CN105741971B - A kind of nanostructured superconduction laminated film and preparation method thereof - Google Patents

A kind of nanostructured superconduction laminated film and preparation method thereof Download PDF

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CN105741971B
CN105741971B CN201610114487.5A CN201610114487A CN105741971B CN 105741971 B CN105741971 B CN 105741971B CN 201610114487 A CN201610114487 A CN 201610114487A CN 105741971 B CN105741971 B CN 105741971B
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superconduction
laminated film
nanostructured
superconducting
substrate
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CN105741971A (en
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代秀红
刘保亭
付跃举
郭建新
周阳
关丽
赵庆勋
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Beijing Antaike Technology Co.,Ltd.
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Hebei University
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    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

Abstract

The invention provides a kind of nanostructured superconduction laminated film and preparation method thereof.Nanostructured superconduction laminated film provided by the present invention is to be co-deposited technique by magnetic control and pulse laser to form superconductor and non-superconducting nano material co-deposition on substrate；The substrate is SrTiO3、LaAlO3, MgO or flexible metal base band etc.；The superconductor is REBa2Cu3O7‑x（The rare earth elements such as RE=Y, Gd, Nd, Sm）Or (LaSr)2CuO4It is MgO, CeO Deng, the non-superconducting nano material2、Y2O3、BaZrO3And BaSnO3In at least one.The present invention adjusts magnetic control and laser splash parameter to realize the control to introducing defect distribution situation in real time by magnetic control and pulse laser cosputtering method in thin film growth process, final to realize the purpose regulated and controled to superconduction laminated film micro-structural and superconductivity.

Description

A kind of nanostructured superconduction laminated film and preparation method thereof
Technical field
The present invention relates to a kind of superconduction laminated film, specifically a kind of nanostructured superconduction laminated film and its preparation Method.
Background technology
The discovery of superconduction in 1911 and 1986 high temperature superconducting materia (HTS) successful exploitation be the scientific and technological progress of 20th century One of significant achievement, is also a key areas of modern science research.Suiperconducting transition of the high temperature superconducting materia in liquid nitrogen temperature Temperature, makes it have tempting answer in fields such as communication, health care, the Non-Destructive Testing of material, microtechnic and geophysicses Use prospect.With science and technology it is growing, the continuous improvement of living standard, the demand to superconductor is increasing, its Application field is also more and more wider, thus prepares and obtain the main object that high performance superconductor body is studied as scientists from all over the world.It is high The application technology part industrialization of temperature superconductive material and related superelectron element simultaneously has obtained successfully transporting in some fields With.At present by the YBa in the high temperature superconducting materia of extensive concern2Cu3O7-δ(being abbreviated as YBCO) turns into most studied, most ripe High-temperature superconducting thin film.YBCO is due to a series of its intrinsic advantage, such as Stability Analysis of Structures, safety non-toxic, superconducting critical transformation Temperature is higher (Tc=92K), can carry larger current etc., it is considered to be the most superconductor of application potential.
The critical current density (Jc) carried yet with YBCO is remarkably decreased with the increase of externally-applied magnetic field, and is surpassed Material is led to apply generally and under externally-applied magnetic field, thus the current capacity improved in magnetic field be current superconducting tape field most Concerned problem, to finally realize the practical of extensive YBCO superconductors.Researcher is always by different Material preparation technology improves the Jc of superconductor.It is in superconductor to improve superconductor Jc most efficient methods so far In be artificially introduced the non-superconducting out-phase nanostructured of certain form, the nanostructured is formed in effectively pin in superconductor The heart.Such as, patent CN 102491740A disclose a kind of yttrium barium copper oxide superconducting film of samarium doping and preparation method thereof, the superconduction Film is used as pinning center by mixing Sm introducings ion defects at Ba, can improve critical electricity of the superconducting thin film under externally-applied magnetic field Current density.But, need first to configure the precursor liquid of various concentrations doping in its preparation process, coat, be pyrolyzed afterwards, at crystallization Reason.Whole preparation process complex process, high cost；Once and precursor liquid configuration successful, the volume integral of prepared superconducting thin film Number is just difficult to change, i.e.,：The superconducting thin film of doping concentration real-time, tunable can not be prepared.
