, and good ductility. First, the silver-based chalcogenide metal-insulator phase-change semiconductor utilizes silver-based chalcogenides as temperature-sensitive materials. The material composition of the silver-based chalcogenide compounds is designed based on detection requirements to regulate their thermal resistivity, Seebeck coefficient, metal-insulator phase-change characteristics, and ductility near room temperature. Second, the prepared silver-based chalcogenide compounds are processed through precision machining into low-dimensional materials such as films or silks with flexible, self-supporting structures. Finally, the prepared silver-based chalcogenide sensitive material films or silks with flexible and self-supporting structures are fabricated into array-type device structures. The fabricated device combines the negative temperature coefficient thermistor properties of the silver-based chalcogenide insulating phase with the characteristic temperature-triggered metal-insulator phase transition to achieve the synergistic application of temperature sensing and thermal switching. Furthermore, by combining the high Seebeck coefficient and thermal resistance coefficient of silver-based chalcogenides near room temperature, it can synergize active detection based on the thermistor effect with passive detection based on the Seebeck effect, further reducing detection noise of thermal disturbance signals.

[0019] Furthermore, the silver-based chalcogenide metal insulator phase change semiconductor is an alloy compound with Ag2S as the parent phase, wherein the silver atomic position can be partially replaced by a positive monovalent element, and the sulfur atomic position can be partially replaced by other sixth main group elements; its chemical formula is Ag 2-x M x S 1-y C y , where M is a monovalent element, preferably Cu or Sn, and x is preferably 0-0.5; C is a Group VI element other than sulfur, preferably Se or Te, and y is preferably 0-0.5. This silver-based chalcogenide metal-insulator phase-change semiconductor exhibits excellent ductility and deformability comparable to metals, enabling material processing at room temperature through forging, extrusion, and drawing. In a preferred embodiment, Ag2S can achieve compression deformation exceeding 50%, bending deformation exceeding 20%, and tensile deformation up to 4.2%. After load removal, compression specimens exhibit approximately 10%–11% recoverability relative to the initial deformation. This deformation value is significantly greater than that observed in typical semiconductors / ceramics (typically less than 1%, though some machinable ceramics such as yttria-stabilized zirconia or Ti3SiC2 may reach 1%–3%), and even higher than that observed in Cu-8.5% Zr alloys.

[0020] Furthermore, the silver-based chalcogenide metal-insulator phase-change semiconductor exhibits reversible metal-insulator phase transition characteristics when triggered by a characteristic temperature. Its functional characteristics are manifested by the material's electrical transport properties exhibiting negative temperature coefficient (NTC) thermistor characteristics below the characteristic temperature. The achieved negative temperature coefficient (NTC) thermistor is comparable to that of conventional NTC thermistors. When the temperature rises to the metal-insulator phase transition temperature, the material's resistivity undergoes a reversible mutation, decreasing by more than an order of magnitude. During this phase transition, the crystal structure of the silver-based chalcogenide compound reversibly transforms from a zigzag, wrinkled, layered monoclinic structure below the characteristic temperature to a body-centered cubic structure. By substituting monovalent positive elements at the silver atomic sites or other Group VI elements at the sulfur atomic sites, the phase transition temperature can be controlled within the 260-460K temperature range, while simultaneously achieving a high Seebeck coefficient and high thermistor coefficient in the temperature range near room temperature. In a preferred embodiment, the metal-insulator phase transition temperature reaches 450K in the Ag2S matrix material, and the resistivity of the material changes by more than 2 orders of magnitude before and after the phase transition; the room temperature Seebeck coefficient reaches 900μV / K, and the room temperature thermal resistance coefficient reaches 4% / K. In another preferred embodiment, in the Ag2S matrix material, the metal-insulator phase transition temperature reaches 450K, and the resistivity of the material changes by more than 2 orders of magnitude before and after the phase transition; the room temperature Seebeck coefficient reaches 900μV / K, and the room temperature thermal resistance coefficient reaches 4% / K. 0.85 Te 0.15 The metal-insulator phase transition temperature reaches 260K, and the material resistivity changes by more than two orders of magnitude before and after the phase transition. 0.7 Se 0.3 The metal-insulator phase transition temperature reached 380K, and the resistivity of the material before and after the phase transition changed by more than one order of magnitude; the room temperature Seebeck coefficient reached 300μV / K, and the room temperature thermistor coefficient reached 6% / K.

[0021] Furthermore, based on the good ductility of the silver-based chalcogenide metal insulator phase change semiconductor at room temperature and above, it can be directly processed into an alloy foil with a thickness in the range of 1-100 microns through a rolling and extrusion process, or processed into an alloy wire with a diameter in the range of 1-100 microns through a wire drawing process. The prepared silver-based chalcogenide compound alloy foil and alloy wire are flexible self-supporting structures and maintain the original thermosensitive electrical properties of the material. Further, according to the design requirements of the thermosensitive device, the above-mentioned alloy foil and alloy wire based on the silver-based chalcogenide metal insulator phase change semiconductor can be directly cut into the required size, and discrete sensitive resistor devices can be prepared to realize temperature sensing and thermal switch applications, or transferred to an array device bracket to prepare a bridge film or bridge wire structure to realize thermal disturbance detection. The prepared silver-based chalcogenide compound alloy foil and alloy wire thermosensitive materials are flexible, which can realize device flexibility and improve the mechanical toughness of the sensitive material, thereby improving the stability of the device.

