Silver-based chalcogenide compound array temperature-pressure synergistic sensor material and its use method

Abstract

A silver-based chalcogenide array-type temperature-pressure collaborative sensor material and a method of use. The prepared sensor array can realize two applications: temperature-pressure sensing in solid, liquid, and gaseous environments, as well as temperature-pressure alarms. The present invention uses silver-based chalcogenides as sensitive materials, selects silver-based chalcogenide material components according to the actual environmental detection range, thereby achieving the design of the relationship between its resistivity and temperature and pressure changes, and collaboratively uses temperature-pressure sensitive components made of multiple components of silver-based chalcogenides to perform collaborative detection and alarm functions of temperature and pressure. The array-type temperature-pressure sensor prepared by the present invention through the selection of silver-based chalcogenide material components can realize the collaborative measurement of temperature and pressure in solid, liquid, and gaseous environments in the pressure range of 1MPa to 50GPa and the temperature range of 200K to 600K, as well as the application of temperature and pressure alarms in the above-mentioned critical ranges, and has application value in deep-sea exploration, deep earth exploration, oil exploration and mining, etc.

Description

Technical Field

[0001] The present invention belongs to the field of sensors, and in particular relates to an array-type temperature and pressure sensor using a silver-based chalcogenide compound semiconductor electronic phase change material as a sensitive material and a method for using the same. Background Art

[0002] The development of a new generation of pressure sensing materials and devices suitable for high pressure ranges above 100 MPa has important scientific significance and application value. Currently, existing pressure sensing technologies such as semiconductor pressure sensitive resistors, strain gauges, and silicon piezoresistive pressure sensors can adapt to pressure sensing and detection in the range of normal pressure to 100 MPa. For example, traditional

[0003] However, humanity's continued exploration of extreme environments, such as the deep sea and deep earth, has challenged the measurement range of traditional pressure sensors. For example, since 2010, manned submersibles such as the Jiaolong and Fendouzhe have successively reached depths of 1,000, 3,000, 5,000, 7,000, and 10,909 meters in the Mariana Trench, corresponding to pressures of 10-100 MPa. Compared to deep-sea exploration, the potential mantle pressures encountered in deep earth exploration range far greater than those of the order of GPa. Furthermore, compared to liquid pressure media such as seawater in the ocean, solid pressure media such as the mantle in deep earth exploration place higher demands on the mechanical properties of sensors. Because existing semiconductor pressure sensors, strain gauges, and silicon piezoresistive pressure sensors struggle to meet pressure detection requirements above 70 MPa, disruptive technological breakthroughs from a material perspective are urgently needed. This involves exploring new materials with excellent pressure sensitivity in the 100 MPa range to transform existing pressure sensor technology. Summary of the Invention

[0004] The purpose of the present invention is to provide a design, production and use method of an array pressure sensor using silver-based chalcogenide compound semiconductors as sensitive materials. The prepared sensor array can realize the application of temperature and pressure sensing and temperature and pressure alarm in solid, liquid and gaseous environments.

[0005] A silver-based chalcogenide array type temperature-pressure synergistic sensor material and its use method, characterized in that the silver-based chalcogenide array type temperature-pressure synergistic sensor material is a temperature and pressure sensitive material, and its chemical formula is Ag 2- x A x S 1-y B y; Wherein A is a silver atomic substitution element, including Cu, Hg, Cs, K elements, 0≤x≤1.5; B is a sulfur atomic substitution element, including Se, Te, O elements, 0≤y≤1; the material can realize the coordinated measurement of pressure and temperature in solid, liquid and gas environments, as well as critical temperature and pressure warning applications; on the one hand, by designing the components of silver-based chalcogenide materials, the relationship between the resistivity of its insulating phase and the temperature and pressure is designed, and silver-based chalcogenide compounds with multiple material components are selected according to the temperature and pressure range of the intended detection environment to make array detection components; the above-mentioned silver-based chalcogenide compounds prepared with different components are measured in the intended detection environment. The resistance of the temperature and pressure detection components is measured, and then multiple binary equations about pressure and temperature are constructed with reference to the standard mathematical expressions of the resistivity, temperature and pressure relationship of the corresponding material components. The ambient pressure and temperature values ​​are obtained by solving the above equations. On the other hand, the critical triggering temperature and critical triggering pressure of the electronic phase transition of the silver-based chalcogenide compound are regulated by the material components, and the resistivity mutation triggered by the electronic phase transition is used to realize the early warning of the critical temperature and pressure in the environment. According to the critical temperature and pressure range to be warned, the critical temperature and pressure warning range can be regulated and designed by using a single material component component or a silver-based chalcogenide component unit with multiple material components.

[0006] Furthermore, the silver-based chalcogenide exhibits metal-insulator phase transition characteristics triggered by a critical temperature and a critical pressure. Below these critical temperatures and pressures, the material is in an insulating phase, and its resistivity gradually decreases with increasing temperature and pressure. When the temperature and pressure rise to the critical triggering threshold for the electronic phase transition, the silver-based chalcogenide transforms into a metal, and its resistivity suddenly decreases. By manipulating the material composition of the silver-based chalcogenide, it is possible to design the gradual change in its insulating phase resistivity with temperature and pressure, as well as the critical triggering temperature and pressure for the electronic phase transition.

