CN110453189B - Continuous device for growing REBCO superconducting film based on dislocation technology - Google Patents
Continuous device for growing REBCO superconducting film based on dislocation technology Download PDFInfo
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- CN110453189B CN110453189B CN201910882975.4A CN201910882975A CN110453189B CN 110453189 B CN110453189 B CN 110453189B CN 201910882975 A CN201910882975 A CN 201910882975A CN 110453189 B CN110453189 B CN 110453189B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
Abstract
The invention provides a continuous device for growing a REBCO superconducting film based on an off-position technology, wherein a reel-to-reel multi-channel reciprocating film coating unit deposits a substance of a target material on a base band to form a metal film by utilizing magnetron sputtering, and the base band enters 3 quartz tubes for heat treatment after passing through two slits of a vacuum trap in sequence, so that the metal film on the base band absorbs oxygen and is converted into the superconducting film with a superconducting phase. The invention overcomes the technical prejudice, uses the magnetron sputtering off-position technology to carry out deposition coating, uses the introduced vacuum trap as a transition device, enables the coating and heat treatment processes to be a continuous system, and simultaneously can ensure that the coating and the heat treatment processes do not interfere with each other, namely the realization of the coating and the superconducting phase can occur in two different and continuous processes, and can use a set of quartz tubes with different thicknesses to realize the effect of vacuum difference, thereby carrying out heat treatment on the film under different oxygen partial pressures and realizing the conversion of the film from a metal film to the superconducting film.
Description
Technical Field
The invention relates to the technical field of superconducting materials, in particular to a continuous device for growing a REBCO superconducting film based on an off-position technology, in particular to a device for preparing a superconducting layer continuous coating film and performing heat treatment by the off-position technology, which is a manufacturing device for a second-generation high-temperature superconducting tape superconducting layer.
Background
Second generation superconducting tapes, which are also referred to as coated conductors, are generally produced by a process of applying a multilayer coating film on a nickel-based alloy substrate because REBCO, which is a superconducting current-carrying core, is inherently hard and brittle. The second generation superconducting tapes generally consist of a metal base tape, a buffer layer (transition layer), a superconducting layer, and a protective layer. The role of the metal substrate is to provide the strip with excellent mechanical properties. The transition layer has the functions of preventing the mutual diffusion between elements of the superconducting layer and the metal substrate, and providing a good template for the epitaxial growth of the superconducting layer by the uppermost transition layer, so that the REBCO crystal grain arrangement quality is improved. The preparation of coated conductors with excellent superconducting properties requires the superconducting layer to have a sharp biaxial texture. The alignment degree (in-plane texture) of the REBCO film in the a/b axis direction is relatively difficult to realize, and the poor in-plane texture can seriously reduce the superconducting performance. It is therefore desirable to epitaxially grow YBCO superconducting films on transition layers that already have biaxial texture and matched crystal lattice. Two main technical routes for realizing the biaxial texture are available in the preparation, one is a rolling assisted biaxial texture base band (RABiTS) technology, and the other is an Ion Beam Assisted Deposition (IBAD) technology. Common techniques for preparing the REBCO superconducting layer are classified into various techniques, such as Pulsed Laser Deposition (PLD), Metal Organic Chemical Vapor Deposition (MOCVD), Metal Organic Decomposition (MOD), Magnetron sputtering (magntron sputtering), reactive Co-evaporation, and the like (Co-evaporation). The last layer is a protective layer, which is mainly used for protecting the superconducting layer, and a silver layer with the thickness of several microns is generally plated on the surface of the superconducting strip.
In the YBCO coated conductor, the base band and buffer layers are the base portions and the superconducting layer is the core portion. Both the RABiTS technique and the IBAD technique provide for high quality coated conductors. With the continuous development of the coated conductor technology, all physical and chemical epitaxy technologies are used for researching the YBCO coated conductor. The plating technique of the superconducting layer can be roughly divided into an in-situ preparation technique and an ex-situ preparation technique. In-situ fabrication techniques refer to films deposited on a substrate that directly possess a superconducting phase, whereas films deposited on a substrate using ex-situ fabrication techniques do not possess a superconducting phase and require subsequent processing to convert to a superconducting phase, such as vacuum differential heat treatment.
