Chromium-based copper spinel chalcogenide thin film material and preparation method thereof

Abstract

The present invention provides a chromium-based copper spinel chalcogenide thin film material and a preparation method thereof, relating to the technical field of spintronics material preparation. The preparation method described in the present invention first adopts a vacuum sealing process to synthesize a CuCr2X4 powder material under a positive X vapor pressure, and then mixes the obtained powder material with an appropriate amount of X powder and sinters it in a low-temperature argon atmosphere to make an X-rich CuCr2X4 target material; then adopts a laser pulse deposition technology to bombard the X-rich CuCr2X4 target material with a high-energy pulse laser, generate a certain X vapor partial pressure in the vacuum chamber, and promote the CuCr2X4 film to become a spinel phase on a high-temperature substrate, so as to achieve stable preparation of the chromium-based copper spinel chalcogenide thin film material. The chromium-based copper spinel chalcogenide thin film material prepared by the present invention has high crystallinity, is ferromagnetic at room temperature (300K), and has a saturation magnetization intensity of 150-250emu / cm 3 , the size meets the needs of spin electronic devices.

Description

Technical Field

[0001] The present invention relates to the technical field of spintronics material preparation, and in particular to a chromium-based copper spinel chalcogenide thin film material and a preparation method thereof. Background Art

[0002] As information technology demands higher storage capacity, faster data processing and data transmission speeds, and longer information storage life, spintronics thin film materials that meet these demands have become an important research direction. Among them, chromium-based copper spinel chalcogenide CuCr2X4 (X = S, Se) materials have a saturation magnetization intensity close to 5μ B / fu, a Curie temperature greater than 400K, and unique magnetoresistance, high Curie temperature, and high spin polarization at the Fermi level make it a candidate material for spintronic properties. Furthermore, theoretical calculations indicate that partial substitution of Cu with halogens, p-group elements, Cd, or Fe can achieve full spin polarization in CuCr2X4 (X = S, Se), inducing a metallic-to-halogen transition in CuCr2X4, making it an ideal candidate for multilayer thin-film spintronic devices.

[0003] However, currently only the chemical vapor transport (CVT) method is used to prepare chromium-based copper spinel chalcogenide CuCr2X4 (X = S, Se) single crystal materials. The resulting single crystal blocks are small in size and cannot be used in thin-film spintronic devices. Therefore, a new method is urgently needed to grow CuCr2X4 (X = S, Se) thin film materials heterogeneously integrated with other materials to meet the needs of multilayer thin-film spintronic devices. Summary of the Invention

[0004] To solve the above problems, the present invention provides a method for preparing a chromium-based copper spinel chalcogenide thin film material, comprising the following steps:

[0005] Step S1: Cu powder, Cr powder, and X powder are mixed, ground, and pressed into tablets, which are then embedded in the X powder. The powder is vacuum sintered and ground to obtain a CuCr2X4 polycrystalline powder. The CuCr2X4 polycrystalline powder and the X powder are mixed, ground, and pressed into tablets, which are then sintered at low temperature under an argon atmosphere to obtain an X-rich CuCr2X4 target; wherein X is at least one of S and Se.

[0006] Step S2: placing the X-rich CuCr2X4 target and a clean substrate in a vacuum chamber of a laser pulse deposition system for vacuum treatment, and then heating the substrate;

[0007] Step S3: bombarding the X-rich CuCr2X4 target material with a laser pulse deposition technique to deposit the X-rich CuCr2X4 target material on the substrate, annealing the target material and naturally cooling it to room temperature to obtain a chromium-based copper spinel chalcogenide thin film material.

[0008] Furthermore, in step S1, the molar ratio of the Cu powder, the Cr powder and the X powder is 1:2:4; the mass ratio of the Cu powder, the Cr powder and the X powder after tableting to the mass ratio of the X powder is (3-10):1; and the mass ratio of the CuCr2X4 polycrystalline powder and the X powder mixed is 2:1.

[0009] Furthermore, in step S1, the vacuum sintering process includes: primary sintering and heat preservation, followed by secondary sintering and heat preservation; the primary sintering temperature is 400-500°C, the heat preservation time is 12-24h, and the secondary sintering temperature is 700-800°C, the heat preservation time is 72-168h.

[0010] Furthermore, in step S1, the sintering temperature of the low-temperature sintering in an argon protective atmosphere is 100-200° C., and the sintering time is 10-15 hours.