[0007] Furthermore, the material components of the silver-based chalcogenide compound used are selected according to the temperature and pressure ranges in the environment to be measured, and are made into sensitive resistor chips one by one, and further connected with leads to the resistance measurement circuit; the shape of the sensitive resistor chip can be cylindrical, filamentous, sheet-like, rectangular, or ellipsoidal; the leads connected to the external circuit are preferably platinum wires, copper wires, aluminum wires, or gold wires; the contact material between the silver-based chalcogenide compound sensitive resistor material and the leads is preferably silver, copper, or aluminum.

[0008] Furthermore, in order to realize the application of temperature and pressure sensing, the sensitive resistor components of the material components of the above-prepared sulfide compounds with different components are arranged into a detection array and placed in the environment to be detected to read their resistance values; multiple binary equations are constructed with reference to the standard mathematical relationship of the resistivity, temperature, and pressure of the corresponding components of the sensitive resistor material used, and the temperature and pressure values ​​in the environment to be measured are solved.

[0009] Furthermore, to achieve temperature and pressure sensing applications, in addition to using multiple silver-based chalcogenide compound sensitive resistor components to form an array as described above, when the ambient temperature to be detected is known and does not change significantly, only one silver-based chalcogenide compound material can be used to make a pressure-sensitive resistor component; by measuring the resistance of the above-mentioned silver-based chalcogenide compound in the environment to be tested and referring to the resistivity-pressure relationship curve of the sensitive resistor material used at the corresponding ambient temperature, the detection of the ambient pressure can be achieved. In addition, only one silver-based chalcogenide compound material whose resistivity changes sensitively with temperature and pressure within the temperature and pressure range of the environment to be measured can be selected to manufacture a pressure-sensitive resistor component; the pressure-sensitive resistor component can be used in conjunction with a thermistor device whose resistivity is sensitive to temperature and insensitive to pressure within the temperature and pressure range of the environment to be measured; in the temperature and pressure environment to be measured, the resistance value of the thermistor whose resistivity is sensitive to temperature and insensitive to pressure and the resistance value of the silver-based chalcogenide compound sensitive resistor whose resistivity is sensitive to both temperature and pressure are measured; the ambient temperature is first obtained based on a comparison between the resistance value of the thermistor and its standard resistance-temperature relationship, and the ambient pressure is further obtained by comparing the corresponding relationship between the resistance value of the silver-based chalcogenide compound sensitive resistor used at the corresponding temperature and pressure.

[0010] Furthermore, in order to realize the application of temperature and pressure critical value warning, the electronic phase change critical trigger temperature and critical trigger pressure of silver-based chalcogenide compounds are designed according to the intended warning temperature and pressure thresholds in the environment; by measuring the sudden change in the resistivity of the silver-based chalcogenide sensitive resistor chip, the critical temperature and critical pressure thresholds in the environment are perceived to realize the warning function; in actual applications, silver-based chalcogenide compounds with different components can also be used in coordination to realize coordinated warning of different critical pressures and critical temperatures in the environment.

[0011] Furthermore, the array-type temperature and pressure sensor prepared by the present invention through the selection of silver-based chalcogenide material components can realize the coordinated measurement of temperature and pressure in solid, liquid and gaseous environments in the pressure range of 1MPa to 50GPa and the temperature range of 200K to 600K, as well as critical threshold warning; the technical method described in the present invention can be applied to the coordinated measurement of temperature and pressure in deep-sea exploration, deep earth exploration, and oil exploration and production environments.

[0012] Compared to traditional semiconductor pressure-sensitive resistor technology, the silver-based chalcogenide used in this invention offers two advantages in its insulating phase: 1) a higher pressure-sensitive resistivity in the high-pressure range above 10 MPa compared to conventional pressure-sensitive materials under high pressure; 2) improved material ductility and plasticity, resulting in higher mechanical stability and compressive strength in gas, liquid, and solid pressure-transmitting media. A temperature-pressure sensor component is constructed using a silver-based chalcogenide as the sensitive material, using electrode leads. The silver-based chalcogenide material components are selected based on the actual environmental detection range to design the relationship between their resistivity and temperature and pressure. Temperature-pressure-sensitive components made from multiple silver-based chalcogenide components are then used in tandem for actual detection. The resistance values ​​of the silver-based chalcogenide components of different compositions are measured at specific pressures and temperatures. Multiple binary equations relating pressure and temperature are constructed using standard mathematical expressions for the resistivity, temperature, and pressure relationships of the corresponding material components. These binary equations are then solved to obtain the ambient pressure and temperature values. Furthermore, the present invention utilizes the sudden change in material resistivity caused by the pressure-triggered electronic phase transition of the silver-based chalcogenide to implement pressure alarm applications. The silver-based chalcogenide array temperature and pressure sensor prepared by the method described in this invention can achieve coordinated measurement of temperature and pressure in solid, liquid, and gaseous environments within the pressure range of 1 MPa to 50 GPa and the temperature range of 200 K to 600 K. It can also provide temperature and pressure alarms within these critical ranges, and has application value in deep-sea and deep-earth exploration, as well as oil exploration and production. Compared with previous temperature and pressure sensing technologies, the technology provided by this invention can simultaneously achieve both coordinated temperature and pressure sensing and early warning functions, and exhibits higher sensitivity in pressure sensing above 70 MPa. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is the X-ray diffraction pattern of the Ag2S material used.

