A ruthenium-doped chromium phosphide material and its preparation method and application

Abstract

This invention discloses a ruthenium-doped chromium phosphide material, its preparation method, and its applications, belonging to the field of sensor material application technology. The chemical formula of this material is Cr. 1‑x Ru x P, where 0.2

Description

Technical Field

[0001] This invention belongs to the field of sensor material application technology, and relates to a ruthenium-doped chromium phosphide material, its preparation method and application, specifically to a ruthenium-doped chromium phosphide material, its preparation method and its application in a wide temperature range temperature sensor. Background Technology

[0002] Temperature sensors are used to measure the temperature of the environment or objects. They are common sensors with wide applications in smart homes, healthcare, industrial automation, and agricultural production. The core component of a temperature sensor is a thermistor, whose resistance changes with temperature. A thermistor has a positive temperature coefficient (PTC) when its resistance increases with temperature; conversely, it has a negative temperature coefficient (NTC) when its resistance decreases with temperature. Due to the inherent properties of the material, thermistors are suitable for various temperature ranges, including extremely low temperatures, normal temperatures, and ultra-high temperatures.

[0003] Traditional temperature sensors such as PT, silicon diodes, thermocouples, and rhodium iron make accurate temperature measurement at low temperatures difficult due to the magnetoresistive effect under a magnetic field. Lake Shore Cryotronics' Cernox thin-film resistance temperature sensor offers high sensitivity at low temperatures, but its sensitivity at room temperature is insufficient. For example, the CX-1030 Cernox temperature sensor exhibits a temperature deviation ΔT = 1 mK at 4.2 K and ΔT = 30 mK at 300 K.

[0004] Therefore, how to develop a temperature sensor suitable for wide-range temperature measurement and applicable to ultra-low temperature strong magnetic field testing is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, the present invention provides a ruthenium-doped chromium phosphide material, its preparation method, and its application in a wide-temperature-range temperature sensor.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A ruthenium-doped chromium phosphide material, wherein the general chemical formula of the ruthenium-doped chromium phosphide material is Cr 1-x Ru x P, where 0.2 <x<0.4。

[0008] Furthermore, the aforementioned ruthenium-doped chromium phosphide material is in the form of a bulk material, a thin film, or a wire.

[0009] This invention also provides a method for preparing ruthenium-doped chromium phosphide material, comprising the following steps:

[0010] (1) According to the above general chemical formula and based on Cr 1-xRu x Calculate x in P and weigh each raw material;

[0011] (2) Mix and grind Cr powder, P powder and Ru powder evenly, press into shape, then wrap with quartz wool and put into quartz tube, draw high vacuum and seal, and finally fire the quartz tube at high temperature to obtain ruthenium-doped chromium phosphide polycrystalline.

[0012] (3) Grind the obtained ruthenium-doped chromium phosphide polycrystalline material into powder, put it into a crucible and add flux, then put the crucible into a quartz tube, draw a high vacuum and seal it, and finally sinter the quartz tube at high temperature and quench it to obtain ruthenium-doped chromium phosphide single crystal, namely the above-mentioned ruthenium-doped chromium phosphide material.

[0013] Furthermore, in step (2), Cr powder, P powder and Ru powder are mixed and ground to a particle size of 0.3 mm.

[0014] Furthermore, in step (2), the high-temperature firing temperature is 1000℃ and the high-temperature firing time is 2 days.

[0015] Furthermore, in step (3), the obtained ruthenium-doped chromium phosphide polycrystalline material is ground into powder with a particle size of 0.3 mm.

[0016] Furthermore, in step (3), the flux is tin particles, and the mass ratio of the ruthenium-doped chromium phosphide polycrystalline material to the flux is 1:2.

[0017] Furthermore, in step (3), the diameter of the tin particles is 1 mm.

[0018] Furthermore, in step (3), the high-temperature firing temperature is 1150℃ and the high-temperature firing time is 10 days.

[0019] Furthermore, in step (3), the specific quenching steps are to cool the temperature to 600°C and then quench it in water.

[0020] The present invention also provides an application of the above-mentioned ruthenium-doped chromium phosphide material in a wide-temperature-range temperature sensor.

[0021] Furthermore, the aforementioned wide-temperature-range temperature sensor includes a ruthenium-doped chromium phosphide material in bulk, electrodes, leads, and a protective coating. The leads are connected to the ruthenium-doped chromium phosphide material through the electrodes. The protective coating encapsulates the ruthenium-doped chromium phosphide material in bulk. The protective coating can be a metal coating, ceramic coating, glass coating, black glue coating, titanium oxide coating, low-temperature grease coating, or epoxy resin coating.

