Zr-Ru-Si-based ternary superconducting single crystal material, preparation method and application thereof, and terminal product

Abstract

The invention relates to the technical field of superconducting single crystal materials, and discloses a Zr-Ru-Si-based ternary superconducting single crystal material, the chemical general formula is ZrxRuySiz, x is equal to 1.8-2.2, y is equal to 2.5-3.5, and z is equal to 3.5-4.5. The superconducting single crystal material belongs to a typical ternary transition metal silicide system, and a Si element is introduced to participate in construction of a crystal skeleton, so that a stable silicide structure is formed; the crystal belongs to a monoclinic system C2 / c space group, and has unique spatial symmetry and a three-dimensional crystal skeleton; and the material has good crystallinity and high purity, and shows a superconducting transition behavior at the temperature of 5.4 K. The growth is carried out by adopting a fluxing agent method, the operation is simple and convenient, the cost is controllable, the method is suitable for large-scale exploration, and a foundation is laid for the development of other potential superconducting phases in a subsequent Zr-Ru-Si ternary system. The invention further discloses a preparation method and application of the Zr-Ru-Si-based ternary superconducting single crystal material and a terminal product.

Description

Technical Field

[0001] This application relates to the field of superconducting single crystal materials technology, such as a Zr-Ru-Si based ternary superconducting single crystal material, its preparation method and application, and end products. Background Technology

[0002] Superconducting materials are a class of important functional materials that exhibit zero resistance and perfect diamagnetism (Meissner effect) at low temperatures, and are widely used in cutting-edge technology fields such as quantum computing, high-field magnets, magnetic levitation transportation, medical imaging (such as MRI), and particle accelerators. In recent years, the system of superconducting materials has been continuously enriched, and the main known categories include copper oxide high-temperature superconductors, iron-based superconductors, heavy fermion superconductors, and some intermetallic compound superconductors.

[0003] Currently, researchers have synthesized polycrystalline Zr₂Ru₃Si₄ using arc melting. This material exhibits excellent chemical stability and corrosion resistance, has a monoclinic crystal system with space group C² / c, and undergoes a superconducting transition at approximately 5 K, demonstrating characteristics of a type II superconductor. It is speculated to possess multi-bandgap or anisotropic bandgap superconducting properties, making it valuable for fundamental research. However, due to its polycrystalline nature, it cannot yet meet the experimental requirements for studying key physical properties such as band structure, Fermi surface morphology, and superconducting anisotropic behavior. Furthermore, the preparation of high-quality single-crystal materials from ternary transition metal silicides faces numerous challenges due to their complex bonding mechanisms and the difficulty in controlling crystal structure, particularly in controlling crystal quality, phase purity, and growth conditions. This limits the systematic study of the electrical and magnetic properties of such materials and hinders their application in low-temperature physics and quantum devices.

[0004] Therefore, there is an urgent need to develop a method for preparing high-quality single-crystal materials suitable for the Zr-Ru-Si ternary system, so as to support in-depth exploration of the basic properties and potential applications of this type of material.

[0005] It should be noted that the information disclosed in the background section above is only used to enhance the understanding of the background of this application, and therefore may include information that does not constitute prior art known to those skilled in the art. Summary of the Invention

[0006] To provide a basic understanding of some aspects of the disclosed embodiments, a brief summary is given below. This summary is not intended as a general commentary, nor is it intended to identify key / important components or describe the scope of protection of these embodiments, but rather as a prelude to the detailed description that follows.

[0007] This disclosure provides a Zr-Ru-Si based ternary superconducting single crystal material, its preparation method, applications, and end products. It aims to provide a Zr-Ru-Si based ternary superconducting single crystal material to support in-depth exploration of the fundamental properties and potential applications of this type of material; and to provide a controllable preparation method that allows for the controllable growth of the single crystal material, resulting in single crystals with good crystallinity and high purity.

[0008] In some embodiments, the Zr-Ru-Si based ternary superconducting single crystal material has the general chemical formula Zr-Ru-Si based ternary superconducting single crystal material. x Ru y Si z , where x = 1.8~2.2, y = 2.5~3.5, z = 3.5~4.5.

[0009] In some embodiments, the preparation method of the Zr-Ru-Si based ternary superconducting single crystal material includes: weighing raw materials with a purity greater than or equal to 98% according to a set stoichiometric ratio: Zr, Ru, Si, and Cu; wherein the set stoichiometric ratio is Zr: Ru: Si: Cu = (1-5): (1-10): (4-10): (10-40); placing the raw materials into a crucible and then sealing them in a quartz tube; wherein the quartz tube is in a vacuum state or filled with an inert atmosphere; heating the sealed quartz tube from room temperature to 1100-1200℃ and holding it at that temperature for 5-50 hours; then using 0.2-2 The temperature is reduced to within the crystal precipitation temperature range at a rate of ℃ / h; the quartz tube is quickly removed from the furnace at the preset crystallization temperature and installed upside down in a centrifuge device for centrifugation to remove the residual flux Cu-Si melt; the quartz tube is opened to obtain a solid mixture containing the target single crystal, and then the solid mixture is purified to obtain Zr-Ru-Si based ternary superconducting single crystal material.