Patent document CN102884594B discloses a method for forming a ceramic wire, in which a ceramic precursor film is deposited on a wire substrate, and then the wire substrate on which the ceramic precursor film is deposited is treated by heating. For treating the wire substrate by heating, the temperature of the wire substrate and/or the oxygen partial pressure of the wire substrate is controlled such that the ceramic precursor film is in a liquid state and the epitaxial ceramic film is formed from the liquid ceramic precursor film on the wire substrate. The literature proposes to prepare a precursor film by using deposition technologies such as a co-evaporation method, a laser ablation method, a chemical vapor deposition method, a Metal Organic Deposition (MOD), a sol-gel method and the like, wherein the co-evaporation method and the MOD method are exemplified in the embodiment, and are not related to a magnetron sputtering method, and the following technical bias is mainly adopted: 1) the magnetron sputtering process atmosphere is rare gas such as argon (Ar), the process vacuum is higher such as 500mTorr (about 66.5Pa), the process atmosphere and the pure oxygen atmosphere (about 100mTorr) of the heat treatment system can generate contradiction, the quality of the superconducting layer is influenced, and the production efficiency is influenced if the process atmosphere is divided into two independent process devices; 2) the magnetron sputtering is difficult to control the molar ratio of different elements and difficult to adjust. 3) The existing cognition can directly plate the oxide superconducting film by utilizing a radio frequency or medium frequency magnetic control process, so that the situation that a metal film is firstly plated by utilizing a direct current magnetic control process and then phase transformation is realized by off-position post-treatment is difficult to think.
Disclosure of Invention
In view of the drawbacks of the prior art, it is an object of the present invention to provide a continuous apparatus for growing REBCO superconducting films based on the ex-situ technique.
The invention provides a continuous device for growing a REBCO superconducting film based on an off-position technology, which comprises a roll-to-roll multi-channel reciprocating film coating unit, a vacuum trap, a vacuum differential heat treatment unit and a rolling unit;
the reel-to-reel multi-channel reciprocating coating unit sputters the material on the composite target onto a plurality of reciprocating base bands by utilizing magnetron sputtering to form a metal mixed film layer with a set element proportion, and the metal mixed film layer is coated on the base bands;
the vacuum trap realizes series connection and atmosphere isolation of a reel-to-reel multi-channel reciprocating coating unit and a vacuum differential heat treatment unit through an adjustable slit, a base band coated with a metal mixed film layer is introduced into the vacuum differential heat treatment unit, and superconducting phase transformation is realized in the differential vacuum and high-temperature environment of the vacuum differential heat treatment unit;
and the winding unit winds the base band after the superconducting phase conversion.
Preferably, the roll-to-roll multi-channel reciprocating coating unit comprises a lifting support, a reciprocating tape transport assembly, a heating assembly and a target material;
the lifting support is arranged opposite to the target, the area between the lifting support and the target is used as a coating area, the lifting support is provided with a reciprocating tape transport assembly, a base tape reciprocates on the reciprocating tape transport assembly to pass through the coating area, a heating assembly is arranged in the coating area, and the base tape moves around the heating assembly;
the target material is a magnetron sputtering base band, the position of the target material can be lifted, and the position of the lifting support can be lifted so as to adjust the target base distance between the target material and the base band.
Preferably, the target material can be an alloy target or a multi-element mixed metal target formed by splicing multiple elemental metal target strips, the multi-element mixed metal target forms a target surface as a sputtering surface, and the number and the position of the elemental metal target strips can be adjusted.
The material of the multi-element mixed metal target is sputtered onto the base band by means of direct current magnetron sputtering.
Preferably, the target base distance is controlled within the range of 0.05m to 0.2m by adjusting the heights of the lifting support and the target respectively.
The process gas of the magnetron sputtering is argon, the sputtering pressure is 3-10 mTorr, and the thickness of the metal mixed film layer on the base band is in the range of 1-2 mu m.
Preferably, the heating assembly comprises any one or more of a heating source, a heating plate, a power supply, a temperature controller and a thermocouple, so as to adjust and control temperature rise, temperature keeping and temperature reduction, and the heating source comprises any one or more of an infrared lamp tube, silicon carbide and a resistance wire.