[0011] Furthermore, in step S2, the vacuum treatment includes: evacuating to a pressure of 2.5-5.0×10 -4 Pa.

[0012] Furthermore, in step S2, the substrate includes one of Si, Al2O3, Mg2O3 and MgAl2O4 substrates.

[0013] Furthermore, in step S2, heating the substrate includes heating the substrate to 500-600° C. and maintaining the temperature for 10-30 minutes.

[0014] Furthermore, in step S3, the laser pulse deposition technology is used to bombard the X-rich CuCr2X4 target with a single pulse energy of 150-200 mJ and a pulse frequency of 3-8 Hz.

[0015] Furthermore, in step S3, the annealing time is 5-20 minutes.

[0016] The method for preparing a chromium-based copper spinel chalcogenide thin film material disclosed herein offers the following advantages over existing methods: The method fills a gap in existing methods for growing chromium-based copper spinel chalcogenide (CuCr2X4) (X = S, Se) thin films, transforming chromium-based copper spinel chalcogenide from a single crystal bulk into a thin film material, enabling its application in thin-film spintronic devices. The method also prepares an X-rich CuCr2X4 target material by combining vacuum sintering with low-temperature sintering in an argon atmosphere. The X vapor partial pressure generated by pulsed laser bombardment of the X-rich CuCr2X4 target material promotes the formation of a spinel phase in the CuCr2X4 thin film on a high-temperature substrate, eliminating the need for an additional X evaporation source and simplifying the preparation process. Furthermore, the chromium-based copper spinel chalcogenide thin film material prepared by the present invention exhibits high crystallinity, a high saturation magnetization at room temperature, and film dimensions that meet the requirements of spintronic devices.

[0017] The present invention also provides a chromium-based copper spinel chalcogenide thin film material, which is prepared according to the above-mentioned method for preparing the chromium-based copper spinel chalcogenide thin film material.

[0018] The beneficial effects of the chromium-based copper spinel chalcogenide thin film material described in the present invention compared with the prior art are the same as the beneficial effects of the preparation method of the chromium-based copper spinel chalcogenide thin film material described in the present invention compared with the prior art, and will not be repeated here. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a flow chart of a method for preparing a chromium-based copper spinel chalcogenide thin film material in an embodiment of the present invention;

[0020] Figure 2 Schematic diagram of the process for producing an X-rich CuCr2X4 target in an embodiment of the present invention;

[0021] Figure 3 Schematic diagram of the partial structure of the pulsed laser deposition system in an embodiment of the present invention;

[0022] Figure 4 is the X-ray diffraction spectrum of the CuCr2X4 target in the embodiment of the present invention;

[0023] Figure 5 is an X-ray diffraction spectrum of a CuCr2S4 polycrystalline thin film grown on a Si substrate in Example 1 of the present invention;

[0024] Figure 6 is the X-ray photoelectron spectrum of the CuCr2S4 polycrystalline thin film grown on the Si substrate in Example 1 of the present invention;

[0025] Figure 7This is the hysteresis loop of the CuCr2S4 polycrystalline thin film grown on the Si substrate in Example 1 of the present invention.

[0026] Description of reference numerals:

[0027] 1-substrate holder; 2-pulsed laser; 3-X vapor; 4-target holder; 5-vacuum pump assembly. DETAILED DESCRIPTION

[0028] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0029] Combine Figure 1 As shown, an embodiment of the present invention provides a method for preparing a chromium-based copper spinel chalcogenide thin film material, comprising the following steps:

[0030] Step S1: Cu powder, Cr powder, and X powder are mixed, ground, and pressed into tablets, which are then embedded in X powder. The powders are vacuum sintered and ground to obtain CuCr2X4 polycrystalline powder. The CuCr2X4 polycrystalline powder and X powder are mixed, ground, and pressed into tablets, which are then sintered at low temperature under an argon atmosphere to obtain an X-rich CuCr2X4 target. X is at least one of S and Se. It should be noted that in this embodiment, Cu powder refers to copper powder, Cr powder refers to chromium powder, S refers to sulfur, and Se refers to selenium, and the same applies hereinafter.

[0031] Step S2: placing the X-rich CuCr2X4 target and a clean substrate in a vacuum chamber of a laser pulse deposition system for vacuum treatment, and then heating the substrate;

[0032] Step S3: bombarding the X-rich CuCr2X4 target material with a laser pulse deposition technique to deposit the X-rich CuCr2X4 target material on a substrate, annealing the target material and naturally cooling the target material to room temperature to obtain a chromium-based copper spinel chalcogenide thin film material.