[0010] In some embodiments, the Zr-Ru-Si based ternary superconducting single crystal material or the Zr-Ru-Si based ternary superconducting single crystal material prepared by the preparation method of the Zr-Ru-Si based ternary superconducting single crystal material is used in the fields of medical imaging, energy transmission, semiconductor manufacturing, rail transportation, scientific research equipment, or quantum communication.

[0011] In some embodiments, the end product includes the Zr-Ru-Si based ternary superconducting single crystal material or the Zr-Ru-Si based ternary superconducting single crystal material prepared by the preparation method of the Zr-Ru-Si based ternary superconducting single crystal material.

[0012] The Zr-Ru-Si based ternary superconducting single crystal material and its preparation method provided in this disclosure can achieve the following technical effects: The Zr-Ru-Si-based ternary superconducting single-crystal material disclosed in this embodiment belongs to a typical ternary transition metal silicide system. Si is introduced to participate in the construction of the crystal framework, forming a stable silicide structure. The crystal structure of this superconducting single-crystal material belongs to the monoclinic C2 / c space group, a relatively complex type of ternary silicide structure, possessing unique spatial symmetry and a three-dimensional crystal framework. Furthermore, this superconducting single-crystal material exhibits good crystallinity and high purity, demonstrating superconducting transition behavior at 5.4K, and possesses significant potential for scientific research and application.

[0013] The Zr-Ru-Si based ternary superconducting single crystal material of this disclosure is a single crystal with a (001) plane, a single crystal size of about 1-2 mm, and a thickness of about 100-500 μm. The size of the single crystal can be controlled by the growth conditions. This single crystal has a distinct strip-shaped shape, with the long side along the

[010] crystal orientation, which avoids the tedious process of determining the crystal orientation of the single crystal and is beneficial to scientific research and industrial production applications.

[0014] The method for preparing Zr-Ru-Si based ternary superconducting single crystal materials disclosed in this embodiment adopts a flux-assisted growth method, which is simple to operate, cost-controllable, suitable for large-scale exploration, and lays the foundation for the development of other potential superconducting phases in the Zr-Ru-Si ternary system.

[0015] The Zr-Ru-Si-based ternary superconducting single-crystal material disclosed in this invention enriches the transition metal silicide superconducting material system and provides a feasible path for the development of novel superconducting materials. This superconducting single-crystal material can be widely used in low-temperature physics, superconducting mechanism analysis, topological superconductivity research, and quantum device development. It possesses advantages such as good crystallinity, high purity, and clear superconducting transition, effectively improving the accuracy of property testing, promoting the exploration of topological quantum materials, and expanding the superconducting material system, thus possessing significant scientific research and application value. Furthermore, utilizing the zero resistance and perfect diamagnetism of the Zr-Ru-Si-based ternary superconducting single-crystal material, it can be applied in multiple fields, showing great application prospects.

[0016] The above general description and the description below are exemplary and illustrative only and are not intended to limit this application. Attached Figure Description

[0017] One or more embodiments are illustrated by way of example with reference to the accompanying drawings. These illustrations and drawings do not constitute a limitation on the embodiments. Elements having the same reference numerals in the drawings are shown as similar elements. The drawings are not to be scaled. And wherein: Figure 1 This is a photograph of a Zr-Ru-Si based ternary superconducting single crystal material provided in an embodiment of this disclosure; Figure 2This is a flowchart illustrating a method for preparing a Zr-Ru-Si based ternary superconducting single crystal material according to an embodiment of this disclosure; Figure 3 This is the X-ray diffraction (XRD) pattern of a Zr-Ru-Si based ternary superconducting single crystal material according to Embodiment 1 of this disclosure; Figure 4 This is the result of energy dispersive X-ray spectroscopy (EDS) elemental analysis of a Zr-Ru-Si based ternary superconducting single crystal material according to Embodiment 1 of this disclosure; Figure 5 This is a graph showing the reduced resistivity of a Zr-Ru-Si based ternary superconducting single crystal material as a function of temperature, according to Embodiment 1 of this disclosure. Figure 6 This is the result of energy dispersive X-ray spectroscopy (EDS) elemental analysis of a Zr-Ru-Si based ternary superconducting single crystal material according to Embodiment 2 of this disclosure; Figure 7 This is the result of energy dispersive X-ray spectroscopy (EDS) elemental analysis of a Zr-Ru-Si based ternary superconducting single crystal material according to Embodiment 3 of this disclosure; Figure 8 This is the result of energy dispersive X-ray spectroscopy (EDS) elemental analysis of a Zr-Ru-Si based ternary superconducting single crystal material according to Embodiment 4 of this disclosure; Figure 9 This is the result of energy dispersive X-ray spectroscopy (EDS) elemental analysis of a Zr-Ru-Si based ternary superconducting single crystal material according to Embodiment 5 of this disclosure; Figure 10 The results of energy-dispersive X-ray spectroscopy (EDS) elemental analysis of the single-crystal material synthesized in Comparative Example 1 of this disclosure are shown. Figure 11 The results are the elemental analysis results of energy dispersive X-ray spectroscopy (EDS) of the single crystal material synthesized in Comparative Example 2 of this disclosure. Detailed Implementation

[0018] To provide a more detailed understanding of the features and technical content of the embodiments of this disclosure, the implementation of the embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. The accompanying drawings are for illustrative purposes only and are not intended to limit the embodiments of this disclosure. In the following technical description, for ease of explanation, several details are used to provide a full understanding of the disclosed embodiments. However, one or more embodiments may still be implemented without these details. In other cases, well-known structures, steps, and apparatus may be simplified to simplify the illustrations.

