A transition metal chalcogenide temperature sensitive layer and temperature sensor

Abstract

The application discloses a transition metal chalcogen compound temperature-sensitive layer and a temperature sensor, wherein the thickness of the temperature-sensitive layer is 1-100 nm; the temperature-sensitive layer is formed by depositing transition metal chalcogen compound and alloy material; the transition metal chalcogen compound is MX2, M=Mo, W or Nb; X=S, Se or Te; the transition metal chalcogen compound alloy is M 1‑x N x X 2(1‑y) Y 2y , M / N=Mo, W or Nb; X / Y=S, Se or Te; wherein x=0-1, y=0-1. When the temperature changes, the resistance of the temperature-sensitive layer changes, and the temperature can be detected by measuring the resistance between the metal interdigital electrodes. The temperature sensor has the advantages of simple structure, low cost, fast response (millisecond level) and high resolution in a super-wide temperature range (-197-1200 DEG C), and can realize high-precision and fast detection of an extremely low-temperature and an extremely high-temperature environment.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of nanomaterials, and particularly relates to a transition metal chalcogenide temperature-sensitive layer and a temperature sensor. BACKGROUND

[0002] The temperature sensor refers to a sensor capable of sensing temperature and converting the temperature into an output signal. The temperature sensor can be divided into a contact type and a non-contact type according to a measurement mode. The contact type temperature sensor has the advantages of high measurement accuracy and real-time response. However, most of the common commercial contact type sensors are made of rigid materials. The emergence of the flexible temperature sensor provides a more comfortable choice for real-time monitoring of wearable devices, greatly facilitating people's daily life. Meanwhile, the flexible temperature sensor has important significance for temperature monitoring and accurate control in the fields of electronics, medicine, metallurgy, national defense engineering and food and industry. In today's science and technology, real-time and accurate wide-temperature-range temperature monitoring plays an irreplaceable role in the development of science and technology. The research and development of the flexible temperature sensor have important value for the progress of contemporary science and technology.

[0003] At present, the temperature sensing elements that are studied more include semiconductors, carbon nanomaterials (graphene) and metals. However, these materials all have respective shortcomings. For example, as a representative of carbon nanomaterials, graphene has high temperature coefficient of resistance (TCR) and mechanical stability, but the response and recovery effect requires a long time, and the low-temperature and high-temperature resistance is poor. While the metal has high precision and fast response time, but the temperature coefficient of resistance (TCR) is low. In addition, the low-dimensional material that is currently concerned has fast response and high TCR, but the preparation process is complex and is limited by the working temperature range of the plastic film. Therefore, it is necessary to develop a temperature sensor with wide temperature range and high TCR for practical application. SUMMARY

[0004] The application aims to provide a transition metal chalcogenide temperature-sensitive layer and a temperature sensor, so as to provide a high-precision temperature sensor with wide temperature range and good stability.

[0005] To achieve the object, the following steps need to be implemented:

[0006] A transition metal chalcogenide temperature-sensitive layer, the thickness of the temperature-sensitive layer is 1-100 nm; the temperature-sensitive layer is formed by deposition of a transition metal chalcogenide and an alloy material thereof;

[0007] The transition metal chalcogenide is MX2, M=Mo, W or Nb; X=S, Se or Te;

[0008] The alloy of the transition metal chalcogenide is M 1-x Nx X 2(1-y) Y 2y M / N=Mo, W or Nb; X / Y=S, Se or Te, wherein x=0-1, y=0-1.

[0009] Optionally, the alloy of the transition metal chalcogenide compound is a molybdenum-tungsten-sulfur alloy, and the molar ratio of Mo / W is (10-0):(0-10).

[0010] Optionally, the alloy of the transition metal chalcogenide compound is a molybdenum-tungsten-sulfur alloy, and the molar ratio of Mo / W is (8-2):(2-8).

[0011] Optionally, the alloy of the transition metal chalcogenide compound is a molybdenum-tungsten-sulfur alloy, and the molar ratio of Mo / W is (6-4):(4-6).

[0012] The application of the transition metal chalcogenide temperature-sensitive layer in any of the application to the preparation of a temperature sensor.

