A processing method, superconducting layer and superconducting material for improving superconducting current-carrying performance

Abstract

The application discloses a processing method for improving the current-carrying performance of a second-generation high-temperature superconductor, a superconducting layer and a superconducting material. The processing method comprises the following steps: performing ion implantation on a superconducting layer which has not been subjected to an oxidation heat treatment, and introducing nanoscale defects into the superconducting layer; the types of the implantation ions include non-metal gas ions and metal ions; then, a silver film is plated on the surface of the superconducting layer after the ion implantation treatment; and then, high-temperature oxidation heat treatment is performed, so that at least part of the nanoscale defects form nanoscale oxide particles under the action of the implantation ions and the oxidation treatment. The processing method is beneficial to improving the current-carrying performance of the superconducting tape, and the cost is relatively low.

Description

Technical Field

[0001] This invention relates to the field of second-generation high-temperature superconducting technology, specifically to a processing method, a superconducting layer, and a superconducting material that are beneficial to improving superconducting current-carrying performance. Background Technology

[0002] Superconducting tapes are key materials for energy generation, conversion, transmission, and storage, and are used in many scientific and industrial fields, such as nuclear magnetic resonance imaging (MRI) in medicine, the Large Hadron Collider in particle accelerators, and the International Thermonuclear Experimental Reactor (ITER) magnetic confinement fusion device. Facing the explosive growth in demand for second-generation high-temperature superconducting tapes in the future, it is imperative to vigorously develop the fabrication technology of second-generation high-temperature superconducting tapes, and further improve their superconducting current-carrying performance in high-field environments. This is expected to significantly reduce the production cost of high-temperature superconducting tapes and promote their widespread application in more industries.

[0003] There are several ways to improve the electrical properties of high-temperature superconducting tapes: reducing the thickness of the substrate, increasing the thickness of the REBCO superconducting layer, and introducing nano-pinning defects to increase the critical current or the superconducting critical temperature. The REBCO superconducting layer has a quaternary system structure, which is more complex than that of typical superconductors, and its oxidative stress plays a decisive role in its performance. The inherent supersaturation level of the superconducting layer determines its nanolayered structure, thus affecting the electrical properties of the high-temperature superconducting tape. Epitaxial thin film growth methods are needed to obtain grain orientations with a certain biaxial texture, allowing for unimpeded current transmission along the tape's length. Furthermore, pinning defects capable of controlling flux need to be artificially engineered at the nanoscale. Types of nano-pinning defects generally include point defects, stacking faults, nanorods, and nanoparticles. While superconducting layer deposition methods such as metal-organic chemical vapor deposition (MOCVD), metal-organic chemical solution deposition (MOD), and pulsed laser deposition (PLD) can introduce pinning defects such as nanorods and nanoparticles to some extent by controlling the supersaturation of chemical components, there is still room for further improvement in the number density, so as to further enhance the superconducting current-carrying performance in high-field applications.

[0004] Numerous studies have shown that moderate irradiation of superconducting materials can introduce a large number of irradiation defects, such as extremum peaks, atom-depleted regions, vacancies, interstitial atoms, dislocations, stacking faults, voids, defect clusters, and new precipitated phases, which can increase magnetic flux pinning strength and density, and improve critical current density. However, using neutron and proton irradiation sources to improve the current-carrying properties of superconducting materials has drawbacks such as high cost and long research cycles. In particular, second-generation high-temperature superconducting tapes are prone to radioactivity after neutron irradiation, and this irradiation can degrade the properties of other structures such as cladding and insulating layers. Summary of the Invention

[0005] The technical problem to be solved by this invention is: how to improve the current carrying capacity of superconducting tapes. This invention provides a processing method, a superconducting layer, and a superconducting material that are beneficial to improving the current carrying capacity of superconducting tapes and have relatively low cost.

[0006] This invention is achieved through the following technical solution:

[0007] A method for improving the current-carrying capacity of second-generation high-temperature superconducting tapes involves ion implantation into a superconducting layer that has not undergone oxidation heat treatment, introducing nanoscale defects within the superconducting layer. The implanted ions include non-metallic gas ions and metallic ions. The method further includes depositing a silver film onto the surface of the superconducting layer after ion implantation, followed by high-temperature oxidation heat treatment. This allows the superconducting layer to absorb oxygen through the silver film, thereby acquiring superconducting properties. At least some of the nanoscale defects are transformed into nano-oxide particles under the combined effects of ion implantation and oxidation treatment.

