CN1024859C - Composite oxides superconductive wire rod and their manufacture method - Google Patents
Composite oxides superconductive wire rod and their manufacture method Download PDFInfo
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- CN1024859C CN1024859C CN92102035A CN92102035A CN1024859C CN 1024859 C CN1024859 C CN 1024859C CN 92102035 A CN92102035 A CN 92102035A CN 92102035 A CN92102035 A CN 92102035A CN 1024859 C CN1024859 C CN 1024859C
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- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 239000010409 thin film Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 12
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000010408 film Substances 0.000 claims description 121
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 229910002367 SrTiO Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910001316 Ag alloy Inorganic materials 0.000 claims 2
- 229910001020 Au alloy Inorganic materials 0.000 claims 2
- 229910001260 Pt alloy Inorganic materials 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 39
- 238000005240 physical vapour deposition Methods 0.000 abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- 230000003746 surface roughness Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 43
- 239000002887 superconductor Substances 0.000 description 35
- 238000005266 casting Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 14
- 238000005245 sintering Methods 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910002480 Cu-O Inorganic materials 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 235000019628 coolness Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000005668 Josephson effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910016063 BaPb Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000005491 wire drawing Methods 0.000 description 1
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
Landscapes
- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Improvement in a superconducting thin film of compound oxide represented by the formula: LnBa2Cu3O7- delta (Ln is lanthanide) or (La1-x alpha x)2CuO4 ( alpha is Ba or Sr) deposited on a substrate or core made of MgO, SrTiO3 or ZrO2 by physical vapor deposition technique, the surface roughness Rmax (datum length=1,000 mu m) of the superconducting thin film being less than 0.2 mu m.
Description
The invention relates to superconducting thin film and film build method thereof, in detail, exactly about having improved the superconducting compound oxide film and the manufacture method thereof of critical current density significantly.
Resulting superconducting thin film is when having high critical current according to the present invention, also have high superconduction critical temperature and aspect other characteristics such as flatness also excellent characteristic, particularly useful aspect the wiring material of integrated circuit and various electronic devices.
And the present invention also is about superconducting wire and manufacture method thereof, in detail, and about composite oxides superconductive wire rod and the manufacture method thereof that has improved critical current density significantly.
Resulting superconducting wire also has high superconduction critical temperature when having high critical current according to the present invention, can be used for that electric power is carried and as the wiring material of various electronic devices.
What is called is the superconducting phenomenon that electronics changes mutually, and promptly the resistance of conductor is zero and presents the phenomenon of perfect diamganetism under given conditions, and the various superconductive devices in electronic applications are known.Representative, can exemplify out as under the weak each other condition that engages of superconductor, utilize the device that shows the josephson effect of quantum effect by impressed current on a macro scale.
To tunnel juntion type Josephson device, expect its switching device as the hypervelocity low power consumption owing to the energy gap of superconductor is very little.And owing to show correct quantum appearance for the josephson effect in electromagnetic wave and magnetic field, expectation utilizes the hypersensitivity transducer of Josephson device as magnetic field, microwave, radioactive ray etc.And, having reached in the very-high speed computer field of the cooling capacity limit at the power consumption of per unit area, urgent expectation is developed as the ultrahigh speed arithmetic unit or as the superconductive device of low loss wiring material.
Thereby, the expectation superconducting wire as mainly be used in electric power transportation art and coil and in various field of electrical components as second wiring material.For example: because in very-high speed computer, along with increasing of electronic circuit integrated level, the electric energy loss of per unit area has reached the cooling capacity limit, and therefore urgent expectation is with the superconductor conduct of the no current loss various electronic component wiring materials based on the IC assembly.
On the one hand, although through various effort, the superconduction critical temperature Tc of superconductor did not have to surpass Nb in a very long time
3The 23K of Ge.
Yet in 1986, the superconductor of the high Tc composite oxides class of being found with Miu Le now by shellfish moral slave was opened the possibility (Bednorz, M ü ller, " Phys.B64(1986) 189 ") of high-temperature superconductor widely.
The oxide superconductor that shellfish moral slave is found with Miu Le now for (La, Ba)
2CuO
4, this oxide superconductor is called K
2NiF
4The type oxide has similar crystal structure with present known perofskite type oxide, and its Tc reaches the value than the tremendous high about 30K in ground of former superconductor.