[0022] Furthermore, in thermistor and thermal switch applications, silver-based chalcogenide metal-insulator phase change semiconductor alloy foils and wires are directly cut into the desired shape and metal-plated electrodes are used to prepare vertical devices. Temperature sensing is achieved based on the negative temperature coefficient of resistance of the thermistor phase of the insulator phase. The reversible metal-insulator phase transition triggered by a characteristic temperature is used to achieve thermal switch applications. The above negative temperature coefficient of resistance thermistor function and the metal-insulator phase transition function can be used in combination. Under high temperature conditions, the silver ions in Ag2S can migrate between many adjacent positions and are in a low-resistance state. When the temperature is reduced to 450K, the Ag2S structure changes from a body-centered cubic structure to a zigzag, wrinkled, layered monoclinic structure. The Ag ions are fixed in specific positions and cannot migrate between different positions. The resistivity increases sharply, thereby achieving a temperature-controlled switching state transition. In one preferred embodiment, Ag2S is highly sensitive to temperature, with its resistance decreasing as temperature increases. This property can be used to create resistance temperature sensors and current limiting devices. The temperature sensitivity coefficient is approximately five times that of silicon temperature sensors, enabling detection within a temperature range from -100°C to 200°C. In another preferred embodiment, the reversible phase transition properties of metal insulators are utilized in thermal switches.

[0023] Furthermore, in order to realize thermal disturbance detection, the above-mentioned alloy foil and alloy wire based on silver-based chalcogenide metal insulator phase change semiconductor with a self-supporting structure are used as temperature sensitive materials, and are directly transferred to the device support array to prepare a bridge film or bridge wire structure. Infrared absorbing material is further compounded in the middle of the bridge film and bridge wire, and measuring electrodes are grown in two sections in contact with the support, thereby realizing a thermal disturbance detection device. Under a constant temperature, infrared irradiation causes the infrared absorbing material in the middle of the bridge film or bridge wire in the device to heat up and cause a change in the resistance of the silver-based chalcogenide metal insulator phase change semiconductor. Infrared imaging can be realized by measuring the degree of resistivity change of the arrayed bridge film or bridge wire caused by infrared irradiation. In a preferred embodiment, a bridge film structure infrared detector is prepared using silver-based chalcogenide compounds, such as Figure 4 As shown; energy disturbance is applied to the detector, and a current is passed through both ends of the detector in the direction indicated by the arrow, and the change in voltage before and after the energy disturbance is applied is measured to achieve active detection of the energy disturbance. In another preferred embodiment, a bridge wire structure infrared detector is prepared using a silver-based chalcogenide metal insulator phase change semiconductor, such as Figure 5 As shown, its infrared imaging utilizes the metal-insulator phase transition properties of silver-based chalcogenides. When the detector is placed in an energy-swirling environment, the surface light-absorbing layer absorbs energy, causing the local temperature of the silver-based chalcogenide to rise. The filamentous silver-based chalcogenide exhibits excellent temperature sensitivity, causing its resistivity to drop dramatically, enabling active detection of energy disturbances.

[0024] Furthermore, in order to improve the accuracy of thermal disturbance detection, another flexible lead of silver-based chalcogenide metal insulator phase change semiconductor is introduced into the middle of the bridge film and bridge wire in the above-mentioned thermal disturbance detection components, which can measure the Seebeck voltage generated by the local temperature increase caused by the energy disturbance, thereby realizing passive detection of the energy disturbance. Based on the silver-based chalcogenide compound thermistor function, a rapid response to the energy disturbance signal can be achieved, but the signal-to-noise ratio is relatively low; while the passive detection signal based on Seebeck voltage detection has a high signal-to-noise ratio, thereby achieving high detection resolution, but the measurement response is slow. By combining the degree of resistance change of the bridge film and bridge wire due to thermal disturbance, and the voltage amplitude generated by the thermal disturbance in the Seebeck voltage measuring electrode, and supplemented by the above-mentioned active detection and passive detection signal processing, it is possible to reduce the thermal disturbance detection noise. In one embodiment, a thermal disturbance detector is made by combining a silver-based chalcogenide metal insulator phase change material bridge film and a bridge wire structure, such as Figure 6 As shown. Energy disturbance is applied to the detector, a current is passed in the direction indicated by the arrow, and the voltage change before and after the energy disturbance is applied is measured to realize active detection of the energy disturbance; at the same time, the Seebeck voltage generated by the local temperature increase caused by the energy disturbance is measured to realize passive detection of the energy disturbance. In another embodiment, a more compact circular thermal disturbance detector is made of silver-based chalcogenide metal insulator phase change material, such as Figure 7 As shown; an energy disturbance is applied to the center of a circular detector covered with a light-absorbing layer, a current is passed through the two ends of the ring in the direction indicated by the arrow, and the change in voltage before and after the application of the energy disturbance is measured to achieve active detection of the energy disturbance; at the same time, the Seebeck voltage generated by the local temperature increase caused by the energy disturbance is measured in three directions, thereby achieving more accurate passive detection of the energy disturbance.

[0025] Furthermore, the silver-based chalcogenide metal-insulator phase-change semiconductor alloy foil and wire thermistor sensitive materials used in this invention exhibit excellent flexibility and ductility, allowing for bending and facilitating stress release in practical applications. The technology provided by this invention can be applied to intelligent temperature sensing, infrared detection, thermal disturbance detection, thermal switching, and inrush current suppression, achieving flexibility.