[0008] Ion implantation is performed on the exposed, untreated superconducting layer. The implanted ions include at least metal ions. Nanoscale defects are introduced through ion implantation, especially various nanoscale defects such as extrema, atom-depleted regions, vacancies, interstitial atoms, dislocations, stacking faults, voids, defect clusters, and new precipitates. Among these, defects such as extrema, atom-depleted regions, vacancies, and dislocations may disappear due to annealing recovery during heat treatment, but voids, defect clusters, and precipitates may remain. In particular, metal implantation elements can form RE site substitutions (such as Y, Sm, Nd, Gd, etc.) or Cu site substitutions (such as U, Nb, W, Zr, Ta, Bi, Ag, Mo, Ru, Sn, Hf, Fe, Co, Ni, Zn, Al, Ga, Mn, etc.). The metal ion clusters and substitutions formed can combine with oxygen during oxidative heat treatment to generate more high-density nano-oxide particles. These nano-oxide particles, together with the many nanoscale defects generated during ion implantation, produce a stronger magnetic flux pinning effect to further improve the current carrying capacity of high-temperature superconducting materials.

[0009] The injected metal ions include, but are not limited to, combinations of one or more elements from various valence states of Gd, Tb, Zr, Dy, Sm, Sr, Ba, Nd, Y, Au, Ni, Ti, V, Ta, Zn, Ca, Cr, Cu, Fe, Co, W, Mo, Ru, Al, Ga, Mn, U, Nb, Ta, Bi, Ag, Pt, Pd, Hg, Sn, Hf, Ce, La, Eu, Ho, Er, Tm, Yb, Lu, Tl, and Li.

[0010] The types of injected ions may also include non-metallic ions, especially non-metallic gas ions. Non-metallic ions include, but are not limited to, combinations of one or more elements from various valence states of H, He, O, Ar, etc.

[0011] For ion implantation of multiple elements, it can be performed sequentially or simultaneously using dual, triple, or multiple ion beams. The ion beam is generated by a Mevva ion source or a van der Graff generator. The ion beam is accelerated to medium-high energy via an extraction grid or accelerating tube to implant ions into the superconducting layer. The dimensions of the extraction grid or extraction window match the dimensions of the second-generation high-temperature superconducting tape, featuring a narrow and elongated design. The extraction grid is integrally machined from sputter-resistant materials such as tungsten, molybdenum, and graphite, with a width of 5mm-50mm and a length of 500mm-1500mm. The grid holes are arranged in a honeycomb pattern, with a size ≤2.5mm.

[0012] Further optionally, the thickness of the silver film is 1μm-3μm; more preferably, the thickness of the silver film is 2μm. The function of the silver film is not only to protect the superconducting layer, but also to allow oxygen to better penetrate into the superconducting layer during oxidative heat treatment, enabling the superconducting layer to react with oxygen and thus exhibit superconductivity. Additionally, it can serve as a transition layer between the superconducting layer and the copper layer, ensuring a good connection between the two. If the silver film is too thin, it will not provide adequate protection for the superconducting layer; if it is too thick, it may affect the bonding performance between the superconducting layer and the copper layer, potentially leading to delamination of the superconducting tape.

[0013] Further optionally, the high-temperature oxidation heat treatment parameters include: oxidation heat treatment temperature of 450℃-550℃, and / or oxidation holding time of 0.5h-1.5h.

[0014] After ion implantation, a high-temperature superconducting layer is coated with a silver film with a thickness of 1 μm-3 μm, preferably 2 μm. Then, a high-temperature oxidation heat treatment is performed to allow the high-temperature superconducting layer to absorb oxygen through the silver film, thereby acquiring superconducting properties. The oxidation heat treatment temperature is 450℃-550℃, preferably 500℃; the holding time is 0.5h-1.5h, preferably 1h.

[0015] Further optionally, the particle size of the nano-oxide particles is 0.5nm-100nm, and / or the spacing between the nano-oxide particles is 5nm-50nm.

[0016] The preferred particle size of the oxide particles is 5nm-20nm, and the particle spacing is 5nm-50nm. For high-temperature superconducting tapes used at high fields, the particle spacing of the nano-oxide particles should be smaller, such as 5nm recommended at 20T; for low-field applications, the particle spacing should be larger, such as 50nm recommended at 1T; the oxide particle density is 1×10⁻⁶. 15 -1×10 17 / m2 High-density oxide particles act as magnetic flux pinning agents, further improving the current-carrying capacity of high-temperature superconductors.

[0017] Further, optionally, the type of nano-oxide particles depends on the type of ion implantation, including BaO, SrO, SmO, CaO, CoO, PdO, Ag2O, Y2O3, Eu2O3, Ho2O3, Dy2O3, Gd2O3, La2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Bi2O3, Au2O3, Al2O3, Cr2O3, Fe2O3, SnO 2. One or more of the following: UO2, TiO2, ZrO2, ZnO2, HfO2, PtO2, CeO2, WO3, MoO3, TbOx, GaOx, Ta2O5, V2O5, Nb2O5, BaTiO3, BaZrO3, SrTiO3, LaMnO3, LaAlO3, LaNiO3, LaCuO3, SrRuO3, NdGaO3, and NdAlO3.