[0033] The method for preparing a chromium-based copper spinel chalcogenide thin film material described in the present embodiment fills a gap in existing methods for growing chromium-based copper spinel chalcogenide (CuCr2X4) (X=S, Se) thin films. This method transforms chromium-based copper spinel chalcogenide from a single crystal bulk into a thin film material, enabling its application in thin-film spintronic devices. The present embodiment also prepares an X-rich CuCr2X4 target material by combining vacuum sintering with low-temperature sintering in an argon atmosphere. The X vapor partial pressure generated by pulsed laser 2 bombarding the X-rich CuCr2X4 target promotes the formation of a spinel phase in the CuCr2X4 thin film on the substrate, eliminating the need for an additional X evaporation source and simplifying the preparation process. Furthermore, the chromium-based copper spinel chalcogenide thin film material prepared in the present embodiment exhibits high crystallinity, a high saturation magnetization at room temperature, and film dimensions that meet the requirements of spintronic devices.

[0034] Specifically, combined Figure 2 As shown, the purity of the Cu powder, Cr powder, and X powder in step S1 is all above 99.9%. After mixing, they are placed in an agate mortar for preliminary mixing and grinding, and then placed in a cylindrical mold of a powder tablet press to press into disc A. Disc A is placed in a vacuum quartz tube, and the volume ratio of disc A to the vacuum quartz tube is controlled to be 1:(30-50). After adding X powder into the vacuum quartz tube, the vacuum quartz tube is placed in a box furnace for sintering to obtain CuCr2X4 polycrystalline powder. The CuCr2X4 polycrystalline powder is then mixed with the X powder and ground thoroughly, and similarly placed in a cylindrical mold of a powder tablet press to press into disc B. Disc B is sintered at low temperature in a high-purity argon protective atmosphere to ultimately obtain an X-rich CuCr2X4 target.

[0035] Specifically, combined Figure 3 and Figure 4 As shown, in step S2, an X-rich CuCr2X4 target and a clean substrate are placed on a target holder 4 and a substrate holder 1 in a vacuum chamber of a laser pulse deposition system. The vacuum chamber is evacuated using a mechanical pump and a molecular pump to achieve the vacuum level required for thin film growth. The substrate is then slowly heated and the temperature is kept stable for subsequent thin film growth.

[0036] Specifically, in step S3, an excimer laser in a laser pulse deposition system is used to bombard an X-rich CuCr2X4 target. The single pulse energy and pulse frequency are controlled. At this time, a certain X vapor partial pressure of 3 is generated in the vacuum chamber, which promotes the deposition of the CuCr2X4 material on the substrate and forms a spinel phase. After the deposition is completed, in-situ annealing is performed and the material is naturally cooled to room temperature to obtain a chromium-based copper spinel chalcogenide thin film material. The resulting chromium-based copper spinel chalcogenide thin film material has high crystallinity, a large saturation magnetization at room temperature, and a film size that meets the requirements of spintronic devices.

[0037] In some embodiments, in step S1, the molar ratio of Cu powder, Cr powder, and X powder is 1:2:4; the mass ratio of the pressed Cu powder, Cr powder, and X powder to the X powder is (3-10):1; and the mass ratio of the mixed CuCr2X4 polycrystalline powder to the X powder is 2:1. Thus, precisely controlling the original ratios facilitates the production of high-performance chromium-based copper spinel chalcogenide thin film materials, making them more suitable for application in spintronic devices.

[0038] In some embodiments, in step S1, the vacuum sintering process includes: a primary sintering and holding process followed by a secondary sintering and holding process; the primary sintering temperature is 400-500°C for a holding time of 12-24 hours, and the secondary sintering temperature is 700-800°C for a holding time of 72-168 hours. Thus, after sintering and holding, a CuCr2X4 polycrystalline powder suitable for subsequent thin film growth is obtained to the greatest extent possible.

[0039] In some embodiments, in step S1, the sintering temperature of the low-temperature sintering under an argon protective atmosphere is 100-200° C., and the sintering time is 10-15 hours, thereby obtaining a high-purity X-rich CuCr2X4 target.

[0040] In some embodiments, in step S2, the vacuum treatment includes: evacuating to a pressure of 2.5-5.0×10 -4 Pa.