Preferably, the reel-to-reel multi-channel reciprocating coating unit further comprises a first baffle and a second baffle, the shielding area of the first baffle can be adjusted and is arranged at the edge of the coating area to adjust the coating area, and the second baffle is arranged between the material placing disc for containing the base band and the target material to prevent pollution to the material placing disc.
Preferably, the reel-to-reel multi-channel reciprocating coating unit further comprises a material discharge tray, a speed wheel and a tension wheel, wherein the base band extends out of the material discharge tray and enters a coating area by the rotation of the speed wheel and the tension wheel in sequence;
the tape running speed of the base tape is monitored through the speed wheel, the reverse tension is monitored through the tension wheel, and the tape running speed and the reverse tension are fed back to the rear motor and the magnetic powder brake of the discharging disc so as to control the tape running speed and the reverse tension of the base tape.
Preferably, the vacuum trap comprises a first slit, a second slit, a vacuum gauge;
the first slit and the second slit are respectively positioned at two sides of the vacuum trap and are respectively adjustable slits;
the vacuum gauge vacuumizes the vacuum trap and reflects the real-time vacuum degree of the vacuum trap.
Preferably, the vacuum differential thermal treatment unit comprises a first quartz tube, a second quartz tube, a third quartz tube, a second vacuum gauge, a third vacuum gauge, an oxygenation assembly and a heater;
the first quartz tube, the second quartz tube and the third quartz tube are communicated in sequence, wherein the diameter of the second quartz tube is smaller than that of the first quartz tube and that of the second quartz tube so as to realize vacuum difference;
the oxygenation assembly comprises an oxygen mass flow meter and a stainless steel elbow, wherein the mass flow meter is used for controlling oxygen flow, and the stainless steel elbow guides oxygen into one side of the third quartz tube;
the heater consists of a plurality of heating areas along the advancing direction of the base band, and different heating areas are provided with different heating temperatures;
the second vacuum gauge and the third vacuum gauge are used for monitoring the oxygen partial pressure of the first quartz tube and the third quartz tube respectively, and the oxygen partial pressure is used for adjusting the oxygen charging amount of the oxygen charging assembly, the length of the second quartz tube and the size of an adjustable slit of the vacuum trap.
Preferably, the winding unit comprises a material collecting disc, a fourth vacuum pump, a second tension pulley, a second speed pulley and a fourth vacuum gauge;
the base band enters a material receiving disc for winding after passing through a second tension wheel and a second speed wheel in sequence;
the second tension pulley monitors the tension of the winding unit and feeds the tension back to the magnetic powder brake at the rear side of the discharging disc of the roll-to-roll multi-channel reciprocating coating unit so as to realize constant tension;
the second speed wheel monitors the tape travelling speed of the base tape and feeds the tape travelling speed back to a motor at the rear side of a material discharging disc of the reel-to-reel multi-channel reciprocating coating unit so as to realize constant speed;
the fourth vacuum pump realizes the vacuum environment of the winding unit, and the fourth vacuum gauge monitors the vacuum environment of the winding unit.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can overcome the prejudice of the prior art that the magnetron sputtering technology is used for coating, simplifies the complexity of the equipment and improves the coating efficiency.
2. The invention can use the vacuum trap device to connect the coating and heat treatment processes into a continuous process, and simultaneously can ensure that the coating and the heat treatment processes do not interfere with each other, namely the realization of the coating and the superconducting phase can occur in two different and continuous processes.
3. The invention can realize the effect of vacuum difference by using a set of quartz tubes with different thicknesses, and further carry out heat treatment on the film layer under different oxygen partial pressures, thereby realizing the conversion of the film layer from a metal film to an oxide superconducting film.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a schematic structural diagram of a target assembly;
FIG. 3 is a schematic view of a multi-pass reciprocating tape deck;
FIG. 4 and FIG. 5 are schematic views of a heating module;
FIG. 6 is a schematic view of a vacuum trap;
FIG. 7 is a schematic view of an adjustable slit;
FIG. 8 is a schematic view of an adjustable backing plate.