[0018] Alternatively, the ion implantation temperature is room temperature, or between 200°C and 1000°C.

[0019] The temperature for ion implantation can be room temperature, or between 200℃ and 1000℃, preferably between 700℃ and 850℃. Ion implantation at high temperatures facilitates the formation of nanoprecipitates or nanoclusters by ions reacting with other elements in the superconducting layer, such as oxygen.

[0020] Further optionally, the ion implantation depth is less than the thickness of the superconducting layer, and / or the ion implantation energy is 0.1 MeV-5 MeV, and / or the ion implantation dose is 1 × 10⁻⁶. 11 -10 18 ions / cm 2 And / or the ion beam current range is in the nA-μA range.

[0021] Based on the atomic ratio and other structural parameters of the exposed superconducting layer without oxidation heat treatment, and the types of ions to be implanted, the ion implantation depth and corresponding energy are calculated using SRIM software. The implantation depth should not exceed the thickness of the superconducting layer (e.g., 0.5 μm-3 μm). Ion energy ranges from 0.1 MeV to 5 MeV, with 0.5 MeV-2 MeV being preferred. The energy varies depending on the ion type, and the selected energy must ensure that it reaches more than half the thickness of the superconducting layer but does not exceed the total thickness of the superconducting layer. The ion source voltage is calculated based on the energy. The ion implantation dose range is 1 × 10⁻⁶. 11 -10 18 ions / cm 2 The preferred dosage is 1-5×10 17 ions / cm2 The ion implantation time is determined based on the ion implantation dose, and the ion beam current is calculated. Ion implantation times range from several minutes to several hours. The ion beam current ranges from nA to μA.

[0022] The ion implantation parameters were determined based on the above calculations. Under the action of a medium-to-high energy ion beam, ions were implanted into the interior of the exposed superconducting layer of the second-generation high-temperature superconducting tape. The ion implantation direction is generally at 0° to the normal of the second-generation high-temperature superconducting tape.

[0023] A superconducting layer is obtained by processing it using a method described above that is beneficial to improving superconducting current-carrying performance.

[0024] A superconducting material, comprising the superconducting layer described above, or a superconducting layer obtained by processing using one of the above-described methods to improve superconducting current-carrying performance.

[0025] The superconducting tape with a superconducting layer obtained by the processing method provided by the present invention has a current carrying capacity improvement effect of 110%-300% compared with that before processing, preferably 300%.

[0026] Optionally, the superconducting material further includes a metal substrate layer, an isolation buffer layer, and a coating layer, wherein the metal substrate layer, the isolation buffer layer, the superconducting layer, the silver plating layer, and the coating layer are arranged sequentially from bottom to top.

[0027] For example, a superconducting tape is provided, in which an isolation buffer layer and a superconducting layer are deposited on a mirror-finished metal substrate of Hastelloy or stainless steel with nanoscale surface roughness using methods such as MOCVD, MOD, and PLD. The isolation buffer layer is a multilayer film containing oxides such as Al2O3, Y2O3, MgO, and LaMnO3, with a thickness of 100nm-300nm. The superconducting layer is a REBCO superconducting layer with a thickness of 0.5μm-3μm. At this stage, the superconducting layer has not undergone oxidation heat treatment and only contains elements such as RE, Ba, and Cu, but not O. The obtained superconducting layer is then treated using one of the aforementioned methods to improve its superconducting current-carrying performance.

[0028] Ion implantation of the second-generation high-temperature superconducting tape is performed in a vacuum system with a background vacuum ≤10. -4 Pa. A tape-walking system is used to walk the second-generation high-temperature superconducting tape at a speed ≥30 m / h. A Mevva ion source or van der Graff generator is set up to implant ions into the superconducting layer of the second-generation high-temperature superconducting tape using a medium-to-high energy ion beam. A low-energy electron beam is used to neutralize the ion beam charge and prevent local arcing damage. The required ion implantation time is calculated based on the ion implantation dose. For low doses, such as 10 Pa, the required time is calculated accordingly. 11-15 ions / cm 2At higher doses, the tape-transfer system may only require one pass to complete the ion implantation of the entire tape. For high doses, such as 10... 16-18 ions / cm 2 In this stage, the conveyor system requires multiple cycles to complete the ion implantation of the strip. Ion implantation equipment can be integrated with Ag layer deposition equipment, oxidation heat treatment equipment, cladding layer deposition equipment, etc., or it can be set up independently.

[0029] The present invention has the following advantages and beneficial effects:

[0030] 1. The present invention provides a processing method, superconducting layer, and superconducting material that are beneficial to improving superconducting current carrying performance. First, the superconducting layer without oxidation heat treatment is ion implanted, then a silver layer is deposited, and finally a high-temperature oxidation heat treatment is performed. This can form nanoscale irradiation defects and nano-oxide particles in the subsequent oxidation heat treatment process, thereby increasing the density of magnetic flux pinning defects and thus improving the high-temperature superconducting current carrying performance.