Further, in February, 1987 news report, reported the critical temperature that presents the 90K grade that the neat outstanding people of grade finds be called YBCO, by Y
1Ba
2Cu
3O
7-xRepresented Ba-Y based composite oxide has improved the possibility that non-cryogenic superconductor is realized greatly.
To the superconducting characteristic of these complex oxide superconductors, we can say that the shortcoming of oxygen in the crystallization can realize big distribution, if suitable oxygen shortcoming can not form in the crystallization, Tc just reduces, the difference that transition temperature and resistance are entirely zero temperature becomes big.
As the method for making above-mentioned composite oxide superconductor film, adopt implementing with physical vapor deposition as vapor deposition source widely by the composite oxides of generations such as sintering.
As physical vapor deposition, particularly sputtering method is used always, yet, because its critical temperature Tc height of above-mentioned superconductor film but current density, J c is little, so practicality is very low, still has very big problem in complex oxide superconductor practicability.
And before this, utilizing above-mentioned complex oxide superconductor to make super conductor wire generally is to adopt the method that is filled into above-mentioned composite oxides sintered body in the metal-back and is drawn into line.But, above-mentioned composite oxides are being anisotropic aspect its direction of current flow, promptly easily flow at the C direction of principal axis fluid capacitance that powers on, so filling powder and the above-mentioned existing superconducting wire made is difficult to improve its critical current density jc brokenly, and is still limited as the practicability of actual superconducting wire even critical temperature Tc uprises.
Forming under the condition of the film that is constituted by the oxide type ceramic superconductor with sputtering method on the substrate, when in oxygenous sputter gas, carrying out sputter, by in the sputtering operation process, improving substrate temperature, improved the crystallinity of resultant film, after sputter, by heat-treating in oxygen atmosphere to improve the oxygen content in the film, this is necessary.For example: open by the spy and to be put down in writing in the clear 56-109824 communique.
In this patent, put down in writing: in oxygen-containing atmosphere, form with BaPb with high-frequency sputtering
1-xBi
xO
3(X wherein: for satisfying 0.05～0.35 number) represented composite oxides class superconducting thin film then, is heat-treated under 500-550 ℃ in oxygen-containing atmosphere, and this is necessary.Yet,, can not put down in writing naturally for the membrance casting condition of the high-temperature superconductor film of recent findings.
Before this, making under the situation of composite oxide superconductor film, using by the composite oxides sintered body of same item as the target of main body and carry out physical vapor deposition (generally being to carry out sputter), the superconducting thin film that obtains with existing method, critical current density is low, can not be practical.
The applicant has submitted following patent application about the high-temperature superconductor film manufacture method to:
Submitted No. 152714 U.S. Patent application on February 5th, 1988;
Submitted No. 167895 U.S. Patent application on March 13rd, 1988;
Submitted No. 195147 U.S. Patent application on May 18th, 1988;
Submitted No. 200206 U.S. Patent application on May 31st, 1988.
Although physical vapor depositions such as above-mentioned sputtering method itself are spendable methods, but still wish that critical temperature and critical current density can further improve, the present invention is the development to the applicant's above-mentioned patent application, has further improved these patent applications.
The objective of the invention is: solve above-mentioned the problems of the prior art, composite oxides super conductive wire and manufacture method thereof with high critical current densities Jc are provided.
Of the present invention first to as if about: substrate with contains the superconductivity complex that composite oxide superconductor film was constituted that useful physical vapor deposition forms on this substrate based on composite oxides, this superconductivity complex is characterised in that the substantial portion on above-mentioned composite oxide superconductor film surface is level and smooth.
Of the present invention second to as if about core with containing the superconducting wire that composite oxide superconductor film was constituted that on this core, forms based on composite oxides, the feature of above-mentioned superconducting wire is that the substantial portion of above-mentioned superconducting compound oxide film surface is level and smooth.
Above-mentioned what is called " substantial portion " meaning is: generally carrying out under the situation of large tracts of land physical vapor deposition, the most surfaces except that part of surface that has room, defective etc. inevitably (as: more than 80% of surface) is level and smooth.
Estimate like this observing with method of optics under its surperficial situation in the flatness on above-mentioned superconducting thin film surface: the fineness R of film surface
Max(datum length=1000 μ m) is below the 0.2 μ m.This value is at microscope, is especially got definite with viewing film under SEM.