[0019] The terms "first," "second," etc., used in the specification, claims, and accompanying drawings of this disclosure are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate for the embodiments of this disclosure described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The term "multiple" means two or more. In embodiments of this disclosure, the character " / " indicates an "or" relationship between the preceding and following objects. For example, A / B means: A or B. The term "and / or" describes an association between objects, indicating that three relationships can exist. For example, A and / or B means: A or B, or, A and B.

[0021] It should be noted that, unless otherwise specified, the embodiments and features described in the present disclosure can be combined with each other.

[0022] Those skilled in the art will understand that in the methods described in this application and other parts thereof, for example, in the methods of various embodiments or examples, the order in which the steps are written does not imply a strict execution order and does not constitute any limitation on the implementation process. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps A and B, it means that the method may include steps A and B performed sequentially, or it may include steps B and A performed sequentially. For example, if the method may also include step C, it means that step C can be added to the method in any order. For example, the method may include steps A, B, and C, or it may include steps A, C, and B, or it may include steps C, A, and B, etc.

[0023] In this application, open-ended technical features or solutions described using terms such as "containing," "including," or "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, if A includes a1, a2, and a3, it may also include other members or exclude additional members unless otherwise specified. This can be considered as providing both the feature or solution that "A consists of a1, a2, and a3" and the feature or solution that "A includes not only a1, a2, and a3, but also other members."

[0024] The "range" disclosed in this application can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be independently included or excluded, and they can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0025] In this application, unless otherwise specified, A (e.g., B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0026] This disclosure presents a Zr-Ru-Si based ternary superconducting single-crystal material with the general chemical formula Zr. x Ru y Si z , where x = 1.8~2.2, y = 2.5~3.5, z = 3.5~4.5.

[0027] The Zr-Ru-Si-based ternary superconducting single-crystal material disclosed in this embodiment belongs to a typical ternary transition metal silicide system. Si is introduced to participate in the construction of the crystal framework, forming a stable silicide structure. The crystal structure of this superconducting single-crystal material belongs to the monoclinic C2 / c space group, a relatively complex type of ternary silicide structure, possessing unique spatial symmetry and a three-dimensional crystal framework. Furthermore, this superconducting single-crystal material exhibits good crystallinity, high purity, and a significant superconducting transition. Resistance testing shows a superconducting transition temperature of 5.4 K, providing the basic conditions for conducting system physical property measurements, making it particularly suitable for exploring cutting-edge topics such as superconductivity and cryogenic transport.

[0028] The Zr-Ru-Si based ternary superconducting single crystal material of this disclosure is a single crystal with (001) planes, a single crystal size of approximately 1-2 mm, and a thickness of approximately 100-500 μm. The size of the single crystal can be controlled by the growth conditions. This single crystal has a distinct strip-like shape (see...). Figure 1 As shown), the long side is along the

[010] crystal orientation, which can avoid the tedious process of determining the crystal orientation of a single crystal and is beneficial to scientific research and industrial production applications.

[0029] The Zr-Ru-Si based ternary superconducting single crystal material of this disclosure is glossy black with a smooth surface and regular edges; X-ray diffraction (XRD) shows that the crystal has Zr... x Ru y Si z A series of diffraction peaks were observed; energy dispersive spectroscopy (EDS) confirmed that the elemental composition of the sample conformed to Zr. x Ru y Si z Stoichiometry; resistance measurements indicate that the single crystal undergoes a superconducting transition at approximately 5.4 K, exhibiting typical zero-resistance behavior.

[0030] The Zr-Ru-Si based ternary superconducting single crystal material of this disclosure can be in bulk form.

[0031] In some embodiments, x = 1.9–2.1, y = 2.8–3.2, and z = 3.8–4.2.

[0032] Optionally, x=2, y=3, z=4. The general chemical formula of the Zr-Ru-Si based ternary superconducting single crystal material in this embodiment is Zr2Ru3Si4.

[0033] In some embodiments, the Zr-Ru-Si based ternary superconducting single crystal material has at least one of the following structural parameters: (1) Chemical formula: Zr2Ru3Si4; (2) Relative mass of chemical formula: 598 g·mol -1 ; (3) Test temperature: 296(2) K; (4) Superconducting transition temperature: 5.4 K; (5) Crystal system: Monoclinic; (6) Space group: C2 / c (No. 15); (7) Cell parameters: a = 19.0011(11) Å; b = 5.3526(3) Å; c = 13.2976(8) Å; α = 90°; β = 127.7430(10)°; γ = 90°; (8) Cell volume: 1069.46(11) Å 3 ; (9) Z: 8; (10) Density: 7.428 g·cm³ -3 ; (11) Absorption coefficient: 12.792 mm -1 ; (12) F(000): 2144.