[0022] The electrodes are made of extremely fine metal wires with a diameter of ≤0.1 mm, and are made of gold, silver, copper, platinum, indium, palladium, iridium, aluminum, or nickel.

[0023] Furthermore, the aforementioned protective coating is a black adhesive coating.

[0024] Furthermore, the electrodes are made of gold wire and have a diameter of 0.1 mm.

[0025] Furthermore, the electrode is made of platinum wire and has a diameter of 0.05 mm.

[0026] Furthermore, the aforementioned lead wire is made of copper and has a diameter of 0.1 mm.

[0027] The beneficial effects of this invention are as follows: The ruthenium-doped chromium phosphide material of this invention exhibits resistive behavior without phase transition and possesses positive temperature coefficient linear resistance characteristics in the temperature range of 2-300K. For example, when the ruthenium doping ratio is 0.29, let t be the temperature, and y(t) be the single-crystal Cr thermistor material at different temperatures. 1-x Ru x The resistance value P(x=0.29) and the corresponding temperature conversion formula are: y(t)=a+bt, a=283 ohms, b=0.247.

[0028] The resistive behavior of the ruthenium-doped chromium phosphide material of this invention exhibits a wide linear temperature range. The resistance value across the entire temperature range can be calibrated using epitaxial ultra-low or high temperature methods, which is convenient and quick. This allows it to be applied in the field of wide-temperature-range temperature sensors, reducing packaging and testing costs.

[0029] The magnetoresistance behavior of the ruthenium-doped chromium phosphide material of this invention shows that, at a temperature of 2K, the magnetoresistance of the thermistor changes little (change rate ≈ 5‰) as the magnetic field varies from 0 to 6 Tesla. The change in magnetoresistance caused by each Tesla is less than 1‰, making it suitable for temperature testing in extremely low-temperature environments with strong magnetic fields.

[0030] This invention utilizes the characteristics of ruthenium-doped chromium phosphide material, such as (1) linear resistance across a wide temperature range and (2) low magnetic resistance in a low-temperature, strong magnetic field environment, to provide a novel thermosensitive material for the development of wide-temperature-range temperature sensors, solving the key problem that existing temperature sensors cannot simultaneously measure both extremely low-temperature, strong magnetic fields and room temperature. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the application examples 1-2 of the present invention based on a ruthenium-doped chromium phosphide single crystal temperature sensor. In this diagram, 1 is the bulk material of the ruthenium-doped chromium phosphide single crystal (thermostat), 2 is the protective coating, 3a, 3b, 3c, and 3d are electrodes, and 4a, 4b, 4c, and 4d are leads.

[0032] Figure 2 Example 1 of this invention is based on ruthenium-doped chromium phosphide single crystal Cr. 0.71 Ru 0.29 P's temperature sensor, temperature-resistance curve.

[0033] Figure 3Example 1 of this invention is based on ruthenium-doped chromium phosphide single crystal Cr. 0.71 Ru 0.29 P's temperature sensor, magnetic field-resistance curve.

[0034] Figure 4 Example 1 of this invention is based on ruthenium-doped chromium phosphide single crystal Cr. 0.71 Ru 0.29 P's temperature sensor, magnetization intensity-temperature curve. Detailed Implementation

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1

[0037] The chemical formula of ruthenium-doped chromium phosphide material is Cr 0.8 Ru 0.2 P.

[0038] The preparation method of ruthenium-doped chromium phosphide material includes the following steps:

[0039] (1) Weigh out 0.448 g of Cr powder, 0.334 g of P powder and 0.218 g of Ru powder with purities of 99.999% respectively;

[0040] (2) Mix and grind Cr powder, P powder and Ru powder to a particle size of 0.3 mm, then place it in a tableting mold, apply a pressure of 6 MPa to fix it into shape, then wrap it with quartz wool and put it into a quartz tube, draw a high vacuum and seal it, and finally fire the quartz tube at a high temperature of 1000℃ for 2 days to obtain ruthenium-doped chromium phosphide polycrystalline.

[0041] (3) Grind 1 gram of the obtained ruthenium-doped chromium phosphide polycrystalline material into powder with a particle size of 0.3 mm, put it into a crucible and add 2 grams of flux. The flux is tin particles with a diameter of 1 mm and a purity of 99.999%. Then put the crucible into a quartz tube, draw a high vacuum and seal it. Finally, sinter the quartz tube at a high temperature of 1150°C for 10 days. After cooling to 600°C, quench it in water to obtain ruthenium-doped chromium phosphide single crystal.