[0026] After extensive and in-depth research, the inventors have developed a flexible, thermosensitive semiconductor thermal disturbance detector based on silver-based chalcogenides by improving the preparation process. The main concept of the present invention is that, first, silver-based chalcogenides are used as temperature-sensitive materials, and the material components of the silver-based chalcogenides are designed in combination with detection requirements to regulate their thermal resistance coefficient, Seebeck coefficient, metal-insulator phase transition characteristics near room temperature, and material ductility. Secondly, the prepared silver-based chalcogenides are processed into low-dimensional materials such as films or wires with flexible, self-supporting structures through precision machining methods. Finally, the prepared silver-based chalcogenide sensitive material films or wires with flexible and self-supporting structures are prepared into array-type device structures. The prepared device can combine the negative temperature coefficient thermistor characteristics of the silver-based chalcogenide insulating phase and the metal-insulator phase transition characteristics under characteristic temperature triggering to achieve the synergistic application of the two functional characteristics of temperature sensing and thermal switching. Furthermore, by combining the high Seebeck coefficient and thermal resistance coefficient of silver-based chalcogenides near room temperature, they can synergize active detection based on thermistor effect and passive detection based on the Seebeck effect, further reducing the detection noise of thermal disturbance signals. Compared with existing thermistor technology, the technology provided by this invention has the following advantages: 1) By synergizing the excellent multiple thermal sensitivity and ductility of silver-based chalcogenides, the technology achieves flexibility and self-supporting low-dimensionality for both gradual and sudden thermistors, thereby more easily and flexibly adapting to discrete device applications. 2) By combining the negative temperature coefficient thermistor effect of the insulator phase of silver-based chalcogenides and the metal-insulator phase transition characteristics triggered by characteristic temperatures, the technology achieves the synergistic use of temperature sensing and thermal switching functions. 3) Compared with traditional infrared focal plane thermal disturbance detection technology, the flexible structure of silver-based chalcogenides makes it easier to prepare self-supporting film structures, and the material can further be introduced into a self-supporting Bekk voltage measurement electrode, thereby synergizing the high thermal resistance coefficient and high Seebeck coefficient of silver-based chalcogenides to achieve noise reduction in the detection of thermal disturbance signals. The technical method provided by the present invention is applied to intelligent temperature sensing, infrared detection, thermal disturbance detection, thermal switching, and surge current suppression, and realizes flexibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The resistivity of Ag2S varies with temperature. At room temperature, the resistivity of Ag2S is high, but decreases as the temperature rises. When the temperature rises to around 450K, the resistivity of Ag2S drops sharply, exhibiting metallic properties.

[0028] Figure 2 The temperature coefficient of resistance (TCR) of Ag2S varies with temperature. The room temperature TCR of Ag2S is about 0.04K -1; At around 450K, there is a peak in the TCR-T curve of Ag2S, corresponding to the metal-insulator phase transition of the material.

[0029] Figure 3 The following is a curve showing the Seebeck coefficient of Ag2S as a function of temperature. The Seebeck coefficient of Ag2S is negative throughout the entire temperature range. At room temperature, it is relatively high, approximately 900 μV / K. However, it decreases with increasing temperature. Above 450 K, the Seebeck coefficient drops sharply to 200 μV / K.

[0030] Figure 4 This device structure uses a silver-based chalcogenide bridge film as an energy-sensitive material. Energy perturbations are applied to the surface of a silver-based chalcogenide thin film. A current is passed in the direction indicated by the arrow in the figure, and the voltage change before and after the energy perturbation is measured to achieve active detection of the energy perturbation.

[0031] Figure 5 This is a preferred device structure based on the silver-based chalcogenide bridgewire structure as an energy-sensitive material. Energy perturbation is applied to the surface of the silver-based chalcogenide thin film, a current is passed in the direction indicated by the arrow in the figure, and the voltage (V R ) changes to achieve active detection of energy disturbances.

[0032] Figure 6 This is an optimal device structure based on the combination of a silver-based chalcogenide bridge film structure and a bridge wire structure as an energy-sensitive material. Energy perturbation is applied to the surface of the silver-based chalcogenide thin film, a current is passed in the direction indicated by the arrow in the figure, and the voltage (V R ) changes to achieve active detection of energy disturbances; at the same time, the Seebeck voltage V generated by the local temperature increase caused by the energy disturbance is measured S , thereby realizing passive detection of energy disturbances.