[0031] High-energy ion implantation, building upon traditional superconducting layer fabrication methods such as MOCVD, MOD, and PLD, can introduce various nanoscale defects, including extremal peaks, atom-depleted regions, vacancies, interstitial atoms, dislocations, stacking layers, voids, defect clusters, new precipitates, and RE and Cu substitutions. These nanoscale defects and substitutions can further increase the flux pinning center density, thereby enhancing the current-carrying capacity of superconducting tapes under self-field and high-field conditions. Combined with subsequent oxidation thermal treatment, high-density oxide nanoparticles can be generated. These oxide nanoparticles will also serve as strong flux pinning centers, further increasing the current-carrying density of the tape.

[0032] 2. This invention uses ion implantation combined with silver plating and high-temperature oxidation heat treatment to introduce high-density nano-pinning defects into the superconducting layer to improve the current-carrying performance of second-generation high-temperature superconductors. This method offers advantages such as low cost, ease of operation, and short cycle time. Furthermore, if the ion source extraction gate or ion beam extraction window used in the ion implantation is designed with an ultra-large aspect ratio rectangle that matches the size of the high-temperature superconducting tape, it is suitable for ion implantation of long-strand high-temperature superconductors. Combined with a uniformly advancing tape-carrying system, this can greatly improve working efficiency and increase production capacity. Attached Figure Description

[0033] The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and form part of this application, do not constitute a limitation thereof. In the drawings:

[0034] Figure 1 This is a schematic diagram of ion implantation, where an ion beam is formed through an extraction grid or extraction window to create a rectangular cross-section adapted to the aspect ratio of a high-temperature superconducting tape.

[0035] Figure 2This is a transmission electron microscope (TEM) image of the superconducting layer after Fe ion implantation in Example 1 (ion implantation dose 1*10⁻⁶). 13 ions / cm 2 ).

[0036] Figure 3 This is a transmission electron microscope (TEM) image of the superconducting layer after Ni ion implantation in Example 2 (ion implantation dose 1*10⁻⁶). 17 ions / cm 2 ).

[0037] Figure 4 This is a transmission electron microscope (TEM) image of the superconducting layer after Ag ion implantation in Example 3 (ion implantation dose 1*10⁻⁶). 17 ions / cm 2 ). Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and accompanying drawings. The illustrative embodiments and descriptions of the present invention are only used to explain the present invention and are not intended to limit the present invention.

[0039] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be apparent to those skilled in the art that these specific details are not necessary to practice the invention. In other embodiments, well-known structures, materials, or methods are not specifically described in order to avoid obscuring the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0040] Example 1

[0041] This embodiment provides a processing method to improve the superconducting current-carrying performance and obtain a high-temperature superconducting layer, which is processed in the following steps:

[0042] Step 1: Ion implantation is performed on the superconducting layer without oxidation heat treatment to introduce nanoscale defects into the superconducting layer. The types of implanted ions include metal ions.

[0043] An isolation buffer layer and a superconducting layer were deposited on a 4 mm wide Hastelloy mirror metal substrate using conventional MOCVD. Ion implantation was then performed on the exposed, untreated superconducting layer.

[0044] The superconducting layer has a thickness of 1.1 μm. The implanted ions are Fe ions. Based on the atomic ratio and other structural parameters of the untreated, untreated superconducting layer and the type of ions to be implanted (Fe ions), the ion implantation depth and the corresponding energy are calculated using SRIM software. The implantation depth does not exceed the thickness of the superconducting layer. The ion energy is 0.15 MeV-5 MeV, varying depending on the ion type. The selected energy must be at least half the thickness of the superconducting layer and not exceed its total thickness. The ion source voltage is calculated based on the energy: V = E / C, where V is the voltage, E is the ion energy, and C is the charge per unit ion (determined by the ion type, such as Au). 3+ (C=3). Ion implantation dose range 1×10⁻⁶. 11 -10 18 ions / cm 2 The preferred dosage is 1-5×10 17 ions / cm 2 The ion implantation time is determined based on the ion implantation dose, and the ion beam current is calculated as I = ФCq / t, where I is the ion beam current, Ф is the implantation dose, q is the charge per unit charge, and t is the ion implantation time. The current and ion implantation time must be balanced in the determination process; generally, the ion implantation time should be greater than 5 minutes to control implantation rate error. Depending on the type of ion and the required implantation energy and depth, the implantation time can range from several minutes to several hours. By determining the ion implantation depth, implantation dose, implantation time, ion source voltage, and ion beam current using the above steps, ion implantation of the superconducting layer can be carried out.

