CN103614697A - Growth method of coated conductor DyBCO superconductive layer and DyBCO-coated conductor - Google Patents
Growth method of coated conductor DyBCO superconductive layer and DyBCO-coated conductor Download PDFInfo
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- CN103614697A CN103614697A CN201310557573.XA CN201310557573A CN103614697A CN 103614697 A CN103614697 A CN 103614697A CN 201310557573 A CN201310557573 A CN 201310557573A CN 103614697 A CN103614697 A CN 103614697A
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Abstract
The invention provides a growth method of a coated conductor DyBCO superconductive layer and a DyBCO-coated conductor, and specifically relates to a method of preparing the DyBCO superconductive layer on a metal base band with a cube texture oxide isolating layer, and the method can effectively overcome thickness effect of a YBCO superconductive layer and improve superconductive current-carrying capability. The preparation method utilizing a magnetron sputtering deposition technology comprises the following steps: vacuum-pumping for a reaction chamber until vacuum degree is smaller than and equal to 5*10<-4>Pa, heating the metal base band to 600 DEG C-700 DEG C; 20 minutes-30 minutes later, charging an argon gas and an oxygen gas until gas pressure of a cavity is stabilized to 30 Pa-60 Pa, wherein a proportion of the oxygen gas to the argon gas is 1:2-1:3; taking DyBCO as a target material to start sputtering, cooling to 400 DEG C-450 DEG C after the sputtering is completed, charging the oxygen gas until the gas pressure is maintained at 700 mbar-750 mbar, and carrying out annealing treatment for 40 minutes-80 minutes; and cooling to the room temperature after film-coating is ended to obtain the DyBCO superconductive layer growing on the metal base band with the cube texture oxide isolating layer. The method disclosed by the invention can be utilized to produce the coated conductor with thickness greater than 2mu m of the DyBCO superconductive layer; and the coated conductor does not exist in the prior art.
Description
Technical field
The present invention relates to a kind of growth method of coating conductor DyBCO superconducting layer, the method that refers more particularly to the DyBCO superconducting layer of growing with magnetron sputtering method on the metal base band of cubic texture oxide-isolation layer relates to a kind of DyBCO coating conductor producing by the method simultaneously.
Background technology
Current, supply of electric power day is becoming tight, yet a large amount of electric energy is but wasted on traditional cable.If use superconducting tape, not only these losses can be avoided completely, and can save a large amount of metallic substance.
The study hotspot of current superconducting tape is based on YBCO(yttrium barium copper oxide) s-generation belt material of high temperature superconduct of system, the main method of preparation s-generation Y based high-temperature superconductive strip is the method for coating conductor at present, the lowest layer of coating conductor is metallic baseband layer, is then buffer layer, superconducting coating and stabilizing layer.But there is thickness effect in the coating conductor based on YBCO system, i.e. critical current density, phenomenon that even critical current occur to reduce when its thickness is greater than certain value (approximately 2 μ m), this imagination that makes people attempt to improve by increasing thickness superconduction current capacity is difficult to realize.
Based on DyBCO(dysprosium barium copper oxygen) conductor of high-temperature superconductor coat of system can overcome the thickness effect of superconducting layer effectively.Utilize the DyBCO superconducting layer of the 2 μ m thickness that electron beam evaporation technique prepared on ISD-MgO buffer layer, at 77K, from its critical current density after the match, reach 2.5MA/cm
2, unit width critical current can reach 422A/cm.The thickness of DyBCO superconducting layer is brought up to 5.9 μ m, its critical current density (1.7MA/cm that slightly declines
2), and the critical current of unit width is up to 1018A/cm[reference: DyBa
2cu
3o
7-xsuperconducting coated conductors with critical currents exceeding 1000A cm
-1, Supercond.Sci.Technol.25,105007 (2012)].Therefore, the conductor of high-temperature superconductor coat based on DyBCO system can effectively overcome the thickness effect of superconducting layer, greatly improves the superconduction current capacity of coating conductor.