[0041] Preferably, in this embodiment, a mechanical pump is used to perform pre-vacuum treatment to bring the air pressure to 2.0-3.0 Pa, and then a molecular pump is used to further increase the vacuum degree to 2.5-5.0×10 -4 Pa. It is beneficial to generate X vapor 3 partial pressure in the subsequent deposition process and promotes the formation of spinel phase of CuCr2X4 material on the heated substrate.

[0042] In some embodiments, in step S2, the clean substrate preparation process includes:

[0043] The substrate is placed in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning in sequence, and then the substrate is blown dry with high-purity argon gas or high-purity nitrogen gas to obtain a substrate with a clean surface.

[0044] Specifically, the substrate is placed in a small beaker, 20 mL of acetone is added, and the solution is ultrasonically cleaned at room temperature for 10 minutes. The acetone is then replaced with anhydrous ethanol and the same ultrasonic treatment is repeated to remove the acetone from the substrate surface. Finally, deionized water is ultrasonically treated to remove the anhydrous ethanol from the substrate surface, and the deionized water on the substrate surface is blown dry with high-purity argon (99.999%) or high-purity nitrogen (99.999%), ultimately resulting in a clean substrate surface. This thoroughly cleans the substrate surface, preventing impurities from adversely affecting the thin film growth process and improving the quality of the film growth.

[0045] In some embodiments, in step S2, the substrate comprises one of Si, Al2O3, Mg2O3, and MgAl2O4 substrates. Thus, a variety of substrates can be selected and are suitable for depositing CuCr2X4 material in the laser pulse deposition technology.

[0046] In some embodiments, in step S2, heating the substrate includes heating the substrate to 500-600° C. and maintaining the temperature for 10-30 minutes. Thus, increasing the substrate temperature is beneficial for CuCr2S4 to deposit on the high-temperature substrate to form a spinel phase.

[0047] In some embodiments, in step S3, laser pulse deposition is used to bombard an X-rich CuCr2X4 target with a single pulse energy of 150-200 mJ and a pulse frequency of 3-8 Hz. Thus, the single pulse energy and pulse frequency are controlled to generate a sulfur vapor partial pressure within the vacuum chamber, promoting the formation of a spinel phase in the CuCr2X4 on the high-temperature substrate, ultimately producing a chromium-based copper spinel chalcogenide thin film material with excellent performance.

[0048] In some embodiments, in step S3, the annealing time is 5-20 minutes, thereby obtaining a chromium-based copper spinel chalcogenide thin film material with high crystallinity, large saturation magnetization at room temperature, and a size that meets the requirements of spintronic devices.

[0049] An embodiment of the present invention further provides a chromium-based copper spinel chalcogenide thin film material, which is prepared according to the preparation method of the chromium-based copper spinel chalcogenide thin film material in the above embodiment.

[0050] The beneficial effects of the chromium-based copper spinel chalcogenide thin film material described in the embodiment of the present invention compared with the prior art are the same as the beneficial effects of the preparation method of the chromium-based copper spinel chalcogenide thin film material described in the embodiment of the present invention compared with the prior art, and will not be repeated here.

[0051] Example 1

[0052] The method for preparing the chromium-based copper spinel chalcogenide thin film material according to an embodiment of the present invention comprises the following steps, wherein the X powder is S powder, i.e., sulfur powder:

[0053] Step S1: 2 g of Cu powder (99.9%), Cr powder (99.9%) and S powder (99.9%) in a molar ratio of 1:2:4 were placed in an agate mortar and preliminarily mixed until fully ground. The resulting powder was poured into a cylindrical mold with a diameter of 13 mm, and then the mixture powder was pressed under appropriate pressure using a powder tablet press to obtain a disc A; the disc A was placed in a vacuum quartz tube, 0.5 g of S powder (99.9%) was placed, and the volume inside the vacuum quartz tube was controlled at 23 mL, and then placed in a box furnace for preliminary sintering, the temperature was set to 400° C., and then after keeping warm for 24 hours, the secondary sintering temperature was 700° C., and then kept warm for 72 hours to obtain CuCr2S4 polycrystalline powder;

[0054] CuCr2S4 polycrystalline powder and 0.5 g of S powder (99.9%) were mixed and ground until fully ground. The resulting powder was poured into a cylindrical mold with a diameter of 13 mm, and then the mixture powder was pressed under appropriate pressure using a powder tablet press to obtain a disc B. Disc B was sintered at a low temperature of 105°C and a sintering time of 10 hours under a high-purity argon protective atmosphere to obtain a S-rich CuCr2S4 target.