According to experimental result of the present invention, the fineness R of film surface
MaxSurpass 0.2 μ m, then critical current density jc reduces significantly.
Above-mentioned composite oxide superconductor film can exemplify out to contain the composite oxide film of the represented composite oxides in following general formula (1) and (2).
（1）Ln
1Ba
2Cu
3O
7-X
(wherein: what Ln represented is at least one lanthanide series of selecting the group of forming from La, Nd, Sm, Eu, Gd, Dy, Ho, y, Er, Yb, Tm and Lu, and X is the number that satisfies 0≤X＜1)
Under with the represented composite oxides situation of above-mentioned general formula (1), especially the composite oxides that above-mentioned Ln is Y, Er, Ho, Dy, Tm or Lu are gratifying, and these composite oxides can be thought to be its main body with Ca-Ti ore type or accurate perofskite type oxide.
Above-mentioned lanthanide series Ln is depicted as 1: 2: 3rd with atomic ratio such as the following formula of Ba and Cu, and is gratifying.But be not strictly to be defined as this ratio, their ratio is preferably in ± atomic ratio of 20% range changing constitutes and all be included within the scope of the present patent application in ± 50% scope.That is to say that represented in the claims " to contain the composite oxides that above-mentioned formula is represented " means that superconducting thin film made according to the method for the present invention also includes with the defined Ln of following formula: the atomic ratio of Ba: Cu is the situation beyond 1: 2: 3.
And above-mentioned definition also means the element that contains beyond above-mentioned Ln, Ba, Cu, the O, promptly the unavoidable impurities of sneaking into the ppm order of magnitude and for improve resulting sintered body or film other the purpose of characteristic and the 3rd composition that adds.
Be used as element that the 3rd composition may add and can be Sr, Ca, Mg, Be from cycle II a family element, the periodic table III a family element outside above-mentioned, selected element in periodic table I b, II b, III b, IV a and the VIII a family for example can be enumerated Ti, V etc.
（2）（La
1-xa
x）
2CuO
4
(but: element a is Ba or Sr)
These composite oxides can think that Ca-Ti ore type or accurate perofskite type oxide are its main body.The atomic ratio of above-mentioned La, Ba or Sr, Cu is gratifying in satisfying the scope of following formula, but not strictness to limit ratio for this reason, their ratio is in ± 50% scope, and it all is in presenting the condition of effective superconducting characteristic that the atomic ratio that is preferably in ± changes in 20% the scope constitutes.That is to say that the meaning of expressed " to contain ... be main " is a situation about also having comprised as outside the defined atomic ratio of above-mentioned formula in the claim.
And above-mentioned definition means, can also contain the element beyond the above-mentioned element, i.e. the unavoidable impurities of sneaking into the ppm order of magnitude and serve as to improve the 3rd composition that the purpose of other characteristics of product is added.
The element that may add as the 3rd composition is the element that chooses Sr, Ca, Mg, Be, periodic table III a family element, periodic table I b, II b, III b, IV a and the VIII a family beyond above-mentioned from periodic table II a family element, for example can enumerate Ti, V.
Under the situation of the above-mentioned superconductivity complex that constitutes first object of the present invention, can use substrate, oxide substrate or these Ca-Ti ore type crystallizations of Ca-Ti ore type crystallization or metal substrate and the semiconductor chip that oxide forms as resilient coating as the substrate that forms above-mentioned superconducting compound oxide film.What be used as the ideal basis sheet material is: MgO monocrystalline, SrTiO
3Monocrystalline, ZrO
2Monocrystalline, YSZ single-crystal, Al
2O
3Monocrystalline or polymorph A l
2O
3, and the metal substrate and the semiconductor chip that constitute film forming face with these materials also are gratifying, preferably { 001 } or { 110 } face as MgO monocrystalline or SrTiO
3The film forming face of monocrystal chip.