The content of the invention
An object of the present invention is just to provide a kind of nanostructured superconduction laminated film, the nanostructured superconduction THIN COMPOSITE Film is respectively provided with higher critical current density off field in outfield and certainly.
The second object of the present invention is just to provide a kind of preparation method of nanostructured superconduction laminated film, the preparation method The real-time regulation to impurity concentration in superconducting thin film can be achieved, you can realize to defect pinning concentration, density and defect pinning The regulation and control of the micro-structurals such as size and dimension, the final superconduction laminated film that improves is in self-fields and the ability of outer posting electric current off field.
What an object of the present invention was realized in：A kind of nanostructured superconduction laminated film, the nanostructured surpasses It is to be co-deposited technique by magnetic control and pulse laser superconductor and non-superconducting nano material co-deposition exist to lead laminated film Formed on substrate；The substrate is SrTiO3(strontium titanates is abbreviated as STO), LaAlO3, MgO or flexible metal base band etc.；Institute Superconductor is stated for REBa2Cu3O7-x(rare earth element such as RE=Y, Gd, Nd, Sm) or (LaSr)2CuO4Deng the non-super admittance Rice material is MgO, CeO2、Y2O3、BaZrO3And BaSnO3In one or two kinds of and two or more combinations.
The thickness of the nanostructured superconduction laminated film is 10~10000nm.
It is preferred that, the substrate is SrTiO3Substrate, the superconductor is YBa2Cu3O7-x, the non-superconducting nanometer material Expect for MgO；And MgO and YBa in the nanostructured superconduction laminated film2Cu3O7-xVolume ratio be 1:90~1:100.
The invention provides different types of nanostructured superconduction laminated film, these superconduction laminated films are by magnetic control Technique is co-deposited with pulse laser to form superconductor and non-superconducting nano material co-deposition on substrate, i.e.,：This hair It is bright by magnetic control and pulse laser cosputtering method, give full play to magnetron sputtering and arteries and veins in same set of physics vapour deposition system The respective advantage of impulse light deposition, and then realize the preparation of nanostructured doping superconduction laminated film.By changing pulse laser The sputtering parameter such as sputtering power, frequency and magnetron sputtering power, target-substrate distance, the superconduction that can form various concentrations doping is combined Doping concentration can be adjusted in film, and preparation process in real time.Therefore, the present invention can easily and effectively realize compound to superconduction The regulation and control of the micro-structural such as size and dimension of the concentration of defect pinning, density and defect pinning, finally improve superconduction in film Laminated film is in self-fields and the ability of outer posting electric current off field.
What the second object of the present invention was realized in：A kind of preparation method of nanostructured superconduction laminated film, including Following steps：
A, selection substrate are simultaneously cleaned；The substrate is SrTiO3、LaAlO3, MgO or flexible metal base band etc..Substrate Thickness can be 0.1~1mm.
B, place the substrate in magnetic control and pulse laser and be co-deposited in device；Simultaneously device is co-deposited in magnetic control and pulse laser In magnetic control target position on superconducting target is set, on laser target position set non-superconducting nanometer target.Certainly, superconducting target and non-super The set location of admittance rice target is interchangeable, i.e.,：Non-superconducting nanometer target is set on magnetic control target position, set on laser target position Superconducting target.The superconducting target is REBa2Cu3O7-x(rare earth element such as RE=Y, Gd, Nd, Sm) or (LaSr)2CuO4Target Deng non-superconducting nanometer target can be MgO or other non-super conductive dielectric materials, such as CeO2、Y2O3、BaZrO3 Or BaSnO3Deng can also be two or more the combination in these non-super conductive dielectric materials.
C, opening magnetron sputtering power supply and pulsed laser deposition power supply, by magnetic control and pulse laser cosputtering technique in base Deposition forms the superconduction laminated film of non-superconducting nanostructured doping on piece.
D, to formed non-superconducting nanostructured doping superconduction laminated film make annealing treatment.