[0014] Figure 2 The resistivity-temperature relationship of the Ag2S cylindrical sensitive resistor chip used under atmospheric pressure.

[0015] Figure 3 The resistance-pressure relationship of the Ag2S cylindrical sensitive resistor chip used at room temperature.

[0016] Figure 4 The relationship between the resistance of the Ag2S chip sensitive resistor chip used and the change in temperature and pressure.

[0017] Figure 5 This is a schematic diagram of the structural device composed in Example 7 of the present invention. DETAILED DESCRIPTION

[0018] Example 1: To detect the simulated deep-sea hydrostatic pressure at room temperature, cylindrical Ag2S is used as the sensitive resistor material, and its X-ray diffraction pattern is as follows: Figure 1 As shown. Under standard atmospheric pressure, the sensitive resistor material used has the metal-insulator phase transition characteristics triggered by characteristic temperature, and its resistance-temperature relationship is as follows Figure 2 As shown; at room temperature, its resistance gradually decreases with the increase of pressure, and its typical resistance-pressure relationship curve is shown in Figure 3 As shown in the figure, a cylindrical Ag2S cross-section was coated with silver paste to serve as an electrode, and copper wires were led to the measurement circuit. The fabricated device can measure simulated seawater pressure at room temperature from 100 to 10,000 meters. The device's DC resistance can reflect seawater pressure and further infer seawater depth.

[0019] Example 2: To further achieve the measurement of simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes and Ag2S flakes were used. 0.7 Se 0.3 Two different components of silver-based chalcogenides are used as sensitive resistor materials. Among them, the relationship between the DC resistance of the Ag2S sheet sensitive resistor and temperature and pressure is as follows: Figure 4 As shown, based on Figure 4 The experimental data shown in the figure are combined with mathematical fitting to obtain the functional relationship R of the resistance value-temperature-pressure of the Ag2S sensitive resistor. Ag2S Taylor broadening form of (P,T); A similar method was used to construct a Ag2S 0.7 Se 0.3 Functional relationship R of sensitive resistor's resistance value-temperature-pressure Ag2S0.7Se0.3 (P, T). Under a certain temperature and pressure seawater environment, the flake Ag2S and flake Ag2S were measured respectively. 0.7 Se 0.3 The resistance value R Ag2S ', R Ag2S0.7Se0.3 ', and construct a system of two-variable equations: R Ag2S0.7Se0.3 (P,T)=R Ag2S0.7Se0.3 ', R Ag2S (P,T)=R Ag2S By solving the above binary equations, we can obtain the temperature and pressure of the ocean environment to be detected, and further refer to the seawater density and temperature distribution to calculate the seawater depth.

[0020] Example 3: To further achieve the measurement of simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes and Ag2S flakes are used. 0.7 Se 0.3 Two different components of silver-based chalcogenides are used as sensitive resistor materials. Silver electrodes are made at both ends of the metal sheet and connected to the measurement circuit through platinum wire. Among them, the relationship between the DC resistance of the sheet Ag2S sensitive resistor and temperature and pressure is as follows: Figure 4 As shown, based on Figure 4 The experimental data shown in the figure are combined with mathematical fitting to obtain the functional relationship R of the resistance value-temperature-pressure of the Ag2S sensitive resistor. Ag2S Taylor broadening form of (P,T); A similar method was used to construct a Ag2S 0.7 Se 0.3 Functional relationship R of sensitive resistor's resistance value-temperature-pressure Ag2S0.7Se0.3 (P, T). Under a certain temperature and pressure seawater environment, the flake Ag2S and flake Ag2S were measured respectively. 0.9 Se 0.1 The resistance value R Ag2S ', R Ag2S0.7Se0.3 ', and construct a system of two-variable equations: R Ag2S0.7Se0.3 (P,T)=R Ag2S0.7Se0.3 ', R Ag2S (P,T)=R Ag2S By solving the above binary equations, we can obtain the temperature and pressure of the ocean environment to be detected, and further refer to the seawater density and temperature distribution to calculate the seawater depth.