[0033] Figure 7 This is another preferred device structure based on silver-based chalcogenides as energy-sensitive materials. Energy perturbation is applied to the silver-based chalcogenide covered with a circular light-absorbing layer, and a current is passed along the two ends of the ring in the direction indicated by the arrow, and the voltage (V R ) changes to achieve active detection of energy disturbances; at the same time, the Seebeck voltage V generated by the local temperature increase caused by the energy disturbance is measured in three directions. S1 、V S2 、V S3 , thereby achieving more accurate passive detection of energy disturbances. DETAILED DESCRIPTION

[0034] Example 1:

[0035] Silver powder and sulfur powder are mixed evenly in a stoichiometric ratio and cold pressed into sheets at room temperature. The sheets are then sealed in a vacuum quartz tube and placed in a melting furnace at 1000°C for 12 hours. The resulting bulk compound has a relative density of more than 95%, a phase transition temperature of about 450K, and a sudden change in resistivity of more than two orders of magnitude before and after the phase transition. The room temperature Seebeck coefficient reaches 900μV / K, and the room temperature thermistor coefficient reaches 4% / K. Figure 1 、 Figure 2 、 Figure 3 As shown in the figure, the Ag2S obtained using this method can achieve compression deformation exceeding 50%, bending deformation exceeding 20%, and tensile deformation up to 4.2%. After load removal, the compressed specimens exhibited approximately 10%–11% recoverability compared to the initial deformation. These deformation values are significantly greater than those found in typical semiconductors and ceramics, and at room temperature, they retain the same ductility and deformability as metals. They can be directly processed into alloy foils with thicknesses ranging from 1 to 100 microns through rolling and extrusion, and into alloy wires with diameters ranging from 1 to 100 microns through wire drawing.

[0036] Example 2:

[0037] Silver powder and sulfur powder in a stoichiometric ratio are mixed evenly at room temperature and then cold-pressed into sheets. The sheets are then sealed in a vacuum quartz tube and calcined at 1000°C for 12 hours. The Ag2S alloy foil and wire prepared by rolling, extruding or drawing are flexible, self-supporting structures that maintain the material's original thermal electrical properties. Furthermore, according to the design requirements of the thermal device, the above alloy foil and wire can be directly cut to prepare discrete sensitive resistor devices for temperature sensing. The detector passes a current and reads the voltage V across the two ends. R When the detector is placed in a continuously heated environment, the resistivity of Ag2S decreases due to its high sensitivity to temperature. R The temperature of Ag2S decreases continuously, and the temperature sensing is realized based on the negative temperature coefficient thermistor characteristics of its insulating phase. When the temperature is higher than 450K, the structural transformation of Ag2S allows silver ions to migrate between many adjacent positions, and the resistivity decreases sharply by two orders of magnitude. R Reduced by 99%. The reversible phase transition of the metal-insulator under characteristic temperature triggering enables temperature-controlled switching state transitions. Combining the negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enables the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0038] Example 3:

[0039] Silver powder, sulfur powder and selenium powder were mixed in a stoichiometric ratio of 2:0.85:0.15 and cold pressed into sheets at room temperature. The sheets were then sealed in a vacuum quartz tube and placed in a melting furnace at 1000°C for 12 hours to obtain Ag2S 0.85 Se 0.15 Block sample. As part of the sulfur atoms are replaced by selenium atoms, the phase transition temperature of the compound is reduced to about 410K, and the resistivity of the material changes by more than one order of magnitude before and after the phase transition. In addition, the less substitution does not destroy the slip plane, so that it can still maintain good ductility and deformation ability, and can be processed by forging, extrusion, and drawing methods at room temperature. Further, according to the design requirements of the thermal device, the above alloy foil and alloy wire can be directly cut to prepare discrete sensitive resistor devices to realize temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment. 0.85 Se 0.15 High sensitivity to temperature, the resistivity decreases and V R When the temperature is higher than 410K, Ag2S 0.85 Se 0.15 Due to the structural transformation, the resistivity is reduced by an order of magnitude. R Reduced by 90%. The reversible phase transition of the metal-insulator under characteristic temperature triggering is utilized to achieve temperature-controlled switching state transition. Combining the negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enables the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0040] Example 4:

[0041] Silver powder, sulfur powder and selenium powder were mixed uniformly at a stoichiometric ratio of 2:0.7:0.3 at room temperature and cold pressed into sheets. The sheets were sealed in a quartz tube in a glove box under vacuum and then calcined at 1000 °C for 12 hours to obtain Ag2S 0.7 Se 0.3 Block sample. Since some of the sulfur atoms are replaced by selenium atoms, the phase transition temperature of the compound is reduced to about 380K, and the resistivity of the material changes by more than one order of magnitude before and after the phase transition; the room temperature Seebeck coefficient reaches 300μV / K, and the thermistor coefficient reaches 6% / K at room temperature. In addition, the less substitution does not destroy the slip surface, so that it can still maintain good ductility and deformation ability, and the material can be processed by forging, extrusion, and drawing methods at room temperature. Further, according to the design requirements of the thermal device, the above alloy foil and alloy wire can be directly cut to prepare discrete sensitive resistor devices to realize temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment.0.7 Se 0.3 High sensitivity to temperature, the resistivity decreases and V R When the temperature is higher than 380K, Ag2S 0.7 Se 0.3 Due to the structural transformation, the resistivity decreases sharply, V R The device utilizes the reversible phase transition of the metal-insulator under characteristic temperature triggering to achieve temperature-controlled switching state transition. The combined negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enable the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0042] Example 5:

[0043] Silver powder, sulfur powder and selenium powder were mixed uniformly at a stoichiometric ratio of 2:0.5:0.5 at room temperature and cold pressed into sheets. The sheets were sealed in a quartz tube in a glove box under vacuum and then calcined at 1000 °C for 12 hours to obtain Ag2S 0.5 Se 0.5 Block sample. Since some of the sulfur atoms are replaced by selenium atoms, the phase transition temperature of the compound is reduced to about 350K, and the resistivity of the material before and after the phase transition is less than one order of magnitude. In addition, the less substitution does not destroy the slip surface, so that it can still maintain good ductility and deformation ability, and can be processed by forging, extrusion, and drawing methods at room temperature. Further, according to the design requirements of the thermal device, the above alloy foil and alloy wire can be directly cut to prepare discrete sensitive resistor devices to realize temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment. 0.5 Se 0.5 High sensitivity to temperature, the resistivity decreases and V R When the temperature is higher than 350K, Ag2S 0.5 Se 0.5 Due to the structural transformation, the resistivity decreases sharply, V R The device utilizes the reversible phase transition of the metal-insulator under characteristic temperature triggering to achieve temperature-controlled switching state transition. The combined negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enable the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0044] Example 6:

[0045] Silver powder, sulfur powder and tellurium powder were mixed uniformly at room temperature in a stoichiometric ratio of 2:0.9:0.1 and cold pressed into sheets. The sheets were sealed in a quartz tube in a glove box under vacuum and then calcined at 1000 °C for 12 hours to obtain Ag2S 0.9 Te 0.1 Bulk sample. Since some of the sulfur atoms are replaced by tellurium atoms, the phase transition temperature of the compound is reduced to about 330K, and the resistivity of the material changes by more than two orders of magnitude before and after the phase transition. In addition, the less substitution does not destroy the slip plane, so that it can still maintain good ductility and deformation ability, and can be processed by forging, extrusion, and drawing methods at room temperature. Further, according to the design requirements of the thermal device, the above alloy foil and alloy wire can be directly cut to prepare discrete sensitive resistor devices to realize temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment. 0.9 Te 0.1 High sensitivity to temperature, the resistivity decreases and V R When the temperature is higher than 330K, Ag2S 0.9 Te 0.1 Due to the structural transformation, the resistivity decreases sharply, V R Reduced by 99%. The reversible phase transition of the metal-insulator under characteristic temperature triggering enables temperature-controlled switching state transitions. Combining the negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enables the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0046] Example 7:

[0047] Silver powder, sulfur powder and tellurium powder were mixed uniformly at room temperature in a stoichiometric ratio of 2:0.87:0.13 and cold pressed into sheets. The sheets were sealed in a quartz tube in a glove box under vacuum and then calcined at 1000 °C for 12 hours to obtain Ag2S 0.87 Te 0.13 Bulk sample. Since some of the sulfur atoms are replaced by tellurium atoms, the phase transition temperature of the compound is reduced to about 290K, and the resistivity of the material changes by more than two orders of magnitude before and after the phase transition. In addition, the less substitution does not destroy the slip plane, so that it can still maintain good ductility and deformation ability, and can be processed by forging, extrusion, and drawing methods at room temperature. Further, according to the design requirements of the thermal device, the above alloy foil and alloy wire can be directly cut to prepare discrete sensitive resistor devices to realize temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment. 0.87 Te 0.13High sensitivity to temperature, the resistivity decreases and V R When the temperature is higher than 290K, Ag2S 0.87 Te 0.13 Due to the structural transformation, the resistivity decreases sharply, V R Reduced by 99%. The reversible phase transition of the metal-insulator under characteristic temperature triggering enables temperature-controlled switching state transitions. Combining the negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enables the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0048] Example 8:

[0049] Silver powder, copper powder, sulfur powder and selenium powder were mixed uniformly in a stoichiometric ratio of 1.8:0.2:0.5:0.5 at room temperature and cold pressed into sheets. The sheets were sealed in a quartz tube in a glove box under vacuum and then calcined at 1000 ° C for 12 hours to obtain Ag. 1.8 Cu 0.2 S 0.5 Se 0.5 Bulk sample. As some silver atoms are replaced by copper atoms and some sulfur atoms are replaced by selenium atoms, the phase transition temperature of the compound is reduced to about 340K. Further, according to the design requirements of the thermal device, it is cut to prepare discrete sensitive resistor devices to achieve temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment. 1.8 Cu 0.2 S 0.5 Se 0.5 Highly sensitive to temperature, as the resistivity decreases V R When the temperature is higher than 340K, Ag 1.8 Cu 0.2 S 0.5 Se 0.5 Due to the structural transformation, the resistivity decreases sharply, V R Reduced by 20%. The reversible phase transition of the metal-insulator under characteristic temperature triggering is utilized to achieve temperature-controlled switching state transition. Combining the negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enables the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0050] Example 9:

[0051] Silver powder, tin powder, sulfur powder and selenium powder were mixed uniformly in a stoichiometric ratio of 1.8:0.2:0.5:0.5 at room temperature and cold pressed into sheets. The sheets were sealed in a quartz tube in a glove box under vacuum and then calcined at 1000 ° C for 12 hours to obtain Ag.1.8 Sn 0.2 S 0.5 Se 0.5 Bulk sample. As some silver atoms are replaced by tin atoms and some sulfur atoms are replaced by selenium atoms, the phase transition temperature of the compound is reduced to about 345K. Further, according to the design requirements of the thermal sensor, it is cut to prepare discrete sensitive resistor devices to realize temperature sensing. The detector passes a current and reads the voltage V at both ends. R The detector is placed in a continuously heated environment. 1.8 Sn 0.2 S 0.5 Se 0.5 Highly sensitive to temperature, as the resistivity decreases V R When the temperature is higher than 345K, Ag 1.8 Sn 0.2 S 0.5 Se 0.5 Due to the structural transformation, the resistivity decreases sharply, V R The device utilizes the reversible phase transition of the metal-insulator under characteristic temperature triggering to achieve temperature-controlled switching state transition. The combined negative temperature coefficient thermistor effect and the metal-insulator phase transition characteristics under characteristic temperature triggering enable the coordinated use of low-temperature temperature sensing and high-temperature thermal switching functions.