The concrete technology condition of deposition superconduction laminated film is in step c：Magnetic control and pulse laser are co-deposited device Vacuum chamber is to (0.01~100) × 10-4Pa, it is 1~10cm to set magnetic control target-substrate distance, and laser target-substrate distance is 1~10cm； Argon gas and oxygen are filled with into vacuum chamber, the flow for being filled with argon gas and oxygen is 10~100sccm；Control magnetron sputtering work( Rate is 0~150W, and pulsed laser deposition power density is 0~5J/cm2, pulse laser frequency is 1~10Hz；Sputtering gas is set Press as 1~100Pa, the growth temperature of superconduction laminated film is 500~1000 DEG C.By changing target-substrate distance, ambient pressure, magnetic control Sputtering power, laser splash power and pulse laser frequency etc., can obtain the superconduction laminated film of various concentrations doping.
The general progress under oxygen atmosphere is made annealing treatment in step d, annealing temperature can be controlled between 400~600 DEG C, moved back The fiery time is can be controlled between 30~120min.
If being carried out under the high temperature conditions during growth of superconductive laminated film in step c, it can be annealed in step d through original position Processing.If can be made annealing treatment in growth of superconductive laminated film under cryogenic in step c, step d through high temperature.
The thickness control of superconduction laminated film formed in step c is between 10~10000nm.
It is preferred that, non-superconducting nano material and the volume ratio of superconductor in the superconduction laminated film formed in step c For 1:90~1:100.It is furthermore preferred that non-superconducting nano material and superconductor in superconduction laminated film formed in step c Volume ratio be 1:95.
It is preferred that, superconducting target is YBa in step b2Cu3O7-xTarget, non-superconducting nanometer target is MgO target.
The present invention can be respectively by controlling magnetic control and laser deposition parameter, to realize 0-3,2-2,1-3 type laminated film Prepare, and by controlling the size and shape of the controllable doped nanometer such as depositing temperature, realize and nanostructured is adulterated The microstructure and performance regulation and control of superconduction laminated film.It has also been found that a small amount of non-superconducting nanometer material that adulterated in superconduction laminated film Material can hardly reduce its superconducting transition temperature, therefore by changing the doping of non-superconducting nano material in superconduction laminated film Measure to change the defect concentration in superconduction laminated film.In the case where not reducing superconducting transition temperature, superconduction can be improved and answered Film is closed in self-fields and outer critical current density jc off field.Certainly non-super admittance can also arbitrarily be changed by the inventive method Rice material doping, but doping it is excessive after can reduce the Tc and Jc of superconduction laminated film.
Preparation method provided by the present invention without being pre-configured with precursor liquid, can overcome in the prior art component ratio experiment During be difficult to the shortcoming that changes, can be realized in thin film growth process by adjusting magnetic control and laser splash parameter in real time pair The control of defect distribution situation is introduced, the purpose regulated and controled to superconduction laminated film micro-structural and superconductivity is realized, improves superconduction Laminated film holds current-carrying ability in different warm areas, accelerates superconducting thin film in the practical of light current and field of strong electricity, is superconduction Preparation, research and its application electrically of field composite film material create condition.
Brief description of the drawings
Fig. 1 is the STO bases MgO prepared by the embodiment of the present invention 1:YBCO=1:95 superconduction laminated films and pure ybco film XRD comparison diagrams.
Fig. 2 is the STO bases MgO prepared by the embodiment of the present invention 1:YBCO=1:95 superconduction laminated films and pure ybco film In 77K Jc- H curve comparison figures；Illustration is both R-T curve comparison figures in Fig. 2.
Fig. 3 is the STO bases MgO prepared by the embodiment of the present invention 2:YBCO=1:40 superconduction laminated films and pure ybco film XRD comparison diagrams.
Fig. 4 is the STO bases MgO prepared by the embodiment of the present invention 2:YBCO=1:40 superconduction laminated films and pure ybco film In 65K Jc- H curve comparison figures；Illustration is both R-T curve comparison figures in Fig. 4.
Fig. 5 is the Metal Substrate MgO prepared by the embodiment of the present invention 3:YBCO=1:95 superconduction laminated films and pure YBCO are thin The XRD comparison diagrams of film.
Embodiment
Embodiment 1, STO bases MgO:YBCO=1:The preparation of 95 superconduction laminated films.