[0021] Example 4: To achieve coordinated detection of temperature and pressure in a simulated deep-earth environment, filamentous Ag2S and Ag2S 0.8 Te 0.2 、Ag2S 0.7 Se 0.3 、Ag2S 0.5 Se 0.5 、Ag 1.8 Cu 0.2 S 0.7 Se 0.3 、Ag 1.9 Hg 0.1 Five different types of silver-based chalcogenides were used as sensitive resistor materials, with platinum wires welded at both ends to connect to the measurement circuit. The relationship between the resistance values ​​of the five silver-based chalcogenides and temperature and pressure was measured and the functional relationship between resistance value, temperature and pressure was obtained by mathematical fitting: R Ag2S (P,T),R Ag2S0.8Te0.2 (P,T),R Ag2S0.7Se0.3 (P,T),R Ag2S0.5Se0.5 (P,T),R Ag1.8Cu0.2S0.7Se0.3 (P,T),R Ag1.9Hg0.1S (P, T). Measure the resistance values ​​of the above five silver-based chalcogenide resistors R in the temperature and pressure environment to be measured. Ag2S '、R Ag2S0.8Te0.2 '、R Ag2S0.7Se0.3 '、R Ag2S0.5Se0.5 '、R Ag1.8Cu0.2S0.7Se0.3 '、R Ag1.9Hg0.1S '. Constructing the system of equations: RAg2S (P,T)=R Ag2S ', R Ag2S0.8Te0.2 (P,T)=R Ag2S0.8Te0.2 ', R Ag2S0.7Se0.3 (P,T)=R Ag2S0.7Se0.3 ', R Ag1.8Cu0.2S0.7Se0.3 (P,T)=R Ag1.8Cu0.2S0.7Se0.3 ', R Ag1.9Hg0.1S (P,T)=R Ag1.9Hg0.1S Solve the above equations pairwise to obtain the temperature and pressure; take the average value to obtain the ambient temperature and pressure.

[0022] Example 5: To measure the simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes were used. 0.8 Te 0.2 As a pressure sensitive resistor material, the heavy rare earth element component rare earth nickel-based oxide DyNiO3 ceramic is used as a temperature sensing material. In a certain temperature and pressure seawater environment, the ambient temperature is first measured by DyNiO3 ceramic, and the Ag2S is obtained at the corresponding temperature by referring to the pre-determined relationship between the sensitive resistor resistance, temperature and pressure. 0.8 Te 0.2 The relationship between the DC resistance of the sensitive resistor and the pressure. Further measurement of Ag2S in the test environment 0.8 Te 0.2 The ambient pressure value is obtained by measuring the DC resistance of the sensitive resistor. Through the above method, pressure sensing in the range of 1MPa to 1GPa can be achieved in the temperature range of 0-50 degrees Celsius.

[0023] Example 6: To measure simulated deep-earth pressure under variable temperature conditions, sheet-like Ag2S was used as the pressure-sensitive resistor material, and DyNiO3 ceramic, a rare earth nickel-based oxide composed of heavy rare earth elements, was used as the temperature sensing material. Under a seawater environment with a certain temperature and pressure, the ambient temperature was first measured using the DyNiO3 ceramic. The relationship between the DC resistance of the Ag2S sensitive resistor and pressure was then determined by referring to the previously measured relationship between the sensitive resistor's resistance, temperature, and pressure at the corresponding temperature. The DC resistance of the Ag2S sensitive resistor was further measured in the test environment to obtain the ambient pressure value. This method enables pressure sensing in the range of 10 MPa to 50 GPa within a temperature range of 0-200°C.

[0024] Example 7: To achieve high-precision detection of deep earth pressure over a wide range, Ag flakes are used. 1.7 Cu 0.3 S 0.7 Se 0.3 , Ag2S two silver-based chalcogenides are used as pressure sensitive resistor materials, and heavy rare earth element component rare earth nickel-based oxide DyNiO3 ceramics are used as temperature sensing materials. Figure 5In the seawater environment with the temperature and pressure to be measured, the ambient temperature is first measured by DyNiO3 ceramics, and the Ag is obtained at the corresponding temperature by referring to the pre-determined relationship between the sensitive resistor resistance, temperature and pressure. 1.7 Cu 0.3 S 0.7 Se 0.3 The relationship between the DC resistance and pressure of two silver-based chalcogenide sensitive resistors, Ag2S and Ag2S, is shown in Figure 2. 1.7 Cu 0.3 S 0.7 Se 0.3 The ambient pressure can be detected by measuring the resistance value of Ag2S and comparing it with the standard resistance-pressure relationship at the corresponding temperature. The ambient pressure can be detected by measuring the resistance value of Ag2S and comparing it with the standard resistance-pressure relationship at the corresponding temperature in the high-pressure range of 100MPa-50GPa.

[0025] Example 8: To measure the simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes were used. 0.8 Te 0.2 As a pressure sensitive resistor material, a heavy rare earth element component rare earth nickel-based oxide DyNiO3 ceramic is used as a temperature sensing material. Among them, the relationship between the DC resistance of the sheet Ag2S sensitive resistor and temperature and pressure is as follows: Figure 4 In a certain temperature and pressure seawater environment, the ambient temperature is first measured by DyNiO3 ceramics. Figure 4 The relationship between the DC resistance of the Ag2S sensitive resistor and the pressure is obtained at the corresponding temperature. The DC resistance of the Ag2S sensitive resistor is further measured in the test environment to obtain the environmental pressure value.