[0013] A temperature sensor is provided with a substrate, a metal interdigital electrode is attached to the surface of the substrate, and a temperature-sensitive layer and a passivation layer are sequentially attached to the metal interdigital electrode; the temperature-sensitive layer is the transition metal chalcogenide temperature-sensitive layer in any of the application.

[0014] Optionally, the substrate is selected from one of polyimide, silicon wafer, glass, mica, corundum and sapphire, and the thickness of the substrate is 0.01-2 mm.

[0015] Optionally, the preparation material of the metal interdigital electrode is selected from at least one of gold, platinum and copper; the deposition method of the metal interdigital electrode is vacuum evaporation, magnetron sputtering, electron beam evaporation or physical vapor deposition, the thickness is 5-200 nm, and the interdigital electrode with a line width and line spacing of 0.1 mm is formed on the surface of the substrate by laser etching technology.

[0016] Optionally, the preparation material of the passivation layer is selected from at least one of molybdenum oxide, tungsten oxide, titanium dioxide and aluminum oxide, and the deposition method is thermal evaporation, chemical vapor deposition or atomic layer deposition, and the thickness is 10-100 nm.

[0017] Optionally, the temperature sensor is a flexible temperature sensor, and the preparation method is to use conductive carbon oil as an adhesive between the electrode and the test lead, and after the carbon oil is cured, a temperature sensor is obtained, and a temperature sensor array composed of sensing elements is prepared at the same time, and each element is a square sensor with a side length of 1-10 mm.

[0018] The application has the following advantages:

[0019] The temperature sensor prepared by the application can respond to an ultra-wide temperature range, and the response range is -197-1200 DEG C; the temperature sensor prepared based on the flexible or non-flexible substrate can realize fast response and high resolution, and the response speed is 0.025 s and the resolution is 0.02 DEG C. BRIEF DESCRIPTION OF DRAWINGS

[0020] In order to more clearly illustrate the content of the application, the following will be combined with the specific embodiments and the drawings to make a detailed description.

[0021] Figure 1 It is a structural schematic diagram of the temperature sensor of the application.

[0022] Figure 2 It is a real photo of examples 1-6.

[0023] Figure 3 It is a curve diagram of the resistance change rate with temperature change of example 5.

[0024] Figure 4 It is an optical photo of example 10.

[0025] Figure 5 It is a real photo of example 17. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the application will be described clearly and completely in combination with the drawings. It should be pointed out that, for ordinary people in the technical field, some improvements and refinements can be made without departing from the principles of the application, and these improvements and refinements are also regarded as the protection scope of the application.

[0027] In order to prepare a high-precision and fast-response wide-temperature-range temperature sensor, real-time temperature monitoring in extreme environments and medical treatment is realized. The application provides a preparation method of a wide-temperature-range and fast-response temperature sensor, which can be printed on different substrates to realize flexible or non-flexible temperature sensing.

[0028] The application provides a transition metal chalcogenide temperature-sensitive layer, the thickness of the temperature-sensitive layer is 1-100 nm; the temperature-sensitive layer is deposited by a transition metal chalcogenide and an alloy material of the transition metal chalcogenide; the transition metal chalcogenide is MX2, M=Mo, W or Nb; X=S, Se or Te; the alloy of the transition metal chalcogenide is M 1-x N x X 2(1-y) Y 2y , M / N=Mo, W or Nb; X / Y=S, Se or Te, x=0-1, y=0-1, here, x and y can be an integer of 0 and 1, or a decimal between 0 and 1.

[0029] In the embodiments of the present disclosure, the alloy of the transition metal chalcogenide compound is a molybdenum-tungsten-sulfur alloy, and the molar ratio of Mo / W is (10-0):(0-10).

[0030] Preferably, the alloy of the transition metal chalcogenide compound is a molybdenum-tungsten-sulfur alloy, and the molar ratio of Mo / W is (8-2):(2-8).

[0031] Preferably, the alloy of the transition metal chalcogenide compound is a molybdenum-tungsten-sulfur alloy, and the molar ratio of Mo / W is (6-4):(4-6).