The figures show that:
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention adopts the vacuum trap device, can realize the isolation of the magnetron sputtering process atmosphere and the heat treatment process atmosphere, keeps the relative independence of the magnetron sputtering process atmosphere and the heat treatment process atmosphere, and can connect the two process flows into a continuous process. In addition, the magnetron sputtering target material uses an alloy target or a simple substance element splicing target, namely a metal mixed target formed by splicing Rare Earth (RE), barium (Ba) and copper (Cu) target strips, and the proportion can be conveniently adjusted by adjusting the number (proportion) of the target strips with different elements. Because the magnetron sputtering device has lower cost and higher production rate, compared with other off-position technologies, the magnetron sputtering device has higher cost performance.
As shown in fig. 1, the continuous apparatus for growing REBCO superconducting film based on the off-site technology provided by the invention comprises a roll-to-roll multi-channel reciprocating coating unit 1, a vacuum trap 2, a vacuum differential heat treatment unit 3 and a rolling unit 4;
the reel-to-reel multi-channel reciprocating coating unit 1 sputters materials on the composite target onto a plurality of reciprocating base bands by utilizing magnetron sputtering to form a metal mixed film layer with a set element proportion, and the metal mixed film layer is coated on the base bands;
the vacuum trap 2 realizes the series connection and atmosphere isolation of the reel-to-reel multi-channel reciprocating coating unit 1 and the vacuum differential heat treatment unit 3 through an adjustable slit, introduces the base band coated with the metal mixed film layer into the vacuum differential heat treatment unit 3, and realizes superconducting phase transformation in the differential vacuum and high-temperature environment of the vacuum differential heat treatment unit 3;
and the winding unit 4 winds the baseband converted by the superconducting phase.
Specifically, the roll-to-roll multi-channel reciprocating coating unit 1 comprises a lifting support 14, a reciprocating tape transport assembly 16, a heating assembly 18 and a target 19;
the lifting support 14 and the target 19 are arranged oppositely, the area between the lifting support 14 and the target 19 is used as a coating area, the lifting support 14 is provided with a reciprocating tape transport assembly 16, the base tape reciprocates on the reciprocating tape transport assembly 16 and passes through the coating area, a heating assembly 18 is arranged in the coating area, and the base tape moves around the heating assembly 18; preferably, as shown in fig. 3, the reciprocating belt assembly 16 is composed of a left belt wheel and a right belt wheel, the direction of the base belt can be changed after passing through the belt wheels, and two sets of belt wheel sets with the same number can form a multi-path reciprocating belt type, which is beneficial to increasing the deposition area of the coating film, thereby increasing the coating efficiency.
The target 19 is a magnetron sputtering base band, the position of the target 19 can be lifted, and the position of the lifting support 14 can be lifted so as to adjust the target base distance between the target 19 and the base band.
Specifically, the target 19 is a multi-element mixed metal target formed by splicing multiple element metal target strips, the target surface formed by the multi-element mixed metal target is used as a sputtering surface, and the number and the positions of the element metal target strips can be adjusted; the metal target can be an alloy target or a composite target formed by splicing.
The material of the multi-element mixed metal target is sputtered onto the base band by means of direct current magnetron sputtering. Preferably, as shown in fig. 2, the magnetron sputtering mode is dc/pulsed dc magnetron sputtering, in which the material composition is a multi-element mixed metal target of rare earth RE, barium Ba, copper Cu, and the molar ratio of each element can be adjusted according to the process requirement.
Preferably, the process gas of the magnetron sputtering is argon, the sputtering pressure is 3-10 mTorr, and the thickness of the metal mixed film layer on the base band is in the range of 1-2 μm.
Specifically, the target base distance is controlled within the range of 0.05m to 0.2m by adjusting the heights of the lifting support 14 and the target 19 respectively; preferably, as shown in fig. 8, the target 19 has an adjustable backing plate with a backing distance of 0.1 m.
Specifically, as shown in fig. 4 and 5, the heating assembly 18 includes any one or more of a heating source, a heating plate, a power supply, a temperature controller, and a thermocouple, so as to perform adjustable and controllable temperature rise, temperature maintenance, and temperature reduction, and the heating source includes any one or more of an infrared lamp tube, silicon carbide, and a resistance wire.