Under the situation of the above-mentioned superconducting wire that constitutes second object of the present invention, can use metal wire rod, ceramic wire rod or on metal knot material, form the wire rod of ceramic film as above-mentioned core.As above-mentioned metal, platinum family element Pt, Ag, Au and alloy thereof are gratifying, but are not defined as these.The diameter of this metal wire is thinner better, is preferably below the 1mm.And as the pottery of above-mentioned core or as the pottery of thin layer preferably oxide or composite oxides class pottery.This pottery is monocrystalline or polycrystalline preferably, but uses glass good in some cases.At above-mentioned pottery is under the situation of monocrystalline or polycrystalline, preferably contains the oxide crystallization pottery that similar spacing of lattice is arranged to above-mentioned composite oxides crystal lattice spacing, can exemplify out MgO, SrTiO as this pottery
3Or ZrO
2, to these potteries, in order to make above-mentioned compositing oxide superconducting material film in the growth of C direction of principal axis, its surface preferably has { 001 } face or { 110 } face.
Of the present invention the 3rd to as if the manufacture method of above-mentioned complex oxide superconductor and superconducting wire.
The method according to this invention is characterized in that containing based on the superconductivity complex of the composite oxide superconductor film operation of composite oxides or the manufacture method of superconducting wire about comprising forming on substrate or core by physical vapor deposition, by regulating by (1) film forming speed that the range of definition is arranged below, (2) film forming air pressure, (2) oxygen ratio, (3) at least one parameter of selecting in high frequency power and (4) film forming air pressure, under the substantial portion of final resulting superconducting compound oxide film surface is level and smooth condition, implement above-mentioned physical vapor deposition.
Be elaborated in the back for above-mentioned (1) scope to each sputtering condition of (4).
The present invention's above-mentioned superconducting compound oxide film applicatory is: comprised the composite oxide film with the represented composite oxides in general formula (1) and (2) to be put down in writing in the present invention's first and second invention objects, that is:
(1) Ln
1Ba
2Cu
3O
7-xWith
（2）（La
1-xa
x）
2CuO
4
Can be for these with reference to above-mentioned explanation.
At first the above-mentioned physical vapor deposition as prerequisite of the present invention is described.
Among the present invention, preferably adopt sputtering method, especially the RF magnetron sputtering as physical vapor deposition.This sputtering method itself is known.The atomic ratio that is used as each metallic element of vapor deposition source in this sputtering method is regulated according to the evaporation efficient of these metals with at on-chip adsorption probability.To determine the cooperation ratio according to evaporation efficient, to constitute each metallic element simple substance, its oxide and the carbonate powder mixing of composite oxides and obtain mixed-powder, these mixed-powders of sintering obtain sintered body, it is pulverized once again, is gratifying with resulting sintered powder as vapor deposition source.In some cases, can adopt each the metallic element simple substance that constitutes above-mentioned composite oxides, its oxide and carbonate powder are as Y
2O
3, CuO and BaCuO
2The compound of various powder as vapor deposition source.In addition, not these various powder and each intactly uses, can be divided into vapor deposition source a plurality of.For example: can be divided into the vapor deposition source of having only Cu itself and two of the vapor deposition source formed by (Ba+Y) composite oxides.
Secondly, as above-mentioned substrate, preferably adopt the oxide monocrystal substrate that the spacing of lattice similar to above-mentioned composite oxides crystal lattice spacing arranged, as using MgO monocrystalline, SrTiO
3Monocrystalline or ZrO
2Monocrystalline.As film forming face, preferably adopt MgO monocrystalline or SrTiO
3{ 001 } face of monocrystal chip or { 110 } face.
Under the situation of superconducting wire, can use metal wire rod, ceramic wire rod or on metal wire rod, form the wire rod of ceramic film as core.As above-mentioned metal, particularly platinum family element, Pt, Ag, Au and their alloy are for well.Be limited to this but have more than.The diameter of this metal wire is thinner better, is preferably below the 1mm.And, as the pottery of above-mentioned core or as the pottery of the thin layer pottery of oxide or composite oxides class preferably.This pottery is monocrystalline or polycrystalline preferably, but can be glass in some cases.At above-mentioned pottery is under the situation of monocrystalline or polycrystalline, and the pottery that contains to the oxide crystallization of the similar spacing of lattice of spacing of lattice of above-mentioned composite oxides crystallization is gratifying.Can exemplify out MgO, SrTiO as this pottery
3Or ZrO
2, to these potteries, on the C direction of principal axis, to grow up in order to make above-mentioned compositing oxide superconducting material film, its surface preferably has { 001 } face or { 110 } face.