[0045] like Figure 1 As shown, the angle between the ion beam and the normal of the high-temperature superconducting tape is generally 0°; the second-generation high-temperature superconducting tape is fed into the ion implantation device through a roll-to-roll tape transport system. To ensure the uniformity of ion implantation of the second-generation high-temperature superconducting tape, the tape transport needs to maintain a uniform forward speed, ranging from 30 m / h to 100 m / h, preferably ≥60 m / h, and more preferably 100 m / h.

[0046] In this embodiment, the implanted ion is Fe. + The ion implantation depth is approximately 300-700 nm, the ion implantation energy is 0.4 MeV, and the ion implantation dose is 1*10⁻⁶. 13-17 ions / cm 2 The ion implantation time varies from a few minutes to 20 hours depending on the implantation dose. The ion source voltage is 0.4 MeV, the ion beam current is about 0.5 mA, the ion implantation temperature is room temperature, and the transport speed is 60 m / h.

[0047] Step 2: Deposit a silver film on the surface of the superconducting layer after ion implantation treatment.

[0048] After ion implantation, a high-temperature superconducting layer is coated with an Ag film with a thickness of 2 μm.

[0049] Step 3: Perform high-temperature oxidation heat treatment to form nano-oxide particles from at least some of the nanoscale defects under the action of ion implantation and oxidation treatment.

[0050] After silver plating, a high-temperature heat treatment is performed so that the high-temperature superconducting layer can absorb oxygen through the silver plating layer and thus acquire superconducting properties. The oxidation heat treatment temperature is 500℃ and the holding time is 1 hour.

[0051] like Figure 2 As shown, transmission electron microscopy characterization analysis revealed that the ion implantation dose was 1*102. 13 ions / cm 2 After Fe ion implantation, the nano-oxide particles in the superconducting layer are mainly of the types Fe2O3, Y2O3, and Gd2O3, with a particle size of about 5-20 nm and a spacing of about 10-50 nm.

[0052] Example 2

[0053] This embodiment provides a processing method to improve the superconducting current-carrying performance and obtain a high-temperature superconducting layer, which is processed in the following steps:

[0054] Step 1: Ion implantation is performed on the superconducting layer without oxidation heat treatment to introduce nanoscale defects into the superconducting layer. The types of implanted ions include metal ions.

[0055] An isolation buffer layer and a superconducting layer were deposited on a 4 mm wide Hastelloy mirror metal substrate using conventional MOCVD. Ion implantation was then performed on the exposed, untreated superconducting layer.

[0056] The thickness of the superconducting layer is 1.1 μm. Ni ions are implanted. Based on the atomic ratio and other structural parameters of the untreated, untreated superconducting layer and the type of ions to be implanted, the ion implantation depth and corresponding energy are calculated using SRIM software. The implantation depth does not exceed the thickness of the superconducting layer. The ion energy is 0.15 MeV-5 MeV, varying depending on the ion type. The selected energy must be at least half the thickness of the superconducting layer and not exceed its total thickness. The ion source voltage is calculated based on the energy: V = E / C, where V is the voltage, E is the ion energy, and C is the charge per unit ion (determined by the ion type, such as Au). 3+ (C=3). Ion implantation dose range 1×10⁻⁶. 11 -10 18 ions / cm 2 The preferred dosage is 1-5×10 17ions / cm 2 The ion implantation time is determined based on the ion implantation dose, and the ion beam current is calculated as I = ФCq / t, where I is the ion beam current, Ф is the implantation dose, q is the charge per unit charge, and t is the ion implantation time. The current and ion implantation time must be balanced in the determination process; generally, the ion implantation time should be greater than 5 minutes to control implantation rate error. Depending on the type of ion and the required implantation energy and depth, the implantation time can range from several minutes to several hours. By determining the ion implantation depth, implantation dose, implantation time, ion source voltage, and ion beam current using the above steps, ion implantation of the superconducting layer can be carried out.

[0057] like Figure 1 As shown, the angle between the ion beam and the normal of the high-temperature superconducting tape is generally 0°; the second-generation high-temperature superconducting tape is fed into the ion implantation device through a roll-to-roll tape transport system. To ensure the uniformity of ion implantation of the second-generation high-temperature superconducting tape, the tape transport needs to maintain a uniform forward speed, ranging from 30 m / h to 100 m / h, preferably ≥60 m / h, and more preferably 100 m / h.

[0058] In this embodiment, the ion implantation type is Ni. + The ion implantation depth is approximately 250-600 nm, the ion implantation energy is 0.4 MeV, and the ion implantation dose is 1 × 10⁻⁶. 11 -10 17 ions / cm 2 The ion implantation time varies from a few minutes to 50 hours depending on the implantation dose. The ion source voltage is 0.4 MeV, the ion beam current is about 0.5 mA, the ion implantation temperature is room temperature, and the transport speed is 60 m / h.