The epitaxial growth method of high temperature superconducting coating conductor superconducting layer is roughly divided into and needs vacuum system and without growth two class methods of vacuum system.Growth method without vacuum system is mainly chemical vapour deposition (MOCVD) and deposition of metal organic (MOD).The deposition chamber of MOCVD is without high vacuum, can be on variform matrix plated film, easily expand length and the width of coating conductor.Yet the starting material of MOCVD are the organic compound of Y, Ba, Cu, wherein the more difficult preparation in the organic source of Ba, expensive, thereby limited being widely used of this technique.MOD is a kind of of chemical solution Ji method, and it is without vacuum apparatus, is the preparation method of current conventional coating conductor.Employing trifluoroacetate (Trifluoro-acetate) is prepared the method (TFA-MOD) of YBCO superconducting layer due to COO-root decomposition in TFA, the minimizing of film weight and volumetric shrinkage etc. as precursor, easily occur the defects such as macrocrack, the thickness of the ybco film that this technique obtains is simultaneously limited.And increase the resulting coating conductor superconducting layer of polyethylene-ethylene glycol (polyethy leneglycol) organism raising film thickness by appropriateness in forerunner's solvent, have serious thickness effect, its superconduction current capacity is along with the increase of superconducting layer thickness reduces on the contrary.The current main pulsed laser deposition of vacuum growth method (PLD), however also there are some shortcomings in it, is first that the sedimentation mechanism of atom magnitude makes film growth rates slower; Next is to have film thickness effect, is difficult to make the intact superconducting thin films of texture more than thickness 2 μ m.
Summary of the invention
In order to solve the problems of the technologies described above, the object of the present invention is to provide a kind of prepare DyBCO superconducting layer on metal base band thering is cubic texture oxide-isolation layer method, effectively overcome the thickness effect of YBCO superconducting layer, improve superconduction current capacity.Adopt the method for magnetron sputtering, take DyBCO as target, the DyBCO superconducting layer of growing on the metal base band with cubic texture oxide-isolation layer.
In order to realize foregoing invention object, the present invention by the following technical solutions:
A growth method for coating conductor DyBCO superconducting layer, the step of the method is as follows:
Step 1: carry out clean to having on the metal base band of cubic texture oxide-isolation layer;
Step 2: magnetron sputtering cavity is evacuated to vacuum tightness and is less than or equal to 5 * 10
-4pa, is heated to 600 ℃-700 ℃ by metal base band, after 20-30 minute, be filled with argon gas and oxygen to cavity stable gas pressure at 30-60Pa, oxygen argon gas ratio is 1:2-1:3, take DyBCO as target, starts sputter more than 5 hours;
Step 3: after sputter finishes, be cooled to 400-450 ℃ and be filled with oxygen to air pressure and maintain 700-750mbar, carry out 40-80 minute anneal.Plated film finishes, and cools the temperature to room temperature, obtains having the DyBCO superconducting layer of growing on the metal base band of cubic texture oxide-isolation layer.
Sputtering time in step 2 is 10 hours, and obtaining DyBCO superconducting layer thickness is 3 μ m coating conductors.
Sputtering time in step 2 is 15 hours, and obtaining DyBCO superconducting layer thickness is 5 μ m coating conductors.
The invention provides on a kind of metal base band having cubic texture oxide-isolation layer the method that growth has the coating conductor of DyBCO superconducting layer, its advantage is:
1, the DyBCO superconducting layer of growing on the metal base band with cubic texture oxide-isolation layer can effectively overcome the thickness effect of superconducting layer, the DyBCO superconducting layer thickness that sputter growth gained has biaxial texture is 1-5 μ m, effectively improves the superconduction current capacity of coating conductor;
2, adopt magnetron sputtering technique growth DyBCO superconducting layer to there is higher growth velocity, can reduce production costs;
3, adopt that magnetron sputtering technique growth DyBCO superconducting layer technique is simple, processing parameter is easily controlled in production process.
The DyBCO coating conductor that the thickness obtaining according to the present invention is greater than 2 μ m is that prior art does not have, its advantage is the increase along with superconducting layer thickness, DyBCO superconducting layer has good c-axis orientation and biaxial texture level, so its critical current density does not significantly reduce.Therefore, this coating conductor can be realized the increase of superconduction current capacity by increasing thickness, effectively overcome the thickness effect of YBCO superconducting tape.
Accompanying drawing explanation
The XRD figure spectrum of Fig. 1 DyBCO superconducting layer
The R-T curve of Fig. 2 DyBCO superconducting layer
The critical current density of Fig. 3 DyBCO superconducting layer is with the change curve in magnetic field
Embodiment
The metal base band with cubic texture using in step 1 of the present invention comprises nickel metal, nickelalloy or copper and the alloy thereof with cubic texture; There is cubic texture oxide-isolation layer and comprise cerium oxide (CeO
2), stable zirconium white (YSZ), the yttrium oxide (Y of yttrium
2o
3) or magnesium oxide (MgO).