[0032] The application of the transition metal chalcogenide temperature-sensitive layer of the present application to the preparation of a temperature sensor.

[0033] In combination Figure 1 The temperature sensor of the present application comprises a substrate 1, a metal interdigital electrode 2, a temperature-sensitive layer 3, and a passivation layer 4; the metal interdigital electrode 2 is arranged on the upper surface of the substrate 1, the metal interdigital electrode 2 is covered with a layer of temperature-sensitive layer 3, and the passivation layer 4 is arranged on the upper surface of the temperature-sensitive layer 3.

[0034] The substrate is selected from one of polyimide, silicon wafer, glass, mica, corundum, and sapphire, and the thickness of the substrate is 0.01-2 mm.

[0035] The material of the metal interdigital electrode is at least one of gold, platinum, and copper, the deposition method is vacuum evaporation, magnetron sputtering, electron beam evaporation, or physical vapor deposition, the thickness is 5-200 nm, and the interdigital electrode with a line width and line spacing of 0.1 mm is formed on the surface of the substrate by laser etching technology.

[0036] The material of the passivation layer is at least one of molybdenum oxide, tungsten oxide, titanium dioxide, and aluminum oxide, the deposition method is one of thermal evaporation, chemical vapor deposition, and atomic layer deposition, and the thickness is 10-100 nm.

[0037] The application of the material of the present application to the preparation of a temperature sensor.

[0038] Specifically, the preparation of the flexible temperature sensor specifically includes: the preparation method is to use conductive carbon oil as the adhesive between the electrode and the test lead, and after the carbon oil is cured, a temperature sensor is obtained, and a temperature sensing array composed of sensing elements is prepared at the same time. Each element is a square sensor with a side length of 1-10 mm. Optionally, the preparation of the flexible temperature sensor specifically includes:

[0039] The preparation method of the wide-temperature-range and fast-response temperature sensor is described in detail below through specific embodiments.

[0040] Example 1:

[0041] A gold interdigitated electrode / molybdenum tungsten sulfide alloy / passivation layer temperature sensor deposited on a substrate is provided, which is prepared by the following method:

[0042] (1) Preparation of gold interdigitated electrode:

[0043] Taking PI as the substrate, gold is first plated on the PI substrate by thermal evaporation method, with a thickness of 50 nm, and then the excess gold on the substrate is removed by laser etching technology using a pre-designed pattern to obtain an interdigitated electrode, with a line width and line spacing of 0.1 mm. Then, the gold electrode and PI substrate are subjected to 4 minutes of ultraviolet ozone treatment.

[0044] (2) Preparation of molybdenum tungsten sulfide alloy sensitive layer:

[0045] A precursor (ammonium tetrathiomolybdate and ammonium thiometatungstate) with a Mo / W molar ratio of 2:8 is prepared and deposited on the surface of the gold electrode, and then the deposited precursor is subjected to 400°C annealing treatment by thermal reduction to obtain a molybdenum tungsten sulfide alloy sensitive layer with a thickness of 40 nm;

[0046] (3) Preparation of passivation layer:

[0047] The molybdenum tungsten sulfide alloy temperature sensor is successfully prepared by depositing 50 nm thick aluminum oxide on the surface of the sensitive layer by atomic layer deposition.

[0048] Examples 1-6 provide a gold interdigitated electrode / molybdenum tungsten sulfide alloy / passivation layer temperature sensor deposited on a substrate, except for the conditions described in Table 1, the specific operation process is the same as that in Example 1, Figure 2 are the temperature sensors prepared in Examples 1-6.

[0049] Table 1 Experimental conditions of Examples 1-6

[0050]

[0051]

[0052] Further, conductive carbon oil is used as an adhesive between the gold interdigitated electrode and the test lead wire. After the carbon oil is cured, the temperature sensor provided in Examples 1-6 is subjected to performance testing.

[0053] ① Temperature response range:

[0054] The test lead wire is connected to a digital multimeter, and the temperature sensor is gradually heated from -197°C to 550°C. The digital multimeter is used to record the resistance change during the heating process, and the response temperature range of the temperature sensor is calculated.