[0059] Step 2: Deposit a silver film on the surface of the superconducting layer after ion implantation treatment.

[0060] After ion implantation, a high-temperature superconducting layer is coated with an Ag film with a thickness of 2 μm.

[0061] Step 3: Perform high-temperature oxidation heat treatment to form nano-oxide particles from at least some of the nanoscale defects under the action of ion implantation and oxidation treatment.

[0062] After silver plating, a high-temperature heat treatment is performed to enable the high-temperature superconducting layer to absorb oxygen and exhibit superconducting properties. The oxidation heat treatment temperature is 500℃, and the holding time is 1 hour.

[0063] like Figure 3 As shown, transmission electron microscopy characterization analysis revealed that the ion implantation dose was 1*102. 17 ions / cm 2After Ni ion implantation, the nano-oxide particles in the superconducting layer are LaNiO3, Y2O3, Gd2O3, etc., with a particle size of about 5-30 nm and a spacing of about 20-50 nm.

[0064] Example 3

[0065] This embodiment provides a processing method to improve the superconducting current-carrying performance and obtain a high-temperature superconducting layer, which is processed in the following steps:

[0066] Step 1: Ion implantation is performed on the superconducting layer without oxidation heat treatment to introduce nanoscale defects into the superconducting layer. The types of implanted ions include metal ions.

[0067] An isolation buffer layer and a superconducting layer were deposited on a 4 mm wide Hastelloy mirror metal substrate using conventional MOCVD. Ion implantation was then performed on the exposed, untreated superconducting layer.

[0068] The thickness of the superconducting layer is 0.5 μm. The implanted ions are Ag ions. Based on the atomic ratio and other structural parameters of the untreated, untreated superconducting layer and the type of ions to be implanted, the ion implantation depth and corresponding energy are calculated using SRIM software. The implantation depth does not exceed the thickness of the superconducting layer. The ion energy is 0.15 MeV-5 MeV, varying depending on the ion type. The selected energy must be at least half the thickness of the superconducting layer and not exceed its total thickness. The ion source voltage is calculated based on the energy: V = E / C, where V is the voltage, E is the ion energy, and C is the charge per unit ion (determined by the ion type, such as Au). 3+ (C=3). Ion implantation dose range 1×10⁻⁶. 11 -10 18 ions / cm 2 The preferred dosage is 1-5×10 17 ions / cm 2 The ion implantation time is determined based on the ion implantation dose, and the ion beam current is calculated as I = ФCq / t, where I is the ion beam current, Ф is the implantation dose, q is the charge per unit charge, and t is the ion implantation time. The current and ion implantation time must be balanced in the determination process; generally, the ion implantation time should be greater than 5 minutes to control implantation rate error. Depending on the type of ion and the required implantation energy and depth, the implantation time can range from several minutes to several hours. By determining the ion implantation depth, implantation dose, implantation time, ion source voltage, and ion beam current using the above steps, ion implantation of the superconducting layer can be carried out.

[0069] like Figure 1As shown, the angle between the ion beam and the normal of the high-temperature superconducting tape is generally 0°; the second-generation high-temperature superconducting tape is fed into the ion implantation device through a roll-to-roll tape transport system. To ensure the uniformity of ion implantation of the second-generation high-temperature superconducting tape, the tape transport needs to maintain a uniform forward speed, ranging from 30 m / h to 100 m / h, preferably ≥60 m / h, and more preferably 100 m / h.

[0070] In this embodiment, the implanted ion is Ag. + The ion implantation depth is approximately 100-300 nm, the ion implantation energy is 0.4 MeV, and the ion implantation dose is 1 × 10⁻⁶. 11 -10 17 ions / cm 2 The ion implantation time ranges from several minutes to 20 hours depending on the implantation dose. The ion source voltage is 0.4 MeV, the ion beam current is approximately 0.5 mA, the ion implantation temperature is room temperature, and the transport speed is 60 m / h.

[0071] Step 2: Deposit a silver film on the surface of the superconducting layer after ion implantation treatment.

[0072] After ion implantation, a high-temperature superconducting layer is coated with an Ag film with a thickness of 2 μm.

[0073] Step 3: Perform high-temperature oxidation heat treatment to form nano-oxide particles from at least some of the nanoscale defects under the action of ion implantation and oxidation treatment.

[0074] After silver plating, a high-temperature heat treatment is performed to enable the high-temperature superconducting layer to absorb oxygen and exhibit superconducting properties. The oxidation heat treatment temperature is 500℃, and the holding time is 1 hour.