To having on the metal base band of cubic texture oxide-isolation layer, carry out clean, adopt in order 99.99% acetone, alcohol and deionized water to carry out supersound process, require the surface of clean not stay water mark, spot.Can certainly take other known in the art and general processing modes.
In step 2 of the present invention: adopt the heating unit in cavity to heat metal base band, the homogeneous heating temperature province that heating unit provides metal base band is 3-4 times of sputtering sedimentation region.The distance of target and substrate is that target-substrate distance is 50-100mm.Described sputtering power is 70-120W.
Below in conjunction with the technical solution adopted in the present invention, with different embodiment, be specifically addressed:
Embodiment 1
The present embodiment for preparing the DyBCO superconducting layer that thickness is 1 μ m on the metal base band with cubic texture oxide-isolation layer.Adopt conventional magnetron sputtering deposition technique, in magnetron sputtering equipment, carry out.Concrete technology is as follows:
(1), DyBCO target is contained on the target holder of reaction chamber;
(2) adopt, in order 99.99% acetone, alcohol and deionized water to carry out ultrasonic cleaning to having the metal base band of cubic texture oxide-isolation layer, the base band after clean is placed on the heating unit of magnetron sputtering reaction chamber standby;
(3), reaction chamber is evacuated to 5 * 10
-4pa, is heated to 600 ℃-700 ℃ by metal base band, after 20-30 minute, be filled with argon gas and oxygen to cavity stable gas pressure at 30Pa-60pa, oxygen argon gas ratio is 1:2-1:3.Utilize magnetron sputtering to start to deposit DyBCO superconducting layer, sputtering time is 5 hours, and gained DyBCO superconducting layer thickness is about 1 μ m.
(4), after sputter finishes, be cooled to 400 ℃-450 ℃ and be filled with oxygen to air pressure and maintain 700-750mbar, carry out 40-80 minute anneal.Plated film finishes, and cools the temperature to room temperature, obtains having the DyBCO superconducting layer that the thickness of growing on the metal base band of cubic texture oxide-isolation layer is 1 μ m.
Embodiment 2
The present embodiment for preparing the DyBCO superconducting layer that thickness is 3 μ m on the metal base band with cubic texture oxide-isolation layer.Adopt conventional magnetron sputtering deposition technique, in magnetron sputtering equipment, carry out.Concrete technology is as follows:
It is different from embodiment 1 that the preparation method of the present embodiment removes step (3), and all the other repeat the step in embodiment 1, and concrete technology is as follows:
(1), repeat the step (1) in embodiment 1;
(2), repeat the step (2) in embodiment 1;
(3), reaction chamber is evacuated to 5 * 10
-4pa, metal base band is heated to 600 ℃-700 ℃, after 20-30 minute, be filled with argon gas and oxygen to cavity stable gas pressure at 30Pa-60pa, oxygen argon gas ratio is 1:2-1:3, utilize magnetron sputtering to start to deposit DyBCO superconducting layer, sputtering time is 10 hours, and gained DyBCO superconducting layer thickness is about 3 μ m.
(4) step (4) the acquisition thickness, repeating in embodiment 1 is the DyBCO superconducting layer of 3 μ m.
Embodiment 3
The present embodiment for preparing the DyBCO superconducting layer that thickness is 5 μ m on the metal base band with cubic texture oxide-isolation layer.Adopt conventional magnetron sputtering deposition technique, in magnetron sputtering equipment, carry out.Concrete technology is as follows:
It is different from embodiment 1 that the preparation method of the present embodiment removes step (3), and all the other repeat the step in embodiment 1, and concrete technology is as follows:
(1), repeat the step (1) in embodiment 1;
(2), repeat the step (2) in embodiment 1;
(3), reaction chamber is evacuated to 5 * 10
-4pa, metal base band is heated to 600 ℃-700 ℃, after 20-30 minute, be filled with argon gas and oxygen to cavity stable gas pressure at 30Pa-60pa, oxygen argon gas ratio is 1:2-1:3, utilize magnetron sputtering to start to deposit DyBCO superconducting layer, sputtering time is 15 hours, and gained DyBCO superconducting layer thickness is about 5 μ m.