[0055] Step S2: Place the CuCr2S4 target and the Si clean substrate on the target holder 4 and substrate holder 1 in the vacuum chamber respectively. Use a mechanical pump to pre-vacuum the chamber until the pressure reaches 3.0 Pa. Then use a molecular pump to further evacuate the chamber to a pressure of 5.0×10 -4 Pa; heat the substrate, slowly raise the temperature to 500 ° C, and stabilize the temperature for 10 minutes;

[0056] The cleaning process of the substrate includes: placing the Si substrate in a small beaker, adding 20 mL of acetone, placing the beaker in an ultrasonic cleaning machine, ultrasonically cleaning at room temperature for 10 minutes, replacing the acetone with anhydrous ethanol for ultrasonic cleaning to remove the acetone on the substrate surface, and finally ultrasonically cleaning with deionized water to remove the anhydrous ethanol on the substrate surface, and then blowing the deionized water on the substrate surface with high-purity argon (99.999%) or high-purity nitrogen (99.999%) to obtain a substrate with a clean surface;

[0057] Step S3: Use an excimer laser in laser pulse deposition technology to bombard the S-rich CuCr2S4 target, control the single pulse energy to 200mJ, and the pulse frequency to 4Hz, to generate a certain S vapor partial pressure in the vacuum chamber, so as to promote the deposition of the CuCr2S4 material on the heated substrate to form a spinel phase. After the deposition is completed, in-situ annealing is performed for 10 minutes, and finally naturally cooled to room temperature to obtain a chromium-based copper spinel chalcogenide thin film material.

[0058] Depend on Figure 5X-ray diffraction spectrum of CuCr2S4 polycrystalline thin film grown on Si substrate, Figure 6 X-ray photoelectron spectroscopy of CuCr2S4 polycrystalline thin films grown on Si substrates, and Figure 7 The hysteresis loop of the CuCr2S4 polycrystalline film grown on the Si substrate, where IP represents the magnetic field parallel to the film and OP represents the magnetic field perpendicular to the film, shows that the X-ray diffraction spectrum of the CuCr2S4 polycrystalline film prepared in this example is in good agreement with the standard card PDF#97-062-5769, which is a typical CuCr2S4 spinel phase; and the X-ray photoelectron spectroscopy shows that the Cr element is mainly present in the CuCr2S4 polycrystalline film as Cr 3+ and Cr 4+ There are two valence states, and the ratio of Cu to Cr is about 1:1.1, which is consistent with the element ratio of the CuCr2S4 molecular formula. The hysteresis loop IP and OP of the CuCr2S4 polycrystalline film are slightly different, showing isotropy, and the saturation magnetization intensity at room temperature reaches 3μ B / fu, which is consistent with the powder experimental data and has strong ferromagnetism.

[0059] Example 2

[0060] The method for preparing the chromium-based copper spinel chalcogenide thin film material according to an embodiment of the present invention comprises the following steps, wherein the X powder is Se powder, i.e., selenium powder:

[0061] Step S1: 2 g of Cu powder (99.9%), Cr powder (99.9%) and Se powder (99.9%) in a molar ratio of 1:2:4 were placed in an agate mortar and preliminarily mixed until fully ground. The resulting powder was poured into a cylindrical mold with a diameter of 13 mm, and then the mixture powder was pressed under appropriate pressure using a powder tablet press to obtain a disc A; the disc A was placed in a vacuum quartz tube, 0.2 g of Se powder (99.9%) was placed, and the volume inside the vacuum quartz tube was controlled at 35 mL, and then placed in a box furnace for preliminary sintering, the temperature was set to 500°C, and then kept warm for 24 hours, and the secondary sintering temperature was 800°C, and then kept warm for 168 hours to obtain CuCr2Se4 polycrystalline powder;

[0062] CuCr2Se4 polycrystalline powder and 0.5 g of Se powder (99.9%) were mixed and ground until fully ground. The resulting powder was poured into a cylindrical mold with a diameter of 13 mm, and then the mixture powder was pressed under appropriate pressure using a powder tablet press to obtain a disc B. Disc B was sintered at a low temperature of 200°C and a sintering time of 10 hours under a high-purity argon protective atmosphere to obtain a Se-rich CuCr2Se4 target.