[0026] Example 9: To realize pressure alarm under the environment pressure of deep sea hydrostatic pressure at room temperature, a cylindrical Ag2S 0.6 Se 0.4 As a sensitive resistor material, its resistivity decreases slowly with increasing pressure until the pressure reaches 120MPa, triggering the metal-insulator phase transition of the material and causing a sudden 12-fold decrease in resistivity. 0.6 Se 0.4 The shape is designed to achieve a low resistance state of the metal phase at a critical pressure, with a resistance of 10 ohms, and is connected to the trigger external circuit through a silver electrode and a platinum wire. 0.6 Se 0.4 As a sensitive resistor, it sends out an electrical signal when the resistance is lower than 10 ohms, and triggers an alarm when the pressure exceeds 120MPa.

[0027] Example 10: To achieve a pressure alarm at room temperature under ambient pressure simulating deep-sea hydrostatic pressure, a sheet of Ag2S is used as the sensitive resistor material. Its resistivity slowly decreases with increasing pressure until the pressure reaches 50 GPa, triggering a metal-insulator phase transition in the material and resulting in a sudden 10-fold decrease in resistivity. The Ag2S shape is designed to achieve a low-resistance metallic state of 100 ohms at a critical pressure. Silver electrodes are connected to platinum wires via external trigger circuits. When the detection circuit detects that the resistance of the Ag2S sensitive resistor falls below 100 ohms, an electrical signal is generated, triggering an alarm when the pressure exceeds 50 GPa.

[0028] Example 11: To achieve coordinated detection of temperature and pressure in a simulated deep-earth environment and to provide an alarm for a specific pressure, filamentous Ag2S and Ag2S 0.7 Te 0.3 、Ag2S 0.7 Se 0.3 、Ag2S 0.6 Se 0.4 、Ag 1.9 Cu 0.1 S 0.8 Se 0.2 、Ag 1.8 Hg 0.2 Six different types of silver-based chalcogenides are used as sensitive resistor materials, with platinum wires welded at both ends to connect to the measurement circuit. 0.7 Te 0.3 Two types of silver-based chalcogenide sensitive resistors are used for pressure alarms. Their metal phase resistance is controlled to 10 ohms through shape design. The remaining four types of silver-based chalcogenide sensitive resistor materials are used for temperature and pressure sensing. The relationship between their resistance values ​​and temperature and pressure is measured and combined with mathematical fitting to obtain the functional relationship between their resistance value, temperature, and pressure: Ag2S 0.7 Se 0.3 (P,T), Ag2S 0.6 Se 0.4 (P,T), Ag 1.9 Cu 0.1 S 0.8 Se 0.2 (P,T), Ag 1.8 Hg 0.2 S(P,T). In the temperature and pressure environment to be measured, measure the resistance R of the four silver-based chalcogenide resistors used for sensing. Ag2S0.7Se0.3 '、R Ag2S0.6Se0.4 '、R Ag1.9Cu0.1S0.8Se0.2 '、R Ag1.8Hg0.2S '; Construct four equations based on the pressure and temperature relationship: Ag2S 0.7 Se 0.3 (P,T)=RAg2S0.7Se0.3 ', Ag2S 0.6 Se 0.4 (P,T)=R Ag2S0.6Se0.4 ', Ag 1.9 Cu 0.1 S 0.8 Se 0.2 (P,T)=R Ag1.9Cu0.1S0.8Se0.2 ', Ag 1.8 Hg 0.2 S(P,T)=R Ag1.8Hg0.2S '; Solve the two equations together to obtain temperature and pressure; take the average value to obtain ambient temperature and pressure. At the same time, when Ag2S 0.7 Te 0.3 When the resistance value is less than 10 ohms, it will be used as a 500MPa high pressure alarm. 0.7 Te 0.3 When the resistance value is less than 10 ohms, it acts as a 50GPa high pressure alarm.

[0029] Example 12: To further increase the operating temperature of the silver-based chalcogenide sensor, ion implantation was used to dope sheet-like Ag2S with oxygen as the sensitive resistor material. This eliminated the metal-insulator phase transition characteristics of the material, and its resistivity decreased with increasing temperature and pressure within the temperature range of 200K to 600K and the pressure range of 100MPa-50GPa. The above-mentioned sensitive resistor material was used as a pressure sensing resistor, and DyNiO3 ceramic, a heavy rare earth element component and a rare earth nickel-based oxide, was used as the temperature sensing material. Under a seawater environment with a certain temperature and pressure, the ambient temperature was first measured using the DyNiO3 ceramic. At this temperature, the ambient pressure value was obtained by further measuring the DC resistance of the Ag2S sensitive resistor in the test environment, based on the relationship between the DC resistance and pressure of the prepared oxygen-doped silver-based chalcogenide sensitive resistor.