[0052] Example 10:

[0053] use Figure 1 、 Figure 2 Ag2S with a sudden resistance temperature coefficient as shown is used as energy sensitive material. Figure 4 The structure shown is made into a bridge membrane structure device. A current is passed in the direction indicated by the arrow, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises by 10K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Active detection of energy disturbances is achieved in a relatively short time.

[0054] Example 11:

[0055] use Figure 1 、 Figure 2 Ag2S with a sudden resistance temperature coefficient as shown is used as energy sensitive material. Figure 5 The structure shown is made into a bridge wire structure device. A steady current is applied to both ends of the filament sample as shown in the figure, and the voltage V at both ends is read. RBy applying energy disturbance to the device surface using light waves, the temperature rises by 5K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Active detection of energy disturbances is achieved in a relatively short time.

[0056] Example 12:

[0057] use Figure 1 、 Figure 2 、 Figure 3 Ag2S with the resistance temperature coefficient and Seebeck coefficient as shown is used as energy sensitive material. Figure 6 The structure shown is made into a device combining a bridge membrane structure and a bridge wire structure. R Direction) pass a current and read V R value, at this time V S The value is close to zero. By applying energy disturbance to the surface of the device using light waves, the local temperature of the material rises by 10K after light absorption, making V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S Read a voltage signal of about 270 mV. After stopping the energy perturbation and letting it stand for a while, V R Return to the original value and V S Return to zero point. In active detection, the signal reaction time is short, while in passive detection, the signal-to-noise ratio is high. Therefore, through the comprehensive utilization of active and passive methods, rapid perception of energy disturbance signals and high-precision detection can be achieved.

[0058] Example 13:

[0059] use Figure 1 、 Figure 2 、 Figure 3 Ag2S with the resistance temperature coefficient and Seebeck coefficient as shown is used as energy sensitive material. Figure 7 The structure shown is made into a device. A current is passed through the two ends of the ring and V is read. R value, at this time V S The value is close to zero. When a microwave disturbance signal is applied to the center of the circular structure of the device, the local temperature of the material rises after light absorption, causing V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S1 、V S2 、V S3 The voltage signals of about 162 mV, 160 mV, and 165 mV were read. After stopping the microwave signal and cooling for 30 minutes, V R Return to the original value and V S1-S3Return to zero point. In active detection, the signal reaction time is short, while in passive detection, the signal-to-noise ratio is high. Therefore, through the comprehensive utilization of active and passive methods, rapid perception of energy disturbance signals and high-precision detection can be achieved.

[0060] Example 14:

[0061] Using silver-based chalcogenide Ag2S 0.85 Te 0.15 As energy sensitive materials, Figure 4 The structure shown is made into a device. A current is passed in the direction indicated by the arrow, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises by 10K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Achieve active detection of energy disturbance in a shorter time. Figure 5 The structure shown is made into a bridge wire structure device. A steady current is applied to both ends of the filament sample as shown in the figure, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises by 5K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Achieve active detection of energy disturbance in a shorter time. Figure 6 The structure shown is made into a device combining a bridge membrane structure and a bridge wire structure. R Direction) pass a current and read V R value, at this time V S The value is close to zero. By applying energy disturbance to the surface of the device using light waves, the local temperature of the material rises by 10K after light absorption, making V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S Read a voltage signal of about 350 mV. After stopping the energy perturbation and letting it stand for a while, V R Return to the original value and V S Back to zero. Or follow Figure 7 The structure shown is made into a device. A current is passed through the two ends of the ring and V is read. R value, at this time V S The value is close to zero. When a microwave disturbance signal is applied to the center of the circular structure of the device, the local temperature of the material rises after light absorption, causing V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S1 、V S2 、VS3 Read out voltage signals of about 180 mV, 183 mV, and 185 mV. After stopping the microwave signal and cooling for 30 minutes, V R Return to the original value and V S1-S3 Return to zero point. In active detection, the signal reaction time is short, while in passive detection, the signal-to-noise ratio is high. Therefore, through the comprehensive utilization of active and passive methods, rapid perception of energy disturbance signals and high-precision detection can be achieved.

[0062] Example 15:

[0063] Using silver-based chalcogenide Ag2S 0.9 Te 0.1 As energy sensitive materials, Figure 4 The structure shown is made into a device. A current is passed in the direction indicated by the arrow, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Achieve active detection of energy disturbance in a shorter time. Figure 5 The structure shown is made into a bridge wire structure device. A steady current is applied to both ends of the filament sample as shown in the figure, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises by 5K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Achieve active detection of energy disturbance in a shorter time. Figure 6 The structure shown is made into a device combining a bridge membrane structure and a bridge wire structure. R Direction) pass a current and read V R value, at this time V S The value is close to zero. By applying energy disturbance to the surface of the device using light waves, the local temperature of the material increases after light absorption, making V R changes by 50%; at the same time, the Seebeck voltage V caused by the temperature increase due to local light absorption is measured S Read a voltage signal of about 450 mV. After stopping the energy perturbation and letting it stand for a while, V R Return to the original value and V S Back to zero. Or follow Figure 7 The structure shown is made into a device. A current is passed through the two ends of the ring and V is read. R value, at this time V SThe value is close to zero. When a microwave disturbance signal is applied to the center of the circular structure of the device, the local temperature of the material rises after light absorption, causing V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S1 、V S2 、V S3 The voltage signals were read out to be about 245 mV, 240 mV, and 249 mV. After stopping the microwave signal injection and cooling for 30 minutes, V R Return to the original value and V S1-S3 Return to zero point. In active detection, the signal reaction time is short, while in passive detection, the signal-to-noise ratio is high. Therefore, through the comprehensive utilization of active and passive methods, rapid perception of energy disturbance signals and high-precision detection can be achieved.

[0064] Example 16:

[0065] Using silver-based chalcogenide Ag2S 0.5 Se 0.5 As energy sensitive materials, Figure 4 The structure shown is made into a device. A current is passed in the direction indicated by the arrow, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises by 10K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Achieve active detection of energy disturbance in a shorter time. Figure 5 The structure shown is made into a bridge wire structure device. A steady current is applied to both ends of the filament sample as shown in the figure, and the voltage V at both ends is read. R By applying energy disturbance to the device surface using light waves, the temperature rises by 5K due to local light absorption, causing the material resistivity to decrease, making V R After removing the energy disturbance, V R Return to the original value. Achieve active detection of energy disturbance in a shorter time. Figure 6 The structure shown is made into a device combining a bridge membrane structure and a bridge wire structure. R Direction) pass a current and read V R value, at this time V S The value is close to zero. By applying energy disturbance to the surface of the device using light waves, the local temperature of the material increases after light absorption, making V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S Read a voltage signal of about 190 mV. After stopping the energy perturbation and letting it stand for a while, V R Return to the original value and VS Back to zero. Or follow Figure 7 The structure shown is made into a device. A current is passed through the two ends of the ring and V is read. R value, at this time V S The value is close to zero. When a microwave disturbance signal is applied to the center of the circular structure of the device, the local temperature of the material rises after light absorption, causing V R The Seebeck voltage V is measured due to the temperature rise caused by local light absorption. S1 、V S2 、V S3 The voltage signals were about 121mV, 123mV and 127mV. After stopping the microwave signal and cooling for 30 minutes, V R Return to the original value and V S1-S3 Return to zero point. In active detection, the signal reaction time is short, while in passive detection, the signal-to-noise ratio is high. Therefore, through the comprehensive utilization of active and passive methods, rapid perception of energy disturbance signals and high-precision detection can be achieved.

Claims

1. A silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor, which relates to sensitive resistor materials and devices of semiconductor thermal and thermoelectric composite sensors, characterized in that: Taking into account the three advantages of silver-based chalcogenides, namely high thermal resistivity, high Seebeck coefficient and good ductility near room temperature, silver-based chalcogenides are used as temperature and thermal disturbance sensitive materials; firstly, silver-based chalcogenide metal-insulator phase change semiconductors use silver-based chalcogenides as temperature sensitive materials, and design the material components of silver-based chalcogenides in combination with detection needs, so as to regulate their thermal resistivity, Seebeck coefficient, metal-insulator phase change characteristics and material ductility near room temperature; secondly, the prepared silver-based chalcogenides are processed into membranes, silk and low-dimensional materials with flexible self-supporting structures through precision machining methods. Finally, the prepared silver-based chalcogenide sensitive material film or wire with a flexible and self-supporting structure is prepared into an array device structure device; the prepared device can combine the negative temperature coefficient thermistor characteristics of the silver-based chalcogenide insulating phase and the metal-insulator phase transition characteristics triggered by characteristic temperature to achieve the synergistic application of temperature sensing and thermal switching functions; in addition, the high Seebeck coefficient and thermal resistance coefficient of the silver-based chalcogenide near room temperature can be combined with the active detection method based on the thermistor effect and the passive detection method based on the Seebeck effect to further reduce the detection noise of the thermal disturbance signal; The silver-based chalcogenide metal-insulator phase-change semiconductor has reversible metal-insulator phase transition characteristics when triggered by a characteristic temperature. Its functional characteristics are manifested in that its electrical transport characteristics exhibit negative temperature coefficient thermistor characteristics below the characteristic temperature when the material resistivity is below the characteristic temperature. The achieved negative temperature coefficient thermistor is comparable to that of a traditional NTC thermistor. When the temperature rises to the metal-insulator phase transition temperature, the material resistivity undergoes a reversible mutation and decreases by more than an order of magnitude. During the phase transition, the crystal structure of the silver-based chalcogenide compound reversibly transforms from a zigzag, wrinkled, layered monoclinic structure below the characteristic temperature to a body-centered cubic structure. By substituting a positive monovalent element at the silver atomic position or other Group VI main element at the sulfur atomic position, the phase transition temperature can be controlled within the temperature range of 260-460 K, and a high Seebeck coefficient and a high thermistor coefficient can be simultaneously achieved in the temperature range near room temperature. The silver-based chalcogenide metal-insulator phase-change semiconductor is an alloy compound with Ag2S as the parent phase, wherein the silver atom can be partially replaced by a positive monovalent element, and the sulfur atom can be partially replaced by other sixth main group elements; its chemical formula is Ag 2- x M x S 1-y C y , wherein M is a monovalent element, and C is a sixth main group element other than sulfur; the silver-based chalcogenide metal insulator phase change semiconductor has good ductility and can be processed by forging, extrusion, and drawing methods at room temperature; The M is Cu or Sn, and the value of x is 0.01-0.5; the C is Se or Te, and the value of y is 0.01-0.