Specifically, the reel-to-reel multi-channel reciprocating coating unit 1 further comprises a first baffle 17 and a second baffle 20, the shielding area of the first baffle 17 can be adjusted and is arranged at the edge of the coating area to adjust the coating area, and the second baffle 20 is arranged between the material placing disc 10 for placing the base band and the target 19 to prevent the material placing disc 10 from being polluted.
Specifically, the reel-to-reel multi-channel reciprocating coating unit 1 further comprises a material placing disc 10, a speed wheel 11 and a tension wheel 12, wherein the base band extends out of the material placing disc 10 and enters a coating area through the rotation of the speed wheel 11 and the tension wheel 12 in sequence;
the tape running speed of the base tape is monitored through the speed wheel 11, the reverse tension is monitored through the tension wheel 12, and the tape running speed and the reverse tension are fed back to the rear motor and the magnetic powder brake of the discharging tray 10 so as to control the tape running speed and the reverse tension of the base tape.
Specifically, the vacuum trap 2 includes a first slit 21, a second slit 22, a vacuum gauge 23; as shown in fig. 6 and 7, the first slit 21 and the second slit 22 are respectively located at two sides of the vacuum trap 2, and the first slit 21 and the second slit 22 are respectively adjustable slits; the vacuum gauge 23 evacuates the vacuum trap 2 and reflects the real-time vacuum level of the vacuum trap. The vacuum pump is used for pumping vacuum by adjusting the adjustable slits on the two sides under the premise of ensuring the normal passing of the base band, so that the vacuum trap 2 achieves higher vacuum degree (10)-3Pa) is added. The vacuum trap 2 can make the process atmosphere on the left and right sidesThe enclosure can keep independence and simultaneously can be connected in series to form two technological processes. Preferably, a background vacuum is drawn (e.g., 10)-4Pa), the slit is opened as large as possible, which is beneficial to quickly realizing background vacuum; when the process vacuum is needed to be realized, the slit can be adjusted to be minimum (limit is set in advance), the pressure intensity of the vacuum trap 2 can be two orders of magnitude smaller than the process atmosphere on the two sides by utilizing the slit, and further the process atmospheres on the two sides can be prevented from mutual interference.
Specifically, the vacuum differential thermal treatment unit 3 includes a first quartz tube 32, a second quartz tube 33, a third quartz tube 34, a second vacuum gauge 31, a third vacuum gauge 35, an oxygenation assembly 36, a heater 37;
the first quartz tube 32, the second quartz tube 33 and the third quartz tube 34 are sequentially communicated, wherein the diameter of the second quartz tube 33 is smaller than the diameters of the first quartz tube 32 and the second quartz tube 33, so as to realize different vacuum degrees, i.e. the effect of vacuum difference is realized;
the oxygenation assembly 36 comprises an oxygen mass flow meter to control oxygen flow and a stainless steel elbow that directs oxygen to one side of the third quartz tube 34;
the heater 37 is composed of a plurality of heating zones along the advancing direction of the base band, and different heating zones are provided with different heating temperatures;
the second vacuum gauge 31 and the third vacuum gauge 35 monitor the oxygen partial pressure of the first quartz tube 32 and the third quartz tube 34, respectively, and the oxygen partial pressure is used to adjust the oxygen charging amount of the oxygen charging assembly 36, the length of the second quartz tube 33, and the size of the adjustable slit of the vacuum trap 2.
Specifically, the winding unit 4 comprises a material collecting tray 40, a fourth vacuum pump 41, a second tension pulley 42, a second speed pulley 43 and a fourth vacuum gauge 44;
the base band enters the material receiving disc 40 to be wound after passing through the second tension wheel 42 and the second speed wheel 43 in sequence;
the second tension pulley 42 monitors the tension of the winding unit 4 and feeds the tension back to the magnetic powder brake at the rear side of the discharging disc 10 of the reel-to-reel multi-path reciprocating coating unit 1 to realize constant tension;
the second speed wheel 43 monitors the tape travelling speed of the base tape and feeds the tape travelling speed back to the motor at the rear side of the material discharge disc 10 of the reel-to-reel multi-channel reciprocating coating unit 1 so as to realize constant speed;
the fourth vacuum pump 41 realizes a vacuum environment (10) of the take-up unit 4-3Pa), the fourth vacuum gauge 44 monitors the vacuum environment of the take-up unit 4. Similarly, the vacuum environment of the whole device needs to be provided with vacuum pumps in the reel-to-reel multilayer reciprocating film coating unit 1 and the vacuum trap 2 respectively.