[0034] Combination Figure 2 As shown in the figure, this disclosure presents a method for preparing a Zr-Ru-Si based ternary superconducting single crystal material, comprising the following steps: S10. Weigh the raw materials with a purity greater than or equal to 98% according to the set stoichiometric ratio: Zr, Ru, Si and Cu; wherein the set stoichiometric ratio is Zr : Ru : Si : Cu = (1~5): (1~10): (4~10): (10~40).

[0035] S20. After mixing the raw materials, they are placed into a crucible and then sealed in a quartz tube; wherein the quartz tube is in a vacuum state or filled with an inert atmosphere.

[0036] S30. Heat the encapsulated quartz tube from room temperature to 1100-1200℃ and keep it at that temperature for 5-50 hours; then cool it down to the crystal precipitation temperature range at a rate of 0.2-2℃ / h.

[0037] S40. At the preset crystallization temperature, quickly remove the quartz tube from the furnace and invert it to be installed in a centrifuge device for centrifugation to remove the liquid flux Cu-Si melt.

[0038] S50. Open the quartz tube to obtain a solid mixture containing the target single crystal, and then purify the solid mixture to obtain Zr-Ru-Si based ternary superconducting single crystal material.

[0039] The preparation method of this disclosure can obtain Zr-Ru-Si based ternary superconducting single crystal materials of any of the foregoing embodiments.

[0040] The preparation method disclosed in this embodiment employs a Cu-Si eutectic flux method, avoiding complex multi-step reactions and high-pressure synthesis processes. The operating conditions are relatively mild (growth temperature below 1200 ℃), making it more suitable for single crystal growth under conventional conditions. Furthermore, by controlling the heating and cooling rates and the flux ratio, precise control of crystal nucleation and growth is achieved, improving crystallinity and reproducibility. Moreover, each preparation step (flux method, centrifugation, and purification) exhibits good system compatibility and can be widely applied to the synthesis of other refractory ternary metal silicide single crystals, possessing potential value for the development of a series of materials.

[0041] The establishment of the Zr-Ru-Si ternary single crystal material preparation route in this disclosure provides a platform for subsequent functional material screening and basic physics research, and breaks through the technical barrier that ternary silicide single crystals cannot be obtained in traditional material preparation.

[0042] In step S10, the raw materials include Zr, Ru, Si, and Cu, wherein Zr, Ru, and Si are synthesized to form a Zr-Ru-Si ternary single crystal material (Zr... x Ru y Si z Si (partially) and Cu are used as fluxes to promote crystal growth. Crystal quality and nucleation conditions can be optimized by adjusting the stoichiometric ratio of Zr, Ru, Si, and Cu.

[0043] Optionally, in step S10, the stoichiometric ratio is set as Zr:Ru:Si:Cu=(2~4):(2~8):(4~8):(10~30).

[0044] Optionally, the stoichiometric ratio is set as Zr : Ru : Si : Cu = (2~3): (2~5): (5~8): (15~30).

[0045] Optionally, the stoichiometric ratio is set to Zr:Ru:Si:Cu=2:3:6:20.

[0046] In step S10, the purity of the raw materials is at least high purity, i.e., purity greater than or equal to 98%. Of course, raw materials with higher purity can be used depending on the specific materials. Optionally, the purity of the raw materials is greater than or equal to 99.5%. Optionally, the purity of the raw material Zr is 99.9%. Optionally, the purity of the raw material Ru is 99.95%. Optionally, the purity of the raw material Si is 99.999%. Optionally, the purity of the raw material Cu is 99.99%.

[0047] Optionally, the material state of the raw material may include powder or granules. The appropriate form can be selected based on the specific conditions of the raw material. For example, Zr can be Zr powder, Ru can be Ru powder, Si can be Si granules, and Cu can be Cu granules.

[0048] Optionally, in step S20, the raw materials are mixed and placed into a crucible, and then sealed in a quartz tube. After the raw materials are mixed, they can be fully contacted for reaction.

[0049] Optionally, the order in which the ingredients are mixed is not limited; they can be added simultaneously or sequentially. When added sequentially, the order of addition is not limited.

[0050] Optionally, the raw materials are mixed and then placed into a crucible, including: adding Zr powder and Ru powder into the crucible and mixing them evenly, then adding Si particles and Cu particles to obtain a raw material mixture, and then placing the raw material mixture into the crucible.

[0051] In this embodiment of the disclosure, the crucible in step S20 is a high-temperature resistant crucible that will not react with the raw materials at high temperatures, so as to avoid the raw materials reacting with the crucible at high temperatures. Optionally, the material of the crucible includes alumina or zirconium oxide.

[0052] In this embodiment of the present disclosure, in step S20, the raw material is encapsulated in a quartz tube under vacuum or filled with an inert atmosphere to prevent oxidation and contamination by impurities. Optionally, the quartz tube is in a vacuum state, with a vacuum pressure less than or equal to 10. -3 Pa. Optionally, the quartz tube is filled with an inert atmosphere, which is either nitrogen or argon.

[0053] In some embodiments, step S30, heating the packaged quartz tube from room temperature to 1100–1200°C, includes: heating the packaged quartz tube from room temperature to 1100–1200°C at a first heating rate. The heating rate is controlled to ensure that the raw materials are fully melted and mixed uniformly. For example, the first heating rate is controlled to be within 10°C / min.