[0030] Example 13: To further achieve the measurement of simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes and Ag2S flakes are used. 0.5 Se 0.5 Two different components of silver-based chalcogenides are used as sensitive resistor materials. Among them, the relationship between the DC resistance of the Ag2S sheet sensitive resistor and temperature and pressure is as follows Figure 4 As shown, based on Figure 4 The experimental data shown in the figure are combined with mathematical fitting to obtain the functional relationship R of the resistance value-temperature-pressure of the Ag2S sensitive resistor. Ag2S Taylor broadening form of (P,T); A similar method was used to construct a Ag2S 0.5 Se 0.5 Functional relationship R of sensitive resistor's resistance value-temperature-pressure Ag2S0.5Se0.5(P, T). Under a certain temperature and pressure seawater environment, the flake Ag2S and flake Ag2S were measured respectively. 0.5 Se 0.5 The resistance value R Ag2S ', R Ag2S0.5Se0.5 ', and construct a system of two-variable equations: R Ag2S0.5Se0.5 (P,T)=R Ag2S0.5Se0.5 ', R Ag2S (P,T)=R Ag2S By solving the above binary equations, we can obtain the temperature and pressure of the ocean environment to be detected, and further refer to the seawater density and temperature distribution to calculate the seawater depth.

[0031] Example 14: To further achieve the measurement of simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes and Ag2S flakes are used. 0.5 Se 0.5 Two different components of silver-based chalcogenides are used as sensitive resistor materials. Silver electrodes are made at both ends of the metal sheet and connected to the measurement circuit through platinum wire. Among them, the relationship between the DC resistance of the sheet Ag2S sensitive resistor and temperature and pressure is as follows: Figure 4 As shown, based on Figure 4 The experimental data shown in the figure are combined with mathematical fitting to obtain the functional relationship R of the resistance value-temperature-pressure of the Ag2S sensitive resistor. Ag2S Taylor broadening form of (P,T); A similar method was used to construct a Ag2S 0.5 Se 0.5 Functional relationship R of sensitive resistor's resistance value-temperature-pressure Ag2S0.5Se0.5 (P, T). Under a certain temperature and pressure seawater environment, the flake Ag2S and flake Ag2S were measured respectively. 0.5 Se 0.5 The resistance value R Ag2S ', R Ag2S0.5Se0.5 ', and construct a system of two-variable equations: R Ag2S0.5Se0.5 (P,T)=R Ag2S0.5Se0.5 ', R Ag2S (P,T)=R Ag2S By solving the above binary equations, we can obtain the temperature and pressure of the ocean environment to be detected, and further refer to the seawater density and temperature distribution to calculate the seawater depth.

[0032] Example 15: To achieve coordinated detection of temperature and pressure in a simulated deep-earth environment, filamentous Ag2S and Ag2S 0.9 Te 0.1 、Ag2S 0.8 Se 0.2 、Ag2S 0.7 Se 0.3 、Ag 1.9 Cu 0.1S 0.7 Se 0.3 、Ag 1.8 Hg 0.2 Five different types of silver-based chalcogenides were used as sensitive resistor materials, with platinum wires welded at both ends to connect to the measurement circuit. The relationship between the resistance values ​​of the five silver-based chalcogenides and temperature and pressure was measured and the functional relationship between resistance value, temperature and pressure was obtained by mathematical fitting: R Ag2S (P,T),R Ag2S0.9Te0.1 (P,T),R Ag2S0.8Se0.2 (P,T),R Ag2S0.7Se0.3 (P,T),R Ag1.9Cu0.1S0.7Se0.3 (P,T),R Ag1.8Hg0.2S (P, T). Measure the resistance values ​​of the above five silver-based chalcogenide resistors R in the temperature and pressure environment to be measured. Ag2S '、R Ag2S0.9Te0.1 '、R Ag2S0.8Se0.2 '、R Ag2S0.7Se0.3 '、R Ag1.9Cu0.1S0.7Se0.3 '、R Ag1.8Hg0.2S '. Constructing the system of equations: R Ag2S (P,T)=R Ag2S ', R Ag2S0.9Te0.1 (P,T)=R Ag2S0.9Te0.1 ', R Ag2S0.7Se0.3 (P,T)=R Ag2S0.7Se0.3 ', R Ag1.9Cu0.1S0.7Se0.3 (P,T)=R Ag1.9Cu0.1S0.7Se0.3 ', R Ag1.8Hg0.2S (P,T)=R Ag1.8Hg0.2S Solve the above equations pairwise to obtain the temperature and pressure; take the average value to obtain the ambient temperature and pressure.

[0033] Example 16: To measure the simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes were used. 0.8 Te 0.2 As a pressure sensitive resistor material, the heavy rare earth element component rare earth nickel-based oxide GdNiO3 ceramic is used as a temperature sensing material. In a certain temperature and pressure seawater environment, the ambient temperature is first measured by GdNiO3 ceramic, and the Ag2S is obtained at the corresponding temperature by referring to the pre-determined relationship between the sensitive resistor resistance, temperature and pressure. 0.8 Te 0.2 The relationship between the DC resistance of the sensitive resistor and the pressure. Further measurement of Ag2S in the test environment 0.8 Te 0.2 The ambient pressure value is obtained by measuring the DC resistance of the sensitive resistor. Through the above method, pressure sensing in the range of 1MPa to 1GPa can be achieved in the temperature range above 50 degrees Celsius.