In the specific implementation process, the device comprises a roll-to-roll multi-channel reciprocating coating unit 1, a vacuum trap 2, a vacuum differential heat treatment unit 3 and a rolling unit 4; the reel-to-reel multi-channel reciprocating coating unit 1 deposits the substance of the target material 19 on the base band to form a metal film by magnetron sputtering, and the base band enters 3 quartz tubes for heat treatment after sequentially passing through two slits of the vacuum trap 2, so that the metal film on the base band absorbs oxygen, is liquefied, is solidified and is converted into a superconducting film with a superconducting phase.
Firstly, taking the preparation process of REBCO second-generation high-temperature superconduction as an example (Re represents rare earth elements such as Gd, Eu and the like), the specific implementation mode of the process disclosed by the invention is explained. And coating the base band with the biaxial texture buffer layer in a sputtering cavity. The coating target material is an alloy target or a composite target, the components of the target material are Re, Ba and Cu, and the proportion of the three elements is 1:2: 3. Sputtering target material onto the base band with biaxial texture buffer layer by using direct current magnetron sputtering technology. The base distance of the target is controlled within the range of 0.05m to 0.2m by adjusting the height of the liftable bracket 14 and the height of the target material 19 of the liftable magnetron sputtering target, and the base distance is preferably 0.1 m. The sputtering process gas is preferably Ar, and the sputtering pressure is preferably 8 mTorr. The strip with the biaxially textured buffer layer is passed back and forth through the coating zone in a multi-pass winding manner while the target 19 is at 5W/cm2When the power density of the film is used for sputtering, the film coating speed can reach 0.3 mu m/min. After the coating is finished in the coating area, the thickness of the metal mixture precursor film on the strip can be 1-1.5 mu m.
After finishing the film coating, the strip with the metal mixture precursor film enters a vacuum differential heat treatment unit 3 for carrying out an annealing process. The vacuum differential heat treatment unit comprises a quartz tube, a multi-zone heater, an oxygenation device and a vacuum gauge; different oxygen partial pressures in the quartz tubes, namely the vacuum difference effect can be realized by controlling the flow of the oxygenation device, the pumping speed of the vacuum pump and the like; the base band enters a first section of quartz tube after coming out of the vacuum trap, and the film layer absorbs oxygen in the section and is heated and heated to be even liquefied; then the substrate enters a third section of quartz tube with higher oxygen partial pressure after passing through a thinner quartz tube, and the film layer in the section continuously absorbs oxygen and is rapidly solidified to be converted into a film layer with a superconducting phase. The annealing process is divided into two parts, wherein the first part is a low-oxygen partial pressure temperature-rise liquefaction process, and the second part is a high-oxygen partial pressure phase change and solidification process. The strip with the metal mixture enters the first quartz tube 32 with its oxygen partial pressure controlled between 1mTorr and 50 mTorr. The heater 37 has the function of controlling the temperature, and the temperature of the strip is gradually increased during the process of the first quartz tube 32 until the metal mixture film is transformed into the liquid phase, and the temperature is maintained at 700 ℃ and 950 ℃ before leaving the first quartz tube 32. The strip with the liquid phase metal mixture exits from the first quartz tube 32 as the first annealing chamber and enters the third quartz tube 34 as the second annealing chamber, and the two quartz tubes pass through the second quartz tube 33 of the long and thin pipeline, so that a definite oxygen partial pressure gradient is ensured between the two annealing chambers. The strip with the liquid phase metal mixture is kept in a high temperature and liquid phase state from the first quartz tube 32 to the third quartz tube 34. In the third quartz tube 34, the liquid-phase metal mixture on the strip absorbs oxygen and undergoes phase transition under the condition of high oxygen partial pressure, so that the liquid-phase metal mixture is converted into a second-generation high-temperature superconductor, and the oxygen partial pressure is controlled to be between 80mTorr and 300 mTorr. The strip starts to cool and solidify the reaction product before leaving the third quartz tube 34, and after leaving the third quartz tube 34, the second generation high temperature superconductor film on the base band with biaxial texture buffer layer is formed, and the base band is wound into a material receiving disc through a material receiving chamber 4.