[0063] Step S2: Place the CuCr2Se4 target and the Si clean substrate on the target holder 4 and substrate holder 1 in the vacuum chamber respectively. Use a mechanical pump to pre-vacuum the chamber until the pressure reaches 3.0 Pa. Then use a molecular pump to further evacuate the chamber to a pressure of 5.0×10 -4 Pa; heat the substrate, slowly raise the temperature to 600°C, and keep the temperature stable for 10-30 minutes;

[0064] The cleaning process of the substrate includes: placing the Si substrate in a small beaker, adding 20 mL of acetone, placing the beaker in an ultrasonic cleaning machine, ultrasonically cleaning at room temperature for 10 minutes, replacing the acetone with anhydrous ethanol for ultrasonic cleaning to remove the acetone on the substrate surface, and finally ultrasonically cleaning with deionized water to remove the anhydrous ethanol on the substrate surface, and then blowing the deionized water on the substrate surface with high-purity argon (99.999%) or high-purity nitrogen (99.999%) to obtain a substrate with a clean surface;

[0065] Step S3: Use excimer laser in laser pulse deposition technology to bombard Se-rich CuCr2Se4 target material, control the single pulse energy to 200mJ, and the pulse frequency to 4Hz, to generate a certain Se vapor partial pressure in the vacuum chamber, so as to promote the deposition of CuCr2Se4 material on the heated substrate to form a spinel phase. After the deposition is completed, in-situ annealing is performed for 10 minutes, and finally naturally cooled to room temperature to obtain a chromium-based copper spinel chalcogenide thin film material.

[0066] Although the present invention is disclosed as above, the scope of protection disclosed by the present invention is not limited thereto. Those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the scope of protection of the present invention.

Claims

1. A method for preparing a chromium-based copper spinel chalcogenide thin film material, characterized in that: The steps include: Step S1: After Cu powder, Cr powder and X powder are mixed, ground and pressed into tablets, the powder is embedded in the X powder, vacuum sintered and ground to obtain CuCr2X4 polycrystalline powder, wherein the molar ratio of the Cu powder, the Cr powder and the X powder is 1:2:4, and the mass ratio of the Cu powder, the Cr powder and the X powder after tableting to the mass ratio of the X powder is (3-10):1; after the CuCr2X4 polycrystalline powder and the X powder are mixed, ground and pressed into tablets, the powder is heated in an argon atmosphere. Low-temperature sintering under a protective atmosphere to obtain an X-rich CuCr2X4 target, wherein the mass ratio of the CuCr2X4 polycrystalline powder to the X powder is 2:1; wherein the X is at least one of S and Se; the vacuum sintering process comprises: primary sintering and heat preservation, followed by secondary sintering and heat preservation, the primary sintering temperature being 400-500°C, and the secondary sintering temperature being 700-800°C; the low-temperature sintering under an argon protective atmosphere is sintered at a temperature of 100-200°C; Step S2: placing the X-rich CuCr2X4 target and a clean substrate in a vacuum chamber of a laser pulse deposition system for vacuum treatment, and then heating the substrate; Step S3: bombarding the X-rich CuCr2X4 target material with a laser pulse deposition technique to deposit the X-rich CuCr2X4 target material on the substrate, annealing the target material and naturally cooling it to room temperature to obtain a chromium-based copper spinel chalcogenide thin film material.

2. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S1, the holding time of the primary sintering is 12-24 hours, and the holding time of the secondary sintering is 72-168 hours.

3. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S1, the sintering time of the low-temperature sintering in the argon protective atmosphere is 10-15 hours.

4. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S2, the vacuum treatment includes: evacuating to a pressure of 2.5-5.0×10 -4 Pa.

5. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S2, the substrate includes one of Si, Al2O3, Mg2O3 and MgAl2O4 substrates.

6. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S2, heating the substrate includes heating the substrate to 500-600°C and maintaining the temperature for 10-30 minutes.

7. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S3, the laser pulse deposition technology is used to bombard the X-rich CuCr2X4 target with a single pulse energy of 150-200 mJ and a pulse frequency of 3-8 Hz.

8. The method for preparing the chromium-based copper spinel chalcogenide thin film material according to claim 1, characterized in that: In step S3, the annealing time is 5-20 minutes.

9. A chromium-based copper spinel chalcogenide thin film material, characterized in that: It is prepared according to the preparation method of the chromium-based copper spinel chalcogenide thin film material according to any one of claims 1 to 8.

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