[0054] In step S30, the temperature can be raised to any temperature value in the range of 1100 to 1200°C, for example, to 1100°C, 1110°C, 1120°C, 1150°C, 1160°C, 1180°C or 1200°C.

[0055] Optionally, the first heating rate is 1–10 °C / min. Optionally, the first heating rate is 1–8 °C / min. Optionally, the first heating rate is 2–6 °C / min. Optionally, the first heating rate is 2–3 °C / min.

[0056] In step S30, the heat preservation time is greater than or equal to 5 hours to ensure that the raw materials are fully melted and mixed evenly. Optionally, the heat preservation time can be 5 hours, 8 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, or 50 hours, or any duration within the range of 5 hours to 50 hours.

[0057] Optionally, in step S30, the heat preservation time is 10h to 50h. Optionally, in step S30, the heat preservation time is 20h to 50h. Optionally, in step S30, the heat preservation time is 30h to 50h. Optionally, in step S30, the heat preservation time is 40h.

[0058] In step S30, the cooling rate is controlled within the range of 0.2–2 °C / h to induce slow crystal precipitation during cooling, thereby achieving ordered crystal growth and size control. For example, the cooling rate can be 0.2 °C / h, 0.3 °C / h, 0.5 °C / h, 0.8 °C / h, 1 °C / h, 1.2 °C / h, 1.5 °C / h, 1.8 °C / h, 2 °C / h, or any rate within the range of 0.2–2 °C / h.

[0059] Optionally, the temperature is lowered to the crystal precipitation temperature range at a rate of 0.5–2 °C / h. Optionally, the temperature is lowered to the crystal precipitation temperature range at a rate of 0.6–2 °C / h. Optionally, the temperature is lowered to the crystal precipitation temperature range at a rate of 0.6–1.8 °C / h. Optionally, the temperature is lowered to the crystal precipitation temperature range at a rate of 0.6–1.5 °C / h. Optionally, the temperature is lowered to the crystal precipitation temperature range at a rate of 0.6–1.2 °C / h. Optionally, the temperature is lowered to the crystal precipitation temperature range at a rate of 0.6–1.0 °C / h.

[0060] In some embodiments, in step S30, the crystal precipitation temperature range is 1000–1100°C. The temperature can be lowered to any temperature within this crystal precipitation temperature range.

[0061] In step S40, the preset crystallization temperature is any temperature within the crystal precipitation temperature range, such as 1010℃, 1020℃, 1030℃, 1050℃, 1060℃, 1080℃, or 1100℃.

[0062] It is understandable that the crystal precipitation temperature range is less than the holding temperature before cooling. Optionally, the temperature reduction range is 80 to 120°C, for example, 80°C, 90°C, 100°C, 110°C, 120°C, or any temperature value within the range of 80 to 120°C.

[0063] In this embodiment of the present disclosure, in step S40, centrifugation is performed to discharge the liquid flux Cu-Si melt, achieving preliminary separation of the crystal and the melt. The centrifugation parameters are not limited and are determined according to actual conditions. Optionally, the centrifugation operation includes: a centrifugation speed of 500–2000 rpm and a centrifugation time of 1–3 min.

[0064] Optionally, the centrifugation speed is 800–2000 rpm. Optionally, the centrifugation speed is 1000–2000 rpm. Optionally, the centrifugation speed is 1500–2000 rpm.

[0065] In this embodiment of the present disclosure, step S50, opening the quartz tube to obtain a solid mixture containing the target single crystal, includes: cooling the centrifuged quartz tube to room temperature, breaking the quartz tube and crucible to obtain a solid mixture containing the target single crystal.

[0066] In some embodiments, step S50, purifying the solid mixture, includes: immersing the solid mixture in a strong acid solution to remove residual flux and impurities, followed by washing and drying to obtain a Zr-Ru-Si based ternary superconducting single crystal material. In this embodiment, purification is achieved by acid washing, immersing in a strong acid solution to dissolve residual Cu-Si flux. In this embodiment, the strong acid solution can be concentrated sulfuric acid or concentrated nitric acid. The immersion time is determined according to actual conditions; optionally, immersion is 12–36 hours. Optionally, immersion is 24 hours.

[0067] In this embodiment, the drying method is not limited. Optionally, drying includes drying at a temperature from room temperature to 100°C for 1 to 12 hours. It is understood that the lower the drying temperature, the longer the drying time, as long as complete drying is ensured.

[0068] Optionally, drying includes drying at a temperature of 40°C to 80°C for 1 to 8 hours.

[0069] Optionally, drying includes drying at a temperature of 50°C to 70°C for 1 to 5 hours.

[0070] Optionally, drying includes drying at 60°C for 1 to 3 hours.

[0071] This disclosure also provides applications of the aforementioned Zr-Ru-Si based ternary superconducting single crystal material or the Zr-Ru-Si based ternary superconducting single crystal material prepared by the aforementioned preparation method in the fields of medical imaging, energy and power, semiconductor manufacturing, rail transportation, industrial heating, scientific research equipment, or quantum communication.