[0075] like Figure 4 As shown, transmission electron microscopy characterization analysis revealed that the ion implantation dose was 1*102. 17 ions / cm 2 After Ag ion implantation, the nano-oxide particles in the superconducting layer are of the types Ag2O, Y2O3, and Gd2O3, with a particle size of about 5-30 nm and a spacing of about 10-50 nm.

[0076] Example 4

[0077] For Examples 1-3 above, during ion implantation: a roll-to-roll tape transport system is used for transporting the second-generation high-temperature superconducting tape; a Mevva ion source or a van der Graff generator is used for ion implantation of the second-generation high-temperature superconducting tape; a vacuum system is used to evacuate the ion implantation equipment, requiring a background vacuum ≤10°C before ion implantation. -4To accommodate the dimensions of second-generation high-temperature superconducting tapes, the ion beam extraction grid from the Mevva ion source or the ion beam window accelerated by the van der Graff generator is a rectangular design with an ultra-high aspect ratio. The dimensions of the extraction grid or ion beam window match the dimensions of the second-generation high-temperature superconducting tape, featuring a narrow and elongated design, and are integrally fabricated using sputter-resistant materials such as tungsten, molybdenum, and graphite. The grid holes of the Mevva source extraction grid are arranged in a honeycomb pattern, with a size ≤2.5mm. The ion beam exiting through the extraction grid or ion beam window completely covers the width direction of the second-generation high-temperature superconducting tape, such as 5mm-50mm, and has meter-level coverage capability in the length direction, such as 500mm-1500mm. The ion beam exhibits high energy density and uniform distribution within the ion implantation range.

[0078] Example 5:

[0079] This embodiment provides a superconducting tape, which consists of a 4mm wide Hastelloy mirror metal substrate, an isolation buffer layer, a superconducting layer, a silver plating layer, and a copper cladding layer from bottom to top. The superconducting layer is a superconducting layer processed using the method described in Example 1. The superconducting tape is named Sample 1.

[0080] Example 6:

[0081] This embodiment provides a superconducting tape, which consists of a 4mm wide Hastelloy mirror metal substrate, an isolation buffer layer, a superconducting layer, a silver plating layer, and a copper cladding layer from bottom to top. The superconducting layer is a superconducting layer processed using the method described in Example 2. The superconducting tape is named Sample 2.

[0082] Example 7:

[0083] This embodiment provides a superconducting tape, which consists of a 4mm wide Hastelloy mirror metal substrate, an isolation buffer layer, a superconducting layer, a silver plating layer, and a copper cladding layer from bottom to top. The superconducting layer is a superconducting layer processed using the method described in Example 3. The superconducting tape is named Sample 3.

[0084] Comparative Example 1

[0085] This comparative example provides a superconducting tape comprising, from bottom to top, a 4mm wide Hastelloy mirror metal substrate, an isolation buffer layer, a superconducting layer, a silver plating layer, and a copper cladding layer. The superconducting layer was not ion implanted (superconducting layer deposition was performed only using methods such as MOCVD or PLD), and was subsequently silver-plated and oxidized. This superconducting tape is named Comparative Sample 1.

[0086] Comparative Example 2

[0087] This comparative example provides a superconducting tape consisting of a 4mm wide Hastelloy mirror metal substrate, an isolation buffer layer, a superconducting layer, and a copper cladding layer, from bottom to top. The superconducting layer is only ion implanted and is not silver-plated or oxidized. This superconducting tape is named Comparative Sample 2.

[0088] Comparative Example 3:

[0089] This embodiment provides a superconducting tape, comprising, from bottom to top, a 4mm wide Hastelloy mirror-finished metal substrate, an isolation buffer layer, a superconducting layer, and a copper cladding layer. The superconducting layer is only Fe-coated. + Ion implantation and oxidation heat treatment, without silver plating, the superconducting tape is named Comparative Sample 3.

[0090] Comparative Example 4:

[0091] This embodiment provides a superconducting tape, comprising, from bottom to top, a 4mm wide Hastelloy mirror-finished metal substrate, an isolation buffer layer, a superconducting layer, a silver plating layer, and a copper cladding layer. The superconducting layer is subjected to Fe... + Ion implantation was performed, followed by silver plating and oxidation. The silver plating thickness was 5 μm (higher than the conventional thickness of 2 μm). The superconducting tape was named Comparative Sample 4.

[0092] Comparative Example 5:

[0093] This embodiment provides a superconducting tape, comprising, from bottom to top, a 4mm wide Hastelloy mirror-finished metal substrate, an isolation buffer layer, a superconducting layer, a silver plating layer, and a copper cladding layer. The superconducting layer undergoes Fe... + Ion implantation was performed, followed by silver plating and oxidation treatment. The oxidation heat treatment temperature was 400℃ (lower than the conventional temperature), and the holding time was 0.5h (lower than the conventional time). The superconducting tape was named Comparative Sample 5.