[0034] Example 17: To measure simulated deep-earth pressure under variable temperature conditions, sheet-like Ag2S was used as the pressure-sensitive resistor material, and GdNiO3 ceramic, a heavy rare earth element component and nickel-based oxide, was used as the temperature sensing material. Under a seawater environment with a constant temperature and pressure, the ambient temperature was first measured using the GdNiO3 ceramic. The relationship between the DC resistance of the Ag2S sensitive resistor and pressure was then determined by referring to the previously measured relationship between the sensitive resistor's resistance, temperature, and pressure at the corresponding temperature. The DC resistance of the Ag2S sensitive resistor was further measured in the test environment to obtain the ambient pressure. This method enables pressure sensing in the range of 10 MPa to 50 GPa within a temperature range of 200-400°C.

[0035] Example 18: To measure the simulated deep-sea hydrostatic pressure under variable temperature conditions, Ag2S flakes were used. 0.8 Te 0.2 As a pressure sensitive resistor material, a heavy rare earth element component rare earth nickel-based oxide GdNiO3 ceramic is used as a temperature sensing material. Among them, the relationship between the DC resistance of the sheet Ag2S sensitive resistor and temperature and pressure is as follows: Figure 4 In a certain temperature and pressure seawater environment, the ambient temperature is first measured by GdNiO3 ceramics. Figure 4 The relationship between the DC resistance of the Ag2S sensitive resistor and the pressure is obtained at the corresponding temperature. The DC resistance of the Ag2S sensitive resistor is further measured in the test environment to obtain the environmental pressure value.

[0036] Example 19: To realize pressure alarm under the environment pressure of deep sea hydrostatic pressure at room temperature, a cylindrical Ag2S 0.5 Se 0.5 As a sensitive resistor material, its resistivity decreases slowly with increasing pressure until the pressure reaches 50MPa, triggering the metal-insulator phase transition of the material and causing a sudden 5-fold decrease in resistivity. 0.5 Se 0.5 The shape is designed to achieve a low resistance state of the metal phase at a critical pressure, with a resistance of 1 ohm, and is connected to the trigger external circuit through a silver electrode and a platinum wire. 0.6 Se 0.4 As a sensitive resistor, it sends out an electrical signal when the resistance is lower than 1 ohm, and triggers an alarm when the pressure exceeds 50MPa.

[0037] Example 20: To achieve coordinated detection of temperature and pressure in a simulated deep-earth environment and to provide an alarm for a specific pressure, filamentous Ag2S and Ag2S 0.8 Te 0.2 、Ag2S 0.5 Se 0.5 、Ag2S0.6 Se 0.4 、Ag 1.9 Cu 0.1 S 0.8 Se 0.2 、Ag 1.8 Hg 0.2 Six different types of silver-based chalcogenides are used as sensitive resistor materials, with platinum wires welded at both ends to connect to the measurement circuit. 0.5 Te 0.5 Two types of silver-based chalcogenide sensitive resistors are used for pressure alarms. Their metal phase resistance is controlled to 1 ohm through shape design. The remaining four types of silver-based chalcogenide sensitive resistor materials are used for temperature and pressure sensing. The relationship between their resistance values ​​and temperature and pressure is measured and combined with mathematical fitting to obtain the functional relationship between their resistance value, temperature and pressure: Ag2S 0.8 Te 0.2 (P,T), Ag2S 0.6 Se 0.4 (P,T), Ag 1.9 Cu 0.1 S 0.8 Se 0.2 (P,T), Ag 1.8 Hg 0.2 S(P,T). In the temperature and pressure environment to be measured, measure the resistance R of the four silver-based chalcogenide resistors used for sensing. Ag2S0.8Te0.2 '、R Ag2S0.6Se0.4 '、R Ag1.9Cu0.1S0.8Se0.2 '、R Ag1.8Hg0.2S '; Construct four equations based on the pressure and temperature relationship: Ag2S 0.8 Te 0.2 (P,T)=R Ag2S0.8Se0.2 ', Ag2S 0.6 Se 0.4 (P,T)=R Ag2S0.6Se0.4 ', Ag 1.9 Cu 0.1 S 0.8 Se 0.2 (P,T)=R Ag1.9Cu0.1S0.8Se0.2 ', Ag 1.8 Hg 0.2 S(P,T)=R Ag1.8Hg0.2S '; Solve the two equations together to obtain temperature and pressure; take the average value to obtain ambient temperature and pressure. At the same time, when Ag2S 0.5 Te 0.5 When the resistance value is less than 1 ohm, it will be used as 50MPa low pressure alarm. 0.5 Te 0.5 When the resistance value is less than 1 ohm, it acts as a 50GPa high pressure alarm.