[0072] In this disclosure, the zero resistance and perfect diamagnetism of Zr-Ru-Si based ternary superconducting single crystal materials enable their application in multiple fields. For example, the principle of generating a strong and stable magnetic field using superconducting magnets allows for application in medical imaging; the principle of supporting lossless power transmission and high power density equipment using zero resistance characteristics allows for application in the energy and power sector, especially in transmission and energy storage systems; the principle of suppressing silicon melt convection and improving the quality of single crystal silicon using superconducting magnets allows for application in semiconductor manufacturing; the principle of generating a strong magnetic field using superconducting magnets to achieve non-contact levitation and actuation allows for application in rail transportation; the principle of using high-field-strength superconducting magnets for particle acceleration and fusion research allows for application in scientific research equipment; and the principle of high-speed, low-power signal processing using the Josephson effect allows for application in quantum communication.

[0073] This disclosure also provides a terminal product, including the Zr-Ru-Si based ternary superconducting single crystal material prepared by the aforementioned Zr-Ru-Si based ternary superconducting single crystal material preparation method or the Zr-Ru-Si based ternary superconducting single crystal material preparation method.

[0074] The end product of this disclosure embodiment is a Zr-Ru-Si based ternary superconducting single crystal material, and the properties of the Zr-Ru-Si based ternary superconducting single crystal material are used to realize a tangible product or functional system with specific functions.

[0075] The terminal products of this disclosure vary depending on the application field.

[0076] Optionally, in the field of medical imaging, end products include magnetic resonance imaging (MRI) machines, nuclear magnetic resonance (NMR) spectrometers, etc.

[0077] Optionally, in the energy and power sector, end products include superconducting cables, superconducting transformers, superconducting current limiters, superconducting energy storage systems, and superconducting substations.

[0078] Optionally, in the semiconductor manufacturing field, end products include magnetron Czochralski (MCC) single-crystal silicon equipment for the growth of silicon single crystal rods (e.g., large-size silicon single crystal rods of 12 inches or more) and N-type single-crystal silicon wafers.

[0079] Optionally, in the field of rail transit, end products include maglev train test systems, etc. Optionally, in the field of scientific research equipment, end products include particle accelerators, etc.

[0080] Optionally, in the field of quantum communication, end products include superconducting filters, superconducting qubits, and superconducting single-photon detectors.

[0081] It can be understood that: terminal products refer to tangible products or functional systems that are in the "final delivery stage" of the industrial chain, directly facing specific users, and can independently meet a certain type of core needs of users through means such as magnetic resonance imaging or superconducting cables.

[0082] The following specific embodiments illustrate the Zr-Ru-Si based ternary superconducting single crystal materials, their preparation methods, applications, and end products according to the present disclosure, to more clearly explain the technical problems solved, technical solutions, and beneficial effects of this application. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit this application or its applications.

[0083] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0084] Example 1 A method for preparing Zr2Ru3Si4 ternary superconducting single crystal material includes the following steps: S11. Weigh out the raw materials with a purity greater than or equal to 99.5% according to the set stoichiometric ratio Zr:Ru:Si:Cu=2:3:6:20: Zr powder (99.9%), Ru powder (99.95%), Si particles (99.999%) and Cu particles (99.99%).

[0085] S21. Mix Zr powder and Ru powder evenly in an agate mortar, then add Si particles and Cu particles and mix well to obtain a raw material mixture; then load the raw material mixture into an alumina crucible. Next, place the alumina crucible containing the raw material mixture into a quartz tube and evacuate to 10°C. -3 Pa, and then the quartz tube is sealed by flame sealing to obtain the encapsulated quartz tube.

[0086] S31. The encapsulated quartz tube is heated from room temperature to 1120℃ at a first heating rate of 2℃ / min and held at that temperature for 40h to allow the raw materials to fully melt and mix; then the temperature is lowered to 1030℃ at a rate of 0.8℃ / h.

[0087] S41. At the preset crystallization temperature of 1030℃, quickly remove the quartz tube from the furnace and invert it into a centrifuge. Centrifuge at 2000 rpm for 2 minutes to remove the liquid flux Cu-Si melt, thereby achieving the initial separation of the crystal and the melt.

[0088] S51. After centrifugation, allow the quartz tube to cool naturally to room temperature. Break the quartz tube and crucible with a tool, remove the internal solid product, and obtain a solid mixture containing the target single crystal. Then, place the solid mixture in a concentrated nitric acid solution and soak it at room temperature for 24 hours to dissolve the residual Cu-Si flux. After washing and drying, obtain the Zr2Ru3Si4 ternary superconducting single crystal. Specifically, after removing the crystal, wash it repeatedly with deionized water and finally dry it in a drying oven at 60 °C for 2 hours.

[0089] A photograph of the Zr2Ru3Si4 ternary superconducting single crystal obtained in Example 1 is shown below. Figure 1 As shown, it is glossy black, with a smooth surface and regular edges; it is in the form of a block. For example... Figure 3 As shown, X-ray diffraction (XRD) reveals a series of diffraction peaks in the crystal, indicating that it exhibits Zr₂Ru₃Si₄. Figure 4 As shown, energy dispersive spectroscopy (EDS) confirmed that the elemental proportions of the sample conformed to the stoichiometry of Zr₂Ru₃Si₄. Figure 5 As shown, resistance measurements indicate that the single crystal undergoes a superconducting transition at approximately 5.4 K, exhibiting typical zero-resistance behavior.