[0042] Example 2

[0043] The chemical formula of ruthenium-doped chromium phosphide material is Cr 0.71 Ru 0.29 P.

[0044] The preparation method of ruthenium-doped chromium phosphide material includes the following steps:

[0045] (1) Weigh out 0.380 g of Cr powder, 0.319 g of P powder and 0.302 g of Ru powder with purities of 99.999% respectively;

[0046] (2) Mix and grind Cr powder, P powder and Ru powder to a particle size of 0.3 mm, then place it in a tableting mold, apply a pressure of 6 MPa to fix it into shape, then wrap it with quartz wool and put it into a quartz tube, draw a high vacuum and seal it, and finally fire the quartz tube at a high temperature of 1000℃ for 2 days to obtain ruthenium-doped chromium phosphide polycrystalline.

[0047] (3) Grind 1 gram of the obtained ruthenium-doped chromium phosphide polycrystalline material into powder with a particle size of 0.3 mm, put it into a crucible and add 2 grams of flux. The flux is tin particles with a diameter of 1 mm and a purity of 99.999%. Then put the crucible into a quartz tube, draw a high vacuum and seal it. Finally, sinter the quartz tube at a high temperature of 1150°C for 10 days. After cooling to 600°C, quench it in water to obtain ruthenium-doped chromium phosphide single crystal.

[0048] Example 3

[0049] The chemical formula of ruthenium-doped chromium phosphide material is Cr 0.7 Ru 0.3 P.

[0050] The preparation method of ruthenium-doped chromium phosphide material includes the following steps:

[0051] (1) Weigh out 0.373 g of Cr powder, 0.317 g of P powder and 0.310 g of Ru powder with purities of 99.999% respectively;

[0052] (2) Mix and grind Cr powder, P powder and Ru powder to a particle size of 0.3 mm, then place it in a tableting mold, apply a pressure of 6 MPa to fix it into shape, then wrap it with quartz wool and put it into a quartz tube, draw a high vacuum and seal it, and finally fire the quartz tube at a high temperature of 1000℃ for 2 days to obtain ruthenium-doped chromium phosphide polycrystalline.

[0053] (3) Grind 1 gram of the obtained ruthenium-doped chromium phosphide polycrystalline material into powder with a particle size of 0.3 mm, put it into a crucible and add 2 grams of flux. The flux is tin particles with a diameter of 1 mm and a purity of 99.999%. Then put the crucible into a quartz tube, draw a high vacuum and seal it. Finally, sinter the quartz tube at a high temperature of 1150°C for 10 days. After cooling to 600°C, quench it in water to obtain ruthenium-doped chromium phosphide single crystal.

[0054] Example 4

[0055] The chemical formula of ruthenium-doped chromium phosphide material is Cr 0.69 Ru 0.31 P.

[0056] The preparation method of ruthenium-doped chromium phosphide material includes the following steps:

[0057] (1) Weigh out 0.365 g of Cr powder, 0.315 g of P powder and 0.319 g of Ru powder with purities of 99.999% respectively;

[0058] (2) Mix and grind Cr powder, P powder and Ru powder to a particle size of 0.3 mm, then place it in a tableting mold, apply a pressure of 6 MPa to fix it into shape, then wrap it with quartz wool and put it into a quartz tube, draw a high vacuum and seal it, and finally fire the quartz tube at a high temperature of 1000℃ for 2 days to obtain ruthenium-doped chromium phosphide polycrystalline.

[0059] (3) Grind 1 gram of the obtained ruthenium-doped chromium phosphide polycrystalline material into powder with a particle size of 0.3 mm, put it into a crucible and add 2 grams of flux. The flux is tin particles with a diameter of 1 mm and a purity of 99.999%. Then put the crucible into a quartz tube, draw a high vacuum and seal it. Finally, sinter the quartz tube at a high temperature of 1150°C for 10 days. After cooling to 600°C, quench it in water to obtain ruthenium-doped chromium phosphide single crystal.

[0060] Example 5

[0061] The chemical formula of ruthenium-doped chromium phosphide material is Cr 0.6 Ru 0.4 P.