Claims

1. An application of a silver-based chalcogenide array temperature-pressure synergistic sensor material, characterized in that: The silver-based chalcogenide array temperature-pressure synergistic sensor material is a temperature and pressure sensitive material, and its chemical formula is Ag 2-x A x S 1-y B y ; Wherein A is a silver atomic substitution element, including Cu, Hg, Cs, K elements, 0≤x≤1.5; B is a sulfur atomic substitution element, including Se, Te, O elements, 0≤y≤1; the material can realize the coordinated measurement of pressure and temperature in solid, liquid and gas environments, as well as critical temperature and pressure warning applications; on the one hand, by designing the components of silver-based chalcogenide materials, the relationship between the resistivity of its insulating phase and the temperature and pressure is designed, and silver-based chalcogenide compounds with multiple material components are selected according to the temperature and pressure range of the intended detection environment to make array detection components; the above-mentioned silver-based chalcogenide compounds prepared with different components are measured in the intended detection environment. The resistance of the temperature and pressure detection components is measured, and then multiple binary equations about pressure and temperature are constructed with reference to the standard mathematical expressions of the resistivity, temperature and pressure relationship of the corresponding material components. The ambient pressure and temperature values ​​are obtained by solving the above equations. On the other hand, the critical triggering temperature and critical triggering pressure of the electronic phase transition of the silver-based chalcogenide compound are regulated by the material components, and the resistivity mutation triggered by the electronic phase transition is used to realize the early warning of the critical temperature and pressure in the environment. According to the critical temperature and pressure range to be warned, the critical temperature and pressure warning range can be regulated and designed by using a single material component component or a silver-based chalcogenide component unit with multiple material components.

2. The use of the silver-based chalcogenide array temperature-pressure synergistic sensor material according to claim 1, characterized in that: The silver-based chalcogenide compound has metal-insulator phase transition characteristics triggered by critical temperature and critical pressure; The material is in an insulating phase below a critical temperature and a critical pressure, and its resistivity gradually decreases with increasing temperature and pressure. When the temperature and pressure rise to the critical triggering threshold of the electronic phase transition, the silver-based chalcogenide compound transforms into a metal, and its resistivity suddenly decreases. By regulating the material components of the silver-based chalcogenide compound, the relationship between its insulating phase resistivity and temperature and pressure can be designed, as can the critical triggering temperature and critical triggering pressure of its electronic phase transition.

3. The use of the silver-based chalcogenide array temperature-pressure synergistic sensor material according to claim 1, characterized in that: According to the temperature and pressure ranges of the environment to be measured, the material components of the silver-based chalcogenide compound are selected and made into sensitive resistor chips one by one, and further connected with the resistance measurement circuit through leads. The shape of the sensitive resistor chip can be cylindrical, filamentous, sheet-like, rectangular, or ellipsoidal. The leads connected to the external circuit can be platinum wire, copper wire, aluminum wire, or gold wire. The contact material between the silver-based chalcogenide compound sensitive resistor material and the leads can be silver, copper, or aluminum.

4. The use of the silver-based chalcogenide array temperature-pressure synergistic sensor material according to claim 1, characterized in that: To achieve temperature and pressure sensing applications, in addition to using multiple silver-based chalcogenide compound sensitive resistor components to form an array as described above, if the ambient temperature to be detected is known and does not change significantly, only one silver-based chalcogenide compound material can be used to make a pressure-sensitive resistor component. By measuring the resistance of the silver-based chalcogenide compound in the test environment and referring to the resistivity-pressure relationship curve of the sensitive resistor material used at the corresponding ambient temperature, the ambient pressure can be detected. In addition, only one silver-based chalcogenide compound material whose resistivity is sensitive to changes in temperature and pressure within the test ambient temperature and pressure range can be selected to make a pressure-sensitive resistor component. It is used in conjunction with a thermistor device whose resistivity is sensitive to temperature but insensitive to pressure within the temperature and pressure range of the environment to be measured. In the temperature and pressure environment to be measured, the resistance of the thermistor whose resistivity is sensitive to temperature but insensitive to pressure and the resistance of the silver-based chalcogenide compound sensitive resistor whose resistivity is sensitive to both temperature and pressure are measured. The ambient temperature is first obtained by comparing the resistance of the thermistor with its standard resistance-temperature relationship, and the ambient pressure is further obtained by comparing the corresponding relationship between the resistance of the silver-based chalcogenide compound sensitive resistor used at the corresponding temperature and pressure.

5. The use of the silver-based chalcogenide array temperature-pressure synergistic sensor material according to claim 1, characterized in that: By selecting silver-based chalcogenide material components and preparing an array temperature and pressure sensor, it is possible to achieve coordinated measurement of temperature and pressure in solid, liquid, and gaseous environments in the pressure range of 1 MPa to 50 GPa and the temperature range of 200 K to 600 K, as well as critical threshold warning; it can be applied to the coordinated measurement of temperature and pressure in deep-sea exploration, deep earth exploration, and oil exploration and production environments.

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