1st, target prepares and the cleaning of STO substrates：It is co-deposited in magnetic control and pulse laser in device, magnetic control target position is from high-purity MgO (purity>99.95%, Beijing is safe and sound can Science and Technology Ltd.) ceramic target, laser target position selects high-purity YBa2Cu3O7-xIt is (pure Degree>99.95%, Beijing is safe and sound can Science and Technology Ltd.) target.By 0.5mm thickness STO (001) monocrystal chip successively in acetone and Cleaned 10 minutes, dried up with high pure nitrogen with ultrasonic wave in absolute ethyl alcohol, it is ensured that substrate is clean.Substrate is bonded at elargol On sample carrier, sample carrier is then put into magnetic control and is co-deposited with pulse laser in device.
2nd, the preparation of nanostructured MgO doped YBCOs laminated film：The back end vacuum of vacuum chamber is 2 × 10-4Pa, magnetic control Target-substrate distance is 5.5cm, and laser target-substrate distance is 4.5cm, is filled with argon gas and oxygen, argon flow amount is 75sccm, argon gas and oxygen stream Amount is than being 3:1, laser power density is 2J/cm2, laser frequency is 2Hz, and magnetron sputtering power is 60W, and sputtering pressure is 15Pa, growth temperature is 890 DEG C, and sputtering time is that 15min, MgO and YBCO volume ratio are about 1:95.To super after the completion of sputtering Lead laminated film to be made annealing treatment, annealing temperature is 540 DEG C, annealing time is 30min in 1atm oxygen atmospheres, is ultimately formed Laminated film thickness is about 200nm.
3rd, four lead bridge patterns are made using photoetching process, then using pressing indium method to make two on superconduction laminated film Individual current feed and two voltage tester leads.
4th, the critical transition temperature Tc of measurement nanostructured MgO doped YBCO superconduction laminated films and self-fields and it is outer off field Critical current density jc.
Fig. 1 is STO bases MgO prepared in embodiment 1:YBCO=1:95 superconduction laminated films and pure ybco film XRD comparison diagrams.It can be seen that in addition to the diffraction maximum of substrate in itself, being substantially the diffraction of YBCO (00l) orientations Peak.As a result show YBCO superconduction laminated film well-crystallizeds, be epitaxial growth.Illustration shows MgO in Fig. 2:YBCO=1:95 answer Close film Tc and pure ybco film it is almost equal, be 90K or so, it is seen that not interfere with superconduction multiple for heterogeneous phase trace doped Close the Tc of film.But found from Fig. 2, MgO:YBCO=1:The Jc of the 95 purer ybco films of superconduction laminated film has obtained entirety Improve；And in relatively low externally-applied magnetic field, relative to pure ybco film, MgO:YBCO=1:The Jc of 95 superconduction laminated films is to additional Magnetic field H dependence reduction, i.e., with the increase of externally-applied magnetic field, the Jc fall off rates of superconduction laminated film become more slow, Fully demonstrate has superior electricity using the new superconduction laminated film prepared prepared by the method for oxidate compound film Spread Movement Capabilities.
The elongation technology scheme of embodiment 1 is：1-3 is realized by changing the parameters such as sputter temperature, annealing temperature and oxygen pressure The preparation of type and 1 type reducing MgO doped YBCO superconduction laminated films.Realize oxygen content in superconducting thin film, micro-structural and superconductivity The regulation and control of energy.
Embodiment 2, STO bases MgO:YBCO=1:The preparation of 40 superconduction laminated films.
1st, target prepares and the cleaning of STO substrates：It is co-deposited in magnetic control and pulse laser in device, magnetic control target position is from high-purity MgO (purity>99.95%, Beijing is safe and sound can Science and Technology Ltd.) ceramic target, laser target position selects high-purity YBa2Cu3O7-xIt is (pure Degree>99.95%, Beijing is safe and sound can Science and Technology Ltd.) target.By 0.5mm thickness STO (001) monocrystal chip successively in acetone and Cleaned 10 minutes, dried up with high pure nitrogen with ultrasonic wave in absolute ethyl alcohol, it is ensured that substrate is clean.Substrate is bonded at elargol On sample carrier, sample carrier is then put into magnetic control and is co-deposited with pulse laser in device.