[0055] ② Response time

[0056] A heater is attached to the surface of the temperature sensor and a certain voltage is applied to it, thus generating a temperature which is conducted to the sensitive layer of the temperature sensor, causing the resistance of the temperature sensor to change. By analyzing the resistance-time curve recorded by the digital multimeter, the response time can be calculated.

[0057] ③Detection resolution

[0058] The heating rate is precisely controlled, and the temperature sensor is gradually heated to 0.02℃ and 0.05℃. The resistance change is recorded by a digital multimeter. If the regular change of resistance can be detected, it is considered that the detection resolution of 0.02℃ can be achieved.

[0059] The performance test results of Examples 1-6 are shown in Table 2:

[0060] Table 2 Performance test results of Examples 1-6

[0061]

[0062] The resistance change rate of Example 5 as a function of temperature is shown in Figure 3 It can be seen that as the temperature rises from -197℃ to 550℃, the resistance of the temperature sensor gradually decreases, indicating that the sensor has a wide temperature range. From the performance test results of Examples 1-6, it can be seen that as the content of tungsten in the sensitive layer increases, the temperature response range gradually expands, while the response time does not change significantly, remaining between 22-26 ms; in addition, the temperature sensor has a detection resolution of 0.02℃. The main reason for the widening of the temperature response range of the temperature sensor is that the doping of tungsten increases the band gap of the alloy material, and the carrier concentration is increased, so that a higher temperature can be responded. However, when the sensitive layer is tungsten sulfide (Example 6), the temperature response range of the sensor becomes narrower. This is mainly due to the poor conductivity of tungsten sulfide, which exceeds the range of the digital multimeter at low temperatures, so the test results cannot be obtained.

[0063] Examples 7-11 each provide a gold interdigital electrode / molybdenum-tungsten-sulfur alloy / passivation layer temperature sensor deposited on a substrate, which differs from Example 5 in that the PI substrate is replaced in turn by a silicon wafer, glass, mica, corundum, and sapphire, Figure 4 An optical photograph of Example 10.

[0064] Performance test:

[0065] The gold interdigital electrode / molybdenum-tungsten-sulfur alloy / passivation layer temperature sensors deposited on a substrate provided by Examples 7-11 are tested for temperature response range, response time, and detection resolution, using the same test method as Examples 1-6, and the sensor test results are shown in Table 3:

[0066] Table 3 Sensor performance test results of Examples 7-11

[0067]

[0068] As can be seen from Table 3, on inorganic substrates, the temperature sensor with molybdenum-tungsten-sulfur alloy as the sensitive layer can respond to temperature in a super-wide temperature range of -197 to 1200°C, which is mainly because the substrate can withstand the super-wide temperature range; and the response time still remains in the millisecond level, indicating that this method can be implemented on most substrates and is a relatively universal method.

[0069] Embodiments 12-16 respectively provide a temperature sensor deposited on a substrate, which is different from that of Embodiment 11 in that the sensitive layer is in turn tungsten-niobium-selenium (W 1-x Nb x S2) alloy, molybdenum-tungsten-selenium (Mo 1-x W x Se2) alloy, molybdenum-tungsten-tellurium (Mo 1-x W x Te2) alloy, molybdenum-sulfur-selenium (MoS 2(1-x) Se 2x ) alloy, molybdenum-selenium-tellurium (MoSe 2(1-x) Te 2x ) alloy, wherein x = 0.5.

[0070] Performance test:

[0071] The temperature sensor deposited on a substrate provided by Embodiments 12-16 is tested for temperature response range, response time and detection resolution, and the testing method is the same as that of Embodiments 1-6, and the sensing test results are shown in Table 4:

[0072] Table 4 Sensing performance test results of Embodiments 12-16

[0073]

[0074] As can be seen from Table 4, the transition metal chalcogenide alloy with different proportions can all have good temperature response characteristics in a super-wide temperature range, indicating that this method has a certain universality and can use most sensitive materials.