[0094] Superconducting tapes were prepared using the superconducting layers obtained in Examples 5-7 above, and the properties of the obtained superconducting tapes were measured. The test results are given. For comparison, superconducting tapes were prepared using the same method with the superconducting layers obtained in Comparative Examples 1-5 above, and the same measurements were performed. Specifically, the critical current of the superconducting tapes was tested using a four-lead method testing system or a Power Profiling System (PPMS), at test temperatures of 20K and 30K, and a test magnetic field of 0-9T.

[0095] Performance test results:

[0096] All test performance results are shown in the following table and / or description:

[0097] Table 1 Performance Test Results

[0098]

[0099] The measurement results in the table above show that the superconducting tape samples 1-3 obtained in Examples 5-7 exhibit superior critical current-carrying performance at low temperatures of 20K and 30K. However, the superconducting tapes obtained in Comparative Examples 1-5 have lower performance due to factors such as lack of ion implantation, lack of silver plating, lack of oxidation heat treatment, excessively thick silver plating, or excessively low heat treatment temperature. For example, the lack of ion implantation results in insufficient nanodefects and oxides, leading to lower current-carrying performance. In particular, the absence of silver plating or oxidation heat treatment prevents the superconducting layer from absorbing oxygen, resulting in a lack of superconductivity and a current of 0. Performing only ion implantation and oxidation heat treatment without silver plating prevents the superconducting layer from absorbing oxygen through the silver layer, resulting in insufficient oxygen absorption. Furthermore, the lack of a silver layer as a transition layer weakens the bond between the superconducting layer and the copper layer, leading to insufficient superconducting tape performance. If the silver plating thickness is too high, it will hinder oxygen absorption during the oxidation heat treatment; if the oxidation heat treatment temperature is too low and the time is too short, the amount of nano-oxide formed will be insufficient, resulting in poor current carrying capacity of the superconducting tape.

[0100] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A treatment method to improve superconducting current-carrying performance, comprising ion implantation into a superconducting layer that has not undergone oxidation heat treatment, thereby introducing nanoscale defects within the superconducting layer, characterized in that, The types of implanted ions include non-metallic gas ions and metallic ions; The processing methods also include: After ion implantation treatment, a silver film is deposited on the surface of the superconducting layer, and then a high-temperature oxidation heat treatment is performed. This allows the superconducting layer to absorb oxygen through the silver plating layer, thereby acquiring superconducting properties. At least some nanoscale defects are transformed into nano-oxide particles under the action of ion implantation and oxidation treatment. The thickness of the silver film is 1µm-3µm.

2. The processing method for improving superconducting current-carrying performance according to claim 1, characterized in that, The high-temperature oxidation heat treatment parameters include: oxidation heat treatment temperature of 450℃-550℃, and / or oxidation holding time of 0.5h-1.5h.

3. The processing method for improving superconducting current-carrying performance according to claim 1, characterized in that, The nano-oxide particles have a particle size of 0.5nm-100nm and / or a spacing of 5nm-50nm between them.

4. The processing method for improving superconducting current-carrying performance according to claim 1, characterized in that, The types of nano-oxide particles depend on the type of ion implantation, including BaO, SrO, SmO, CaO, CoO, PdO, Ag2O, Y2O3, Eu2O3, Ho2O3, Dy2O3, Gd2O3, La2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Bi2O3, Au2O3, Al2O3, Cr2O3, Fe2O3, SnO2, and U. One or more of the following: O2, TiO2, ZrO2, ZnO2, HfO2, PtO2, CeO2, WO3, MoO3, TbOx, GaOx, Ta2O5, V2O5, Nb2O5, BaTiO3, BaZrO3, SrTiO3, LaMnO3, LaAlO3, LaNiO3, LaCuO3, SrRuO3, NdGaO3, and NdAlO3.

5. The processing method for improving superconducting current-carrying performance according to claim 1, characterized in that, The ion implantation temperature is room temperature, or between 200℃ and 1000℃.

6. The processing method for improving superconducting current-carrying performance according to claim 1, characterized in that, The ion implantation depth is less than the thickness of the superconducting layer, and / or the ion implantation energy is 0.1 MeV-5 MeV, and / or the ion implantation dose is 1 × 10⁻⁶. 11 -10 18 ions / cm 2 And / or the ion beam current range is in the nA-µA range.

7. A superconducting layer, characterized in that, The sample was obtained by processing using a method that improves superconducting current-carrying performance, as described in any one of claims 1 to 6.

8. A superconducting material, characterized in that, It includes the superconducting layer as described in claim 7, or a superconducting layer obtained by a processing method described in any one of claims 1 to 6 that is beneficial for improving superconducting current-carrying performance.

9. A superconducting material according to claim 8, characterized in that, It also includes a metal substrate layer, an isolation buffer layer, and a coating layer, which are arranged sequentially from bottom to top.

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