[0090] Example 2 The difference between Example 2 and Example 1 is that in step S31, the packaged quartz tube is heated from room temperature to 1180°C at a first heating rate of 2°C / min and held at that temperature for 10 hours to allow the raw materials to fully melt and mix; then, it is cooled to 1080°C at a rate of 0.8°C / h. In step S41, the quartz tube is quickly removed from the furnace at the preset crystallization temperature of 1080°C and installed upside down in a centrifuge. All other steps and parameters are the same as in Example 1.

[0091] The Zr2Ru3Si4 ternary superconducting single crystal obtained in Example 2 is the same as that in Example 1. X-ray diffraction (XRD) shows that the crystal has a series of diffraction peaks of Zr2Ru3Si4. Energy dispersive spectroscopy (EDS) confirms that the elemental ratio of the sample conforms to the stoichiometry of Zr2Ru3Si4 (e.g., ...). Figure 6 (As shown).

[0092] Example 3 The difference between Example 3 and Example 1 is that in step S31, the packaged quartz tube is heated from room temperature to 1150°C at a first heating rate of 2°C / min and held at that temperature for 10 hours to allow the raw materials to fully melt and mix; then, it is cooled to 1060°C at a rate of 0.8°C / h. In step S41, the quartz tube is quickly removed from the furnace at the preset crystallization temperature of 1060°C and installed upside down in a centrifuge. All other steps and parameters are the same as in Example 1.

[0093] The Zr2Ru3Si4 ternary superconducting single crystal obtained in Example 3 is the same as that in Example 1. Energy dispersive spectroscopy (EDS) confirmed that the elemental ratios of the sample conform to the stoichiometry of Zr2Ru3Si4 (e.g., ...). Figure 7 (As shown).

[0094] Example 4 The difference between Example 4 and Example 1 is that in step S31, the packaged quartz tube is heated from room temperature to 1100°C at a first heating rate of 2°C / min and held at that temperature for 10 hours to allow the raw materials to fully melt and mix; then, it is cooled to 1010°C at a rate of 0.8°C / h. In step S41, the quartz tube is quickly removed from the furnace at the preset crystallization temperature of 1010°C and installed upside down in a centrifuge. All other steps and parameters are the same as in Example 1.

[0095] The Zr2Ru3Si4 ternary superconducting single crystal obtained in Example 4 is the same as that in Example 1. Energy dispersive spectroscopy (EDS) confirmed that the elemental ratios of the sample conform to the stoichiometry of Zr2Ru3Si4 (e.g., ...). Figure 8 (As shown).

[0096] Example 5 The difference between Example 5 and Example 1 is that in step S11, raw materials with a purity greater than or equal to 99.5% are weighed according to the set stoichiometric ratio Zr:Ru:Si:Cu=2:4:8:30.

[0097] In Example 5, a ternary superconducting single crystal with the general chemical formula Zr₂Ru₃Si₄ was obtained. Energy dispersive spectroscopy (EDS) confirmed that the elemental ratio of the sample conformed to the stoichiometry of Zr₂Ru₃Si₄ (e.g., ...). Figure 9 (As shown).

[0098] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that in step S31, the packaged quartz tube is heated from room temperature to 1080°C at a first heating rate of 2°C / min and held at that temperature for 40 hours to allow the raw materials to fully melt and mix; then, it is cooled to 980°C at a rate of 0.8°C / h. In step S41, the quartz tube is quickly removed from the furnace at the preset crystallization temperature of 980°C and installed upside down in a centrifuge. All other steps and parameters are the same as in Example 1.

[0099] The material obtained in Comparative Example 1 was the binary compound Ru2Si3 (see...). Figure 10 The energy dispersive spectroscopy (EDS) results are shown below.

[0100] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that in step S11, raw materials with a purity greater than or equal to 99.5% are weighed according to the set stoichiometric ratio Zr:Ru:Si:Cu=1:1:1:8. The remaining steps and parameters are the same as in Example 1.

[0101] The material obtained in Comparative Example 2 was the Zr-Cu-Si ternary compound Zr3Cu4Si4 (see [link]). Figure 11 The energy dispersive spectroscopy (EDS) results are shown below.

[0102] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0103] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A Zr-Ru-Si based ternary superconducting single crystal material, characterized in that, The chemical general formula of the Zr-Ru-Si-based ternary superconducting single crystal material is Zr x Ru y Si z wherein x = 1.8-2.2, y = 2.5-3.5, and z = 3.5-4.

5.

2. The Zr-Ru-Si based ternary superconducting single-crystal material of claim 1, wherein, x = 1.9-2.1, y = 2.8-3.2, z = 3.8-4.

2.