5.

2. The silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor according to claim 1, characterized in that: The silver-based chalcogenide metal-insulator phase-change semiconductor has reversible metal-insulator phase transition characteristics when triggered by a characteristic temperature. Its functional characteristics are manifested in that its electrical transport characteristics exhibit negative temperature coefficient thermistor characteristics when the material resistivity is below the characteristic temperature, and the achieved negative temperature coefficient thermistor is comparable to that of a traditional NTC thermistor. When the temperature rises to the metal-insulator phase transition temperature, the material resistivity undergoes a reversible mutation and decreases by more than an order of magnitude. During the phase transition, the crystal structure of the silver-based chalcogenide compound reversibly transforms from a zigzag, wrinkled, layered monoclinic structure below the characteristic temperature to a body-centered cubic structure. By substituting a positive monovalent element at the silver atomic position or other Group VI elements at the sulfur atomic position, the phase transition temperature can be controlled in the temperature range of 260-460 K, and a high Seebeck coefficient and a high thermistor coefficient can be simultaneously achieved in the temperature range near room temperature.

3. An application of the silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor according to claim 1, characterized in that: The silver-based chalcogenide metal insulator phase change semiconductor has good ductility at room temperature and above, and can be directly processed into alloy foil with a thickness in the range of 1-100 microns through rolling and extrusion processes, or processed into alloy wire with a diameter in the range of 1-100 microns through wire drawing processes; the prepared silver-based chalcogenide compound alloy foil and alloy wire have a flexible self-supporting structure and maintain the original thermal sensitive electrical properties of the material; further, according to the design requirements of the thermal sensitive device, the alloy foil and alloy wire based on the silver-based chalcogenide metal insulator phase change semiconductor can be directly cut into the required size, and discrete sensitive resistor devices can be prepared to realize temperature sensing and thermal switch applications, or transferred to an array device bracket to prepare bridge membrane and bridge wire structures to realize thermal disturbance detection; the prepared silver-based chalcogenide compound alloy foil and alloy wire thermal sensitive materials are flexible, which can realize device flexibility and improve the mechanical toughness of the sensitive material, thereby improving the stability of the device.

4. An application of the silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor according to claim 1, characterized in that: In thermistor and thermal switch applications, the alloy foil and alloy wire of the silver-based chalcogenide metal-insulator phase change semiconductor are directly cut into the required shape and the two-section metal-plated electrodes are used to prepare a vertical device; temperature sensing is achieved based on the negative temperature coefficient thermistor characteristics of its insulating phase; and thermal switch applications are realized by utilizing its reversible metal-insulator phase change triggered by a characteristic temperature; the above negative temperature coefficient thermistor function and the metal-insulator phase change function can be used in combination.

5. An application of the silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor according to claim 1, characterized in that: In order to realize thermal disturbance detection, alloy foil and alloy wire based on silver-based chalcogenide metal insulator phase change semiconductor with self-supporting structure are used as temperature sensitive materials, and are directly transferred to the device support array to prepare bridge film or bridge wire structure; infrared absorption material is further compounded in the middle of the bridge film and bridge wire, and two measuring electrodes are grown in contact with the support, so as to further realize thermal disturbance detection device; under constant temperature, infrared irradiation causes the infrared absorption material in the middle of the bridge film or bridge wire in the device to heat up and cause the change of the resistance of the silver-based chalcogenide metal insulator phase change semiconductor, and infrared imaging can be realized by measuring the degree of resistivity change of the arrayed bridge film or bridge wire caused by infrared irradiation; in order to improve the accuracy of thermal disturbance detection, Another flexible lead of silver-based chalcogenide metal insulator phase change semiconductor is introduced into the middle of the bridge membrane and bridge wire in the device, which can measure the Seebeck voltage generated by the local temperature increase caused by energy disturbance, thereby realizing passive detection of energy disturbance; based on the silver-based chalcogenide compound thermistor function, a fast response to the energy disturbance signal can be achieved, but the signal-to-noise ratio is relatively low; while the passive detection signal based on Seebeck voltage detection has a high signal-to-noise ratio, thus achieving high detection resolution, but the measurement response is slow; the degree of resistance change of the bridge membrane and bridge wire due to thermal disturbance, as well as the voltage amplitude generated by the thermal disturbance in the Seebeck voltage measurement electrode are comprehensively considered, and supplemented by signal processing of active and passive detection, the thermal disturbance detection noise can be reduced.

6. An application of the silver-based chalcogenide metal insulator phase change flexible semiconductor thermal sensor according to claim 1, characterized in that: Alloy foil and alloy wire thermistor sensitive materials using silver-based chalcogenide metal insulator phase change semiconductors have good flexibility and ductility. They can be bent in actual use and are conducive to stress release. They can be applied to intelligent temperature sensing, infrared detection, thermal disturbance detection, thermal switches, and surge current suppression, and can achieve flexibility.

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