In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (9)
1. A continuous device for growing REBCO superconducting films based on an off-site technology is characterized by comprising a roll-to-roll multi-channel reciprocating film coating unit (1), a vacuum trap (2), a vacuum differential heat treatment unit (3) and a rolling unit (4);
the reel-to-reel multi-channel reciprocating coating unit (1) sputters materials on a composite target onto a multi-channel reciprocating base band by utilizing magnetron sputtering to form a metal mixed film layer with a set element proportion, and the metal mixed film layer is coated on the base band;
the vacuum trap (2) realizes series connection and atmosphere isolation of a reel-to-reel multi-channel reciprocating coating unit (1) and a vacuum differential heat treatment unit (3) through an adjustable slit, a base band coated with a metal mixed film layer is introduced into the vacuum differential heat treatment unit (3), and superconducting phase transformation is realized in the differential vacuum and high-temperature environment of the vacuum differential heat treatment unit (3);
the winding unit (4) winds the base band after superconducting phase conversion;
the roll-to-roll multi-channel reciprocating coating unit (1) comprises a target (19); the target material (19) is a multi-element mixed metal target formed by splicing metal target strips containing various elements, and a target surface formed by the multi-element mixed metal target is used as a sputtering surface; or the target material (19) is a composite target formed by splicing;
the vacuum trap (2) comprises a first slit (21), a second slit (22) and a vacuum gauge (23); the first slit (21) and the second slit (22) are respectively positioned at two sides of the vacuum trap (2), and the first slit (21) and the second slit (22) are respectively adjustable slits; the vacuum gauge (23) vacuumizes the vacuum trap (2) and reflects the real-time vacuum degree of the vacuum trap; the adjustable slits on the two sides are adjusted to ensure that the baseband normally passes through, a vacuum pump is used for pumping vacuum, and the vacuum trap (2) ensures that the process atmospheres on the left side and the right side are independent and can be connected in series to form two process flows; when the process vacuum is needed to be realized, the slit is firstly adjusted to be minimum, the pressure intensity of the vacuum trap (2) is two orders of magnitude smaller than the process atmosphere on the two sides by utilizing the slit, and further the process atmospheres on the two sides are not interfered with each other.
2. The continuous device for growing REBCO superconducting films based on the dislocation technology according to claim 1, wherein the roll-to-roll multi-channel reciprocating coating unit (1) comprises a lifting bracket (14), a reciprocating tape assembly (16) and a heating assembly (18);
the lifting support (14) and the target (19) are arranged oppositely, the area between the lifting support (14) and the target (19) is used as a coating area, a reciprocating tape transport assembly (16) is arranged on the lifting support (14), the base tape reciprocates on the reciprocating tape transport assembly (16) to pass through the coating area, a heating assembly (18) is arranged in the coating area, and the base tape moves around the heating assembly (18);
the target (19) is a magnetron sputtering base band, the position of the target (19) can be lifted, and the position of the lifting support (14) can be lifted so as to adjust the target base distance between the target (19) and the base band.
3. The apparatus for growing REBCO superconducting films according to claim 2, wherein the target material (19) is an alloy target or a multi-element mixed metal target formed by splicing multiple elemental metal target strips, the multi-element mixed metal target forms a target surface as a sputtering surface, and the number and the position of the elemental metal target strips can be adjusted;
the material of the multi-element mixed metal target is sputtered onto the base band by means of direct current magnetron sputtering.
4. The apparatus for growing REBCO superconducting films according to claim 2, wherein the target base distance is controlled within the range of 0.05-0.2 m by adjusting the heights of the lifting support (14) and the target (19), respectively;
the process gas of the magnetron sputtering is argon, the sputtering pressure is 3-10 mTorr, and the thickness of the metal mixed film layer on the base band is 1-2 mu m.