(4) step (4) the acquisition thickness, repeating in embodiment 1 is the DyBCO superconducting layer of 5 μ m.
According to the DyBCO superconducting layer of technical solution of the present invention gained, XRD figure spectrum as shown in Figure 1, can find out that DyBCO superconducting layer has good c-axis orientation; Further ω scanning and φ scanning show that DyBCO superconducting layer has good biaxial texture.
According to the resulting thickness of above-described embodiment, be 1 μ mDyBCO superconducting layer, DyBCO superconducting layer R-T curve as shown in Figure 2, the zero resistance transition temperature of DyBCO superconducting layer is about 86.0K.If the critical current density of Fig. 3 superconducting layer is with as shown in the variation relation curve in magnetic field, its critical current density is about 1.0 * 10 when null field, 77K
6a/cm
2.
According to the embodiment of the present invention 2 and embodiment 3, can also obtain the DyBCO coating conductor that thickness is greater than 2 μ m, this coating conductor is that prior art does not have, its advantage is the increase along with superconducting layer thickness, DyBCO superconducting layer has good c-axis orientation and biaxial texture level, so its critical current density does not significantly reduce.Therefore, this coating conductor can be realized the increase of superconduction current capacity by increasing thickness, effectively overcome the thickness effect of YBCO superconducting tape.
Claims (5)
1. a growth method for coating conductor DyBCO superconducting layer, the step of the method is as follows:
Step 1: carry out clean to having on the metal base band of cubic texture oxide-isolation layer;
Step 2: magnetron sputtering cavity is evacuated to vacuum tightness and is less than or equal to 5 * 10
-4pa, is heated to 600 ℃-700 ℃ by metal base band, after 20-30 minute, be filled with argon gas and oxygen to cavity stable gas pressure at 30-60Pa, oxygen argon gas ratio is 1:2-1:3, take DyBCO as target, starts sputter more than 5 hours;
Step 3: after sputter finishes, be cooled to 400-450 ℃ and be filled with oxygen to air pressure and maintain 700-750mbar, carry out 40-80 minute anneal, plated film finishes, cool the temperature to room temperature, obtain having the DyBCO superconducting layer of growing on the metal base band of cubic texture oxide-isolation layer.
2. a kind of growth method of coating conductor DyBCO superconducting layer according to claim 1, is characterized in that in step 2, sputtering time is 10 hours.
3. a DyBCO coating conductor of producing according to method described in claim 2, the thickness that it is characterized in that DyBCO superconducting coating is 3 μ m.
4. a kind of growth method of coating conductor DyBCO superconducting layer according to claim 1, is characterized in that: in step 2, sputtering time is 15 hours.
5. a DyBCO coating conductor of producing according to method described in claim 4, is characterized in that: the thickness of DyBCO superconducting coating is 5 μ m.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105525267A (en) * | 2016-01-20 | 2016-04-27 | 南京邮电大学 | Growing method of Y<1-x>RE<x>BCO superconducting layer of coated conductor through magnetron sputtering method |
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| CN1035395A (en) * | 1987-12-20 | 1989-09-06 | 住友电气工业株式会社 | Superconducting compound oxide film or wire rod and manufacture method thereof |
| CN1045311A (en) * | 1990-03-28 | 1990-09-12 | 中国科学院物理研究所 | The high-tc-super conductor method for manufacturing thin film |
| CN1943053A (en) * | 2004-04-08 | 2007-04-04 | 美国超能公司 | Biaxially-textured film deposition for superconductor coated tapes |
-
2013
- 2013-11-08 CN CN201310557573.XA patent/CN103614697A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035395A (en) * | 1987-12-20 | 1989-09-06 | 住友电气工业株式会社 | Superconducting compound oxide film or wire rod and manufacture method thereof |
| CN1045311A (en) * | 1990-03-28 | 1990-09-12 | 中国科学院物理研究所 | The high-tc-super conductor method for manufacturing thin film |
| CN1943053A (en) * | 2004-04-08 | 2007-04-04 | 美国超能公司 | Biaxially-textured film deposition for superconductor coated tapes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105525267A (en) * | 2016-01-20 | 2016-04-27 | 南京邮电大学 | Growing method of Y<1-x>RE<x>BCO superconducting layer of coated conductor through magnetron sputtering method |
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Application publication date: 20140305 |