[0075] Embodiment 17 respectively provides a gold interdigital electrode / molybdenum-tungsten-sulfur alloy / passivation layer temperature sensor array deposited on a substrate, which is different from Embodiment 5 in that a 6x6 temperature sensor array composed of sensing units is designed and prepared, as shown in Figure 5 , which can realize multi-point temperature detection and has wide application.

[0076] Performance test:

[0077] The gold interdigital electrode / molybdenum-tungsten sulfide alloy / passivation layer temperature sensor array deposited on the substrate provided by Example 17 was subjected to temperature response range, response time and detection resolution tests, and the test method was the same as that of Examples 1-6. The sensor test results showed that the temperature response range was -197-550°C, the response time was 25.6 ms, and the detection resolution was 0.02°C.

[0078] In addition, it should be noted that each specific technical feature described in the foregoing specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the present disclosure.

[0079] Furthermore, various different embodiments of the present disclosure can also be combined in any appropriate manner, as long as they do not contradict the idea of the present disclosure, and they should also be considered as disclosed in the present disclosure.

Claims

1. A transition metal chalcogenide thermosensitive layer, characterized in that, The thickness of the temperature-sensitive layer is 1–100 nm; The temperature-sensitive layer is formed by deposition of an alloy material of transition metal chalcogenides; The alloy of the transition metal chalcogenide is M. 1-x N x X 2（1-y） Y 2y M = Mo, W, or Nb; N = Mo, W, or Nb; X = S, Se, or Te; Y = S, Se, or Te. Where x = 0 to 1, y = 0 to 1, and x and y do not take endpoint values ​​at the same time; When M and N have the same element, X and Y do not have the same element; when X and Y have the same element, M and N do not have the same element.

2. The transition metal chalcogenide thermosensitive layer according to claim 1, characterized in that, The alloy of the transition metal chalcogenide is a molybdenum-tungsten-sulfur alloy, with a molar ratio of Mo to W of (10-0):(0-10).

3. The transition metal chalcogenide thermosensitive layer according to claim 1, characterized in that, The alloy of the transition metal chalcogenide is a molybdenum-tungsten-sulfur alloy, with a molar ratio of Mo to W of (8-2):(2-8).

4. The transition metal chalcogenide thermosensitive layer according to claim 1, characterized in that, The alloy of the transition metal chalcogenide is a molybdenum-tungsten-sulfur alloy, with a molar ratio of Mo to W of (6-4):(4-6).

5. The application of the transition metal chalcogenide thermosensitive layer according to any one of claims 1-4 in the preparation of temperature sensors.

6. A temperature sensor, characterized in that, A substrate (1) is provided, and a metal interdigitated electrode (2) is attached to the surface of the substrate (1). A temperature-sensitive layer (3) and a passivation layer (4) are sequentially covered on the metal interdigitated electrode (2). The temperature-sensitive layer (3) is a transition metal chalcogenide temperature-sensitive layer as described in any one of claims 1-4.

7. The temperature sensor according to claim 6, characterized in that, The substrate (1) is selected from one of polyimide, silicon wafer, glass, mica, corundum and sapphire, and the substrate thickness is 0.01 to 2 mm.

8. The temperature sensor according to claim 6, characterized in that, The material used to prepare the metal interdigitated electrode is selected from at least one of gold, platinum, and copper; The metal intercalation electrodes are deposited by vacuum evaporation, magnetron sputtering, electron beam evaporation or physical vapor deposition, with a thickness of 5 to 200 nm. Intercalation electrodes with a linewidth and line spacing of 0.1 mm are formed on the substrate surface by laser etching technology.

9. The temperature sensor according to claim 6, characterized in that, The passivation layer is prepared from at least one of molybdenum oxide, tungsten oxide, titanium dioxide, and aluminum oxide, and is deposited by thermal evaporation, chemical vapor deposition, or atomic layer deposition, with a thickness of 10–100 nm.

10. The temperature sensor according to claim 6, characterized in that, The temperature sensor is a flexible temperature sensor. The preparation method is to use conductive carbon oil as an adhesive between the electrode and the test lead. After the carbon oil is cured, the temperature sensor is obtained. At the same time, a temperature sensing array composed of sensing elements is prepared, each element being a square sensor with a side length of 1 to 10 mm.

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