5. The apparatus for growing REBCO superconducting films according to claim 2, wherein the heating assembly (18) comprises any one or more of a heating source, a heating plate, a power supply, a temperature controller, and a thermocouple, so as to adjust and control the temperature rise, temperature maintenance, and temperature reduction, and the heating source comprises any one or more of an infrared lamp tube, silicon carbide, and a resistance wire.
6. The apparatus for continuously growing REBCO superconducting films based on the dislocation technology as claimed in claim 2, wherein the reel-to-reel multi-pass reciprocating coating unit (1) further comprises a first baffle plate (17) and a second baffle plate (20), the shielding area of the first baffle plate (17) can be adjusted and is arranged at the edge of the coating area to adjust the coating area, and the second baffle plate (20) is arranged between the material placing tray (10) for placing the base tapes and the target material (19) to prevent the material placing tray (10) from being polluted.
7. The apparatus for continuously growing REBCO superconducting films based on the dislocation technology according to claim 2, wherein the reel-to-reel multi-channel reciprocating film coating unit (1) further comprises a material discharge tray (10), a speed wheel (11) and a tension wheel (12), wherein the base tape extends out of the material discharge tray (10) and enters the film coating area by the rotation of the speed wheel (11) and the tension wheel (12);
the tape running speed of the base tape is monitored through the speed wheel (11), the reverse tension is monitored through the tension wheel (12), and the tape running speed and the reverse tension are fed back to the rear motor and the magnetic powder brake of the discharging disc (10) so as to control the tape running speed and the reverse tension of the base tape.
8. The continuous device for growing REBCO superconducting films based on the ex-situ technique according to claim 1, characterized in that the vacuum differential thermal treatment unit (3) comprises a first quartz tube (32), a second quartz tube (33), a third quartz tube (34), a second vacuum gauge (31), a third vacuum gauge (35), an oxygenation assembly (36), a heater (37);
the first quartz tube (32), the second quartz tube (33) and the third quartz tube (34) are communicated in sequence, wherein the diameter of the second quartz tube (33) is smaller than that of the first quartz tube (32) and that of the second quartz tube (33) so as to realize vacuum difference;
the oxygenation assembly (36) comprises an oxygen mass flow meter to control oxygen flow and a stainless steel elbow that directs oxygen to one side of the third quartz tube (34);
the heater (37) consists of a plurality of heating areas along the advancing direction of the base band, and different heating areas are provided with different heating temperatures;
the second vacuum gauge (31) and the third vacuum gauge (35) respectively monitor the oxygen partial pressure of the first quartz tube (32) and the third quartz tube (34), and the oxygen partial pressure is used for adjusting the oxygen charging amount of the oxygen charging assembly (36), the length of the second quartz tube (33) and the size of an adjustable slit of the vacuum trap (2).
9. The apparatus for continuously growing REBCO superconducting film based on the off-site technology according to claim 1, wherein the winding unit (4) comprises a material collecting tray (40), a fourth vacuum pump (41), a second tension wheel (42), a second speed wheel (43), a fourth vacuum gauge (44);
the base band enters a material receiving disc (40) for winding after passing through a second tension wheel (42) and a second speed wheel (43) in sequence;
the second tension pulley (42) monitors the tension of the winding unit (4), and feeds the tension back to a magnetic powder brake at the rear side of a discharging disc (10) of the reel-to-reel multi-channel reciprocating coating unit (1) so as to realize constant tension;
the second speed wheel (43) monitors the tape moving speed of the base tape and feeds the tape moving speed back to a motor at the rear side of a material placing disc (10) of the reel-to-reel multi-channel reciprocating coating unit (1) to realize constant speed;
the fourth vacuum pump (41) realizes the vacuum environment of the winding unit (4), and the fourth vacuum meter (44) monitors the vacuum environment of the winding unit (4).
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| CN114959627A (en) * | 2022-06-09 | 2022-08-30 | 清华大学 | Ultra-clean PLD sample preparation and transfer system and method |
| CN116904956A (en) * | 2023-07-27 | 2023-10-20 | 上海超导科技股份有限公司 | Roll-to-roll magnetron sputtering coating device |
| CN116641037B (en) * | 2023-07-27 | 2023-10-20 | 上海超导科技股份有限公司 | Equipment for double-side plating superconductive strip protective layer |
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