[0062] The preparation method of ruthenium-doped chromium phosphide material includes the following steps:

[0063] (1) Weigh out 0.304 g of Cr powder, 0.302 g of P powder and 0.394 g of Ru powder with purities of 99.999% respectively;

[0064] (2) Mix and grind Cr powder, P powder and Ru powder to a particle size of 0.3 mm, then place it in a tableting mold, apply a pressure of 6 MPa to fix it into shape, then wrap it with quartz wool and put it into a quartz tube, draw a high vacuum and seal it, and finally fire the quartz tube at a high temperature of 1000℃ for 2 days to obtain ruthenium-doped chromium phosphide polycrystalline.

[0065] (3) Grind 1 gram of the obtained ruthenium-doped chromium phosphide polycrystalline material into powder with a particle size of 0.3 mm, put it into a crucible and add 2 grams of flux. The flux is tin particles with a diameter of 1 mm and a purity of 99.999%. Then put the crucible into a quartz tube, draw a high vacuum and seal it. Finally, sinter the quartz tube at a high temperature of 1150°C for 10 days. After cooling to 600°C, quench it in water to obtain ruthenium-doped chromium phosphide single crystal.

[0066] Application Example 1

[0067] Preparation of ruthenium-doped chromium phosphide single crystals based on Example 2 0.71 Ru 0.29 P's temperature sensor includes ruthenium-doped chromium phosphide single crystal Cr. 0.71 Ru 0.29 P's bulk material (thermometer), electrodes, leads, and protective coating, such as Figure 1 As shown, (1) the prepared Cr 0.71 Ru 0.29 P-crystal bulk material is fixed as a thermistor;

[0068] (2) Electrodes are fabricated using the four-lead method, with the leads passing through the electrodes and Cr. 0.71 Ru 0.29 The P-crystal bulk material is connected, with the electrode being a gold wire with a diameter of 0.1 mm and the lead wire being a copper material with a diameter of 0.1 mm.

[0069] (3) Apply a protective coating to Cr 0.71 Ru 0.29 P-monocrystalline bulk packaging with a protective coating of GE 7031 Vanish low-temperature grease.

[0070] Application Example 2

[0071] Preparation of ruthenium-doped chromium phosphide single crystals based on Example 4 0.69 Ru 0.31 P's temperature sensor includes ruthenium-doped chromium phosphide single crystal Cr. 0.69 Ru 0.31 P consists of the bulk material (thermometer), electrodes, leads, and protective coating.

[0072] (1) Prepare Cr 0.69 Ru 0.31 P-crystal bulk material is fixed as a thermistor;

[0073] (2) Electrodes are fabricated using the four-lead method, with the leads passing through the electrodes and Cr. 0.69 Ru 0.31 The P-crystal bulk material is connected, with the electrode being a gold wire with a diameter of 0.1 mm and the lead wire being a copper material with a diameter of 0.1 mm.

[0074] (3) Apply a protective coating to Cr 0.7 Ru 0.3 The P-type single-crystal bulk package is protected with a LoctiteStycast2850FT black adhesive coating.

[0075] Effect Experiment

[0076] 1) The output behavior of the temperature sensor in Application Example 1 is measured using the four-lead method, such as... Figure 2 As shown. The temperature sensor exhibits resistive behavior without a phase transition, displaying a positive temperature coefficient linear resistivity characteristic in the temperature range of 2-300K. Let t be the temperature, and y(t) be the Cr... 1-x Ru x The resistance value of the temperature sensor is P(x=0.29), and the corresponding temperature conversion formula is: y(t)=a+bt, a=283 ohms, b=0.247.

[0077] 2) The output behavior of the temperature sensor in Application Example 2 was measured using the four-lead method. The temperature sensor exhibits resistive behavior without a phase change and displays positive temperature coefficient linear resistance characteristics in the temperature range of 2-300K. Cr 1-x Ru x The resistance value of the temperature sensor is P(x=0.31), and the corresponding temperature conversion formula is: y(t)=a+bt, where a=297 ohms and b=0.255.

[0078] 3) The temperature sensors prepared in Application Examples 1 and 2 exhibit resistive behavior with a wide linear temperature range. The resistance value across the entire temperature range can be calibrated conveniently and quickly using epitaxial ultra-low or high temperature methods, making them suitable for wide-temperature-range temperature sensor applications. Compared to other temperature sensors where the resistance value undergoes a phase change with temperature, hindering calibration, the temperature sensors in Application Examples 1 and 2 demonstrate linear resistance across a wide temperature range. The resistance-temperature curves measured near room temperature can be extended to lower or higher temperatures, reducing testing costs.