3. The Zr-Ru-Si based ternary superconducting single-crystal material of claim 1, wherein, has at least one of the following multiple structure parameters: Chemical formula: Zr2Ru3Si4; Chemical Formula Relative mass: 598 g-mol -1 ; Test temperature: 296(2) K; Superconducting transition temperature: 5.4 K; Crystal system: monoclinic; Space group: C2 / c (No. 15); Cell parameters: a = 19.0011(11) Å; b = 5.3526(3) Å; c = 13.2976(8) Å; α = 90°; β = 127.7430(10) °; γ = 90°; Cell dimensions: 1069.46(11) A3 3 ; Z：8； Density: 7.428 g-cm -3 ; Absorption coefficient: 12.792 mm -1 ; F(000)：2144。 4. The method of producing a Zr-Ru-Si based ternary superconducting single-crystal material according to any one of claims 1 to 3, wherein including: The raw materials with a purity greater than or equal to 98% are weighed according to the set stoichiometric ratio: Zr, Ru, Si and Cu; wherein the set stoichiometric ratio is Zr: Ru: Si: Cu = (1-5): (1-10): (4-10): (10-40); After mixing the raw materials, they are loaded into a crucible and then packaged in a quartz tube; wherein the quartz tube is in a vacuum state or filled with an inert atmosphere; The packaged quartz tube is heated from room temperature to 1100-1200℃ and held for 5-50h; then cooled to the crystal precipitation temperature interval at a rate of 0.2-2 ℃ / h; The quartz tube is quickly removed from the furnace at the preset crystallization temperature and installed upside down in a centrifugal device for centrifugal operation to remove the residual Cu-Si solvent melt; Open the quartz tube to obtain a solid mixture containing the target single crystal, and then purify the solid mixture to obtain a Zr-Ru-Si-based ternary superconducting single crystal material.

5. The preparation method of the Zr-Ru-Si-based ternary superconducting single crystal material according to claim 4, wherein, the set stoichiometric ratio is Zr: Ru: Si: Cu = (2-4): (2-8): (4-8): (10-30); or the set stoichiometric ratio is Zr: Ru: Si: Cu = (2-3): (2-5): (5-8): (15-30); or the set stoichiometric ratio is Zr: Ru: Si: Cu = 2:3:6:

20.

6. The method for preparing Zr-Ru-Si based ternary superconducting single crystal material according to claim 4, characterized in that, The quartz tube is in a vacuum state, and the vacuum pressure is less than or equal to 10 -3 Pa; Alternatively, the quartz tube is filled with an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.

7. The preparation method of the Zr-Ru-Si-based ternary superconducting single crystal material according to claim 4, wherein, the packaged quartz tube is heated from room temperature to 1100-1200℃, including: the packaged quartz tube is heated from room temperature to 1100-1200℃ at a first heating rate, wherein the first heating rate is 1-10 ℃ / min; or the first heating rate is 1-8 ℃ / min; or the first heating rate is 2-6 ℃ / min; or the first heating rate is 2-3 ℃ / min.

8. The preparation method of the Zr-Ru-Si-based ternary superconducting single crystal material according to claim 4, wherein, the cooling rate to the crystal precipitation temperature interval is 0.5-2 ℃ / h; or the cooling rate to the crystal precipitation temperature interval is 0.6-2 ℃ / h; or ​ cooling to the crystal precipitation temperature interval at a rate of 0.6-1.8 ℃ / h; or cooling to the crystal precipitation temperature interval at a rate of 0.6-1.5 ℃ / h; or cooling to the crystal precipitation temperature interval at a rate of 0.6-1.2 ℃ / h; or cooling to the crystal precipitation temperature interval at a rate of 0.6-1.0 ℃ / h.

9. The method for preparing the Zr-Ru-Si-based ternary superconducting single crystal material according to any one of claims 4 to 8, characterized in that, the sealed quartz tube is heated from room temperature to 1120-1180 ℃; and / or the crystal precipitation temperature interval is 1000-1100 ℃; and / or the preset crystallization temperature is any temperature within the crystal precipitation temperature interval.

10. The method for preparing the Zr-Ru-Si-based ternary superconducting single crystal material according to any one of claims 4 to 8, characterized in that, the raw materials are placed in the crucible, including: the Zr powder and the Ru powder are added into the crucible and mixed uniformly, and then the Si particles and the Cu particles are added to obtain the raw material mixture; and / or the centrifugation operation includes: the centrifugal speed is 500-2000 rpm, and the centrifugation time is 1-3 min; and / or the quartz tube is opened to obtain the solid mixture containing the target single crystal, including: the quartz tube and the crucible are knocked to obtain the solid mixture containing the target single crystal; and / or the solid mixture is purified, including: the solid mixture is soaked in a strong acid solution to remove residual fluxing agents and impurities, and then washed and dried to obtain the Zr-Ru-Si-based ternary superconducting single crystal material.

11. The application of the Zr-Ru-Si-based ternary superconducting single crystal material according to any one of claims 1 to 3 or the Zr-Ru-Si-based ternary superconducting single crystal material prepared by the method for preparing the Zr-Ru-Si-based ternary superconducting single crystal material according to any one of claims 4 to 10 in the field of medical imaging, the field of energy transmission, the field of semiconductor manufacturing, the field of rail transportation, the field of scientific research devices or the field of quantum communication.

12. A terminal product, characterized in that The Zr-Ru-Si-based ternary superconducting single crystal material according to any one of claims 1 to 3 or the Zr-Ru-Si-based ternary superconducting single crystal material prepared by the method for preparing the Zr-Ru-Si-based ternary superconducting single crystal material according to any one of claims 4 to 10.

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