2nd, the preparation of nanostructured MgO doped YBCOs laminated film：The back end vacuum of vacuum chamber is 2 × 10-4Pa, magnetic control Target-substrate distance is 5.5cm, and laser target-substrate distance is 4.5cm, is filled with argon gas and oxygen, argon flow amount is 75sccm, argon gas and oxygen stream Amount is than being 3:1, laser power density is 2J/cm2, laser frequency is 2Hz, and magnetron sputtering power is 120W, and sputtering pressure is 15Pa, growth temperature is 890 DEG C, and sputtering time is that 15min, MgO and YBCO volume ratio are about 1:40.To super after the completion of sputtering Lead laminated film to be made annealing treatment, annealing temperature is 540 DEG C, annealing time is 30min in 1atm oxygen atmospheres, is ultimately formed Laminated film thickness is about 200nm.
3rd, four lead bridge patterns are made using photoetching process, then using pressing indium method to make two on superconduction laminated film Individual current feed and two voltage tester leads.
4th, the critical transition temperature Tc of measurement nanostructured MgO doped YBCO superconduction laminated films and self-fields and it is outer off field Critical current density jc.
Fig. 3 is STO bases MgO prepared in embodiment 2:YBCO=1:40 superconduction laminated films and pure ybco film XRD comparison diagrams.It can be seen that in addition to the diffraction maximum of substrate in itself, being substantially the diffraction of YBCO (00l) orientations Peak.As a result show YBCO superconduction laminated film well-crystallizeds, be epitaxial growth.But doping concentration it is excessive when, laminated film surpass It is only 76K or so to lead transition temperature Tc, is seriously reduced for the 90K of pure ybco film, as shown in illustration in Fig. 4.Cause This measures the Jc-H curves of superconduction laminated film and pure ybco film under 65K, as shown in Figure 4.MgO as we know from the figure:YBCO =1:The Jc entire lowerings of the purer ybco films of Jc of 40 laminated films.But simultaneously it can be seen that the Jc of the laminated film is to additional Magnetic field H dependence reduction, i.e., with the increase of externally-applied magnetic field, for relatively pure ybco film, reduction of speed under the Jc of laminated film Rate becomes more slow.Illustrating can using this new superconduction laminated film prepared prepared by the method for oxidate compound film To improve its current carrying capacities to a certain extent；Also demonstrate simultaneously using this new oxidate compound film of preparing Method can prepare the laminated film of any doping concentration, it is contemplated that the performance of superconductor, doping concentration can not be excessive, need Control within the specific limits, the non-superconducting nano material of general control incorporation and the volume ratio of superconductor are 1:90~1: 100。
MgO in embodiment 3, flexible metal base band:YBCO=1:The preparation of 95 superconduction laminated films.
1st, target prepares and metal base band cleaning：It is co-deposited in magnetic control and pulse laser in device, magnetic control target position is from high Pure MgO (purity>99.95%, Beijing is safe and sound can Science and Technology Ltd.) ceramic target, laser target position selects high-purity YBa2Cu3O7-x (purity>99.95%, Beijing is safe and sound can Science and Technology Ltd.) target.The metal base band that 0.1mm thicker strip has cushion is existed successively Cleaned 10 minutes, dried up with high pure nitrogen with ultrasonic wave in acetone and absolute ethyl alcohol, it is ensured that base band is clean.With elargol by base Band is bonded on sample carrier, and sample carrier then is put into magnetic control is co-deposited in device with pulse laser.
2nd, the preparation of nanostructured MgO doped YBCOs laminated film：The back end vacuum of vacuum chamber is 2 × 10-4Pa, magnetic control Target-substrate distance is 5.5cm, and laser target-substrate distance is 4.5cm, is filled with argon gas and oxygen, argon flow amount is 75sccm, argon gas and oxygen stream Amount is than being 3:1, laser power density is 2J/cm2, laser frequency is 2Hz, and magnetron sputtering power is 60W, and sputtering pressure is 15Pa, growth temperature is 890 DEG C, and sputtering time is that 15min, MgO and YBCO volume ratio are about 1:95.To super after the completion of sputtering Lead laminated film to be made annealing treatment, annealing temperature is 540 DEG C, annealing time is 30min in 1atm oxygen atmospheres, is ultimately formed Laminated film thickness is about 200nm.