[0079] 3) Application example 1 prepared by Cr 0.71 Ru 0.29 P-single crystal magnetoresistance behavior, such as Figure 3 As shown, at a temperature of 2K, the thermistor's magnetoresistance changes little (rate of change ≈ 5‰) as the magnetic field varies from 0 to 6 Tesla. The change in magnetoresistance caused by each Tesla is less than 1‰, making it suitable for temperature testing in low-temperature environments with strong magnetic fields. Figure 4 It is Cr 0.71 Ru 0.29 The magnetization curves of P single crystal at different temperatures under a magnetic field of 1 Tesla show that the magnetization intensity decreases with temperature.

[0080] As can be seen from the above data, using the ruthenium-doped chromium phosphide material of the present invention as the thermosensitive material, compared with metal temperature sensors such as PT platinum, the ruthenium-doped chromium phosphide material wide-temperature-range temperature sensor has a wide measurement temperature range (applicable temperature range: 2 - 300K), shows a linear relationship between the resistance value and the temperature, is easy to calibrate, saves testing costs, and has a small magnetoresistance in a low-temperature magnetic field environment. In particular, it can provide temperature measurement under extremely low-temperature conditions. In addition, the ruthenium-doped chromium phosphide material Cr 1-x Ru x P single crystal thin film is prepared by methods such as magnetron sputtering, where 0.2 < x < 0.4. When the thin film resistance shows a linear behavior with temperature, a wide-temperature-range thin film temperature sensor can be fabricated.

[0081] The description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A ruthenium-doped chromium phosphide material, characterized in that, The general chemical formula of the ruthenium-doped chromium phosphide material is Cr. 1- x Ru x P, where 0.2 <x<0.4; The preparation method of the ruthenium-doped chromium phosphide material includes the following steps: (1) According to the stated chemical formula and based on Cr 1-x Ru x Calculate x in P and weigh each raw material; (2) Mix and grind Cr powder, P powder and Ru powder evenly, press into shape, wrap with quartz wool and put into quartz tube, draw high vacuum and seal, and finally fire the quartz tube at high temperature to obtain ruthenium-doped chromium phosphide polycrystalline. (3) Grind the obtained ruthenium-doped chromium phosphide polycrystalline powder, put it into a crucible and add flux, then put the crucible into a quartz tube, draw a high vacuum and seal it, and finally sinter the quartz tube at high temperature and quench it to obtain ruthenium-doped chromium phosphide single crystal, that is, the ruthenium-doped chromium phosphide material.

2. The ruthenium-doped chromium phosphide material according to claim 1, characterized in that, The ruthenium-doped chromium phosphide material is in the form of a bulk material, a thin film, or a wire.

3. The ruthenium-doped chromium phosphide material according to claim 1, characterized in that, In step (2), the Cr powder, P powder and Ru powder are mixed and ground to a particle size of 0.3 mm.

4. The ruthenium-doped chromium phosphide material according to claim 1, characterized in that, In step (2), the high-temperature firing temperature is 1000℃ and the high-temperature firing time is 2 days.

5. The ruthenium-doped chromium phosphide material according to claim 1, characterized in that, In step (3), the obtained ruthenium-doped chromium phosphide polycrystalline material is ground into powder with a particle size of 0.3 mm.

6. The ruthenium-doped chromium phosphide material according to claim 1, characterized in that, In step (3), the flux is tin particles, and the mass ratio of the ruthenium-doped chromium phosphide polycrystalline material to the flux is 1:

2.

7. The ruthenium-doped chromium phosphide material according to claim 1, characterized in that, In step (3), the high-temperature firing temperature is 1150℃ and the high-temperature firing time is 10 days.

8. The application of the ruthenium-doped chromium phosphide material of claim 1 in a wide-temperature-range temperature sensor.

9. The application of the ruthenium-doped chromium phosphide material according to claim 8 in a wide-temperature-range temperature sensor, characterized in that, The wide temperature range temperature sensor includes a ruthenium-doped chromium phosphide single crystal bulk material, electrodes, leads, and a protective coating. The leads are connected to the ruthenium-doped chromium phosphide single crystal bulk material through the electrodes. The protective coating encapsulates the ruthenium-doped chromium phosphide single crystal bulk material. The protective coating can be a metal coating, ceramic coating, glass coating, black glue coating, low-temperature grease coating, or epoxy resin coating. The electrode is an extremely fine metal wire with a diameter ≤0.1 mm, and its material is gold, silver, copper, platinum, indium, palladium, iridium, aluminum or nickel.

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