3rd, four lead bridge patterns are made using photoetching process, then using pressing indium method to make two on superconduction laminated film Individual current feed and two voltage tester leads.
4th, the critical transition temperature Tc of measurement nanostructured MgO doped YBCO superconduction laminated films and self-fields and it is outer off field Critical current density jc.
Fig. 5 is MgO prepared on the metal base band with cushion in embodiment 3:YBCO=1:95 superconduction THIN COMPOSITEs The XRD comparison diagrams of film and metal base band.It can be seen that in addition to the diffraction maximum of metal base band in itself, being substantially The diffraction maximum of YBCO (00l) orientations.Illustrate YBCO superconduction laminated films well-crystallized on the metal base band with cushion, be Epitaxial growth.It can be seen that this new method for preparing oxidate compound film may apply to required for scale industry development In the base band of flexible metal.
The above is only the preferred embodiments of the present invention, is not intended to limit the invention.For art Those of ordinary skill for, on the basis of the above description, other various forms of changes or variation can also be made, here There is no need to be exhaustive to all embodiments.Any modification for being made within the spirit and principles of the invention, change Enter, should be included within the scope of the present invention.

Claims (4)

1. a kind of nanostructured superconduction laminated film, it is characterized in that, the nanostructured superconduction laminated film be by magnetic control with Pulse laser is co-deposited technique and forms superconductor and non-superconducting nano material co-deposition on substrate；The substrate is SrTiO3、LaAlO3, MgO or flexible metal base band；The superconductor is REBa2Cu3O7-xOr (LaSr)2CuO4, REBa2Cu3O7-xMiddle RE is Y, Gd, Nd or Sm；The non-superconducting nano material is MgO, CeO2、Y2O3、BaZrO3And BaSnO3In At least one；
Above-mentioned nanostructured superconduction laminated film is to be prepared by the following method to form：
A, selection substrate are simultaneously cleaned；
B, place the substrate in magnetic control and pulse laser and be co-deposited in device；It is co-deposited simultaneously in magnetic control and pulse laser in device Superconducting target is set on magnetic control target position, non-superconducting nanometer target is set on laser target position；Or set non-on magnetic control target position Superconducting nano target, superconducting target is set on laser target position；
C, opening magnetron sputtering power supply and pulsed laser deposition power supply, by magnetic control and pulse laser cosputtering technique on substrate Deposition forms the superconduction laminated film of non-superconducting nanostructured doping；
The concrete technology condition of deposition superconduction laminated film is in step c：Magnetic control and pulse laser are co-deposited to the vacuum of device Room is evacuated to（0.01~100）×10-4 Pa, it is 1 ~ 10cm to set magnetic control target-substrate distance, and laser target-substrate distance is 1 ~ 10cm；To vacuum Interior is filled with argon gas and oxygen, and the flow for being filled with argon gas and oxygen is 10 ~ 100sccm；Control magnetron sputtering power for 0 ~ 150W, pulsed laser deposition power density is 0 ~ 5J/cm2, pulse laser frequency is 1 ~ 10Hz；Set sputtering pressure be 1 ~ 100Pa, the growth temperature of superconduction laminated film is 500 ~ 1000 DEG C；
D, to formed non-superconducting nanostructured doping superconduction laminated film make annealing treatment；Annealing is in oxygen Carried out under atmosphere, annealing temperature is 400 ~ 600 DEG C, annealing time is 30 ~ 120min.
2. nanostructured superconduction laminated film according to claim 1, it is characterized in that, the nanostructured superconduction THIN COMPOSITE The thickness of film is 10 ~ 10000nm.
3. nanostructured superconduction laminated film according to claim 1, it is characterized in that, the substrate is SrTiO3Substrate, institute Superconductor is stated for YBa2Cu3O7-x, the non-superconducting nano material is MgO；And MgO in the nanostructured superconduction laminated film With YBa2Cu3O7-xVolume ratio be 1:90~1:100.
4. nanostructured superconduction laminated film according to claim 3, it is characterized in that, the nanostructured superconduction THIN COMPOSITE Non-superconducting nano material and the volume ratio of superconductor are 1 in film:95.
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