In the present invention, best heated substrate during sputter.Substrate temperature in this case is 200 to 950 ℃, is preferably 500 to 920 ℃.Substrate temperature less than 200 ℃ situation under, the crystallinity of composite oxides degenerates becomes noncrystalline state, just can not obtain superconducting thin film.In addition, if substrate temperature surpasses 950 ℃, crystal structure has just become, and above-mentioned composite oxides can not become superconductor.
For described each sputtering condition in above-mentioned (1) to (4), can under the constant situation of other conditions, select in the scope of they or definition below any two the above conditions of combination to use in the defined below scope separately.These conditions are to see result of the present invention with mutual different viewpoint.
(1) film forming speed
Film forming speed when in the present invention, setting sputter is 0.05～1
/ second, be preferably in 0.1～0.8
In the scope of/second.According to the experimental result that the inventor obtains, the film forming speed when physical vapor deposition surpasses 1
/ second, resulting superconducting thin film critical current density reduces significantly, can not obtain practical film.For film forming speed less than 0.05
/ second, film forming speed is too slow, is unsuitable for industry and uses.
(2) film forming air pressure
In the present invention, the air pressure during sputter is preferably in 0.01～0.3Torr scope in 0.001～0.5Torr scope.
(3) oxygen proportion
In the present invention, the atmosphere during sputter is the mist of inert gas and oxygen, and the ratio of oxygen is 5～95% in this mist, is preferably 10～80%.With this O
2Preferably inert gas, particularly argon of the possible sputter gas of other of Shi Yonging together.
(4) High frequency power
In the present invention, preferably adopt the RF magnetron sputtering method to carry out sputter.When this sputter, for example for the target of φ 10cm, the High frequency power during sputter is 5～200W, promptly is 0.064～2.55W/cm on the per unit sectional area
2
O in sputter gas
2The lower situation of ratio under, preferably add 5～100W, i.e. per unit sectional area 0.064～1.27W/cm
2High frequency power, on the contrary, for the O in the sputter gas
2Ratio is at 30 to 95 molecule percentages, the situation in the scope of 40 to 80 molecule percentages especially, and the scope of High frequency power value is preferably 1.27～2.55W/cm
2
In the present invention, under being level and smooth condition, the substantial portion that guarantees resulting composite oxide superconductor film surface implements above-mentioned sputter.
Observing under the situation of above-mentioned superconducting thin film surface smoothing the fineness R of film surface with method of optics
Max(datum length=1000 μ m) is below the 0.2 μ m.This value can especially be observed under SEM and confirm at microscope.
Under the desirable state of the present invention, for carrying out the resulting film of sputter under these conditions, after film forming, preferably the film that obtains is heated in oxygen-containing atmosphere-the annealing heat treatment of cooling gradually.This heat treatment is preferably carried out under the heating-up temperature in 800-960 ℃ of scope, and the cooling rate during heat treatment is preferably under 10 ℃/minute.Partial pressure of oxygen during this heat treatment is preferably 0.1-10 air pressure, owing to carry out this processing, has adjusted the oxygen shortcoming of above-mentioned composite oxides, its superconducting characteristic of film without this processing worsens, the situation that can not present superconducting characteristic is arranged, thereby, preferably to carry out above-mentioned heat treatment.
Above-mentioned this based composite oxide superconductor concerning its critical current density, has crystal anisotropy.Promptly easily flow at the direction of the plane parallel that is determined with a axle and the b axle fluid capacitance that powers on by crystallization, up to now, in order to reach the purpose that makes the crystallization direction unanimity, use MgO, the SrTiO that similar spacing of lattice is arranged to complex oxide superconductor crystal lattice spacing as substrate
3The certain surface that reaches monocrystalline such as YSZ is as film forming face.Yet for made before this superconducting compound oxide film, owing to not making crystallization direction obtain very reason such as unanimity, critical current density jc can only be brought up to 100,000 A/cm to greatest extent
2Degree.
The present invention is an optimum value by selecting in the condition of above-mentioned (1)-(4) at least one, can make superconducting compound oxide film surface flatness good, reaches 1,000,000/A/cm thereby make critical current density jc improve two figure places at one stroke
2Level.
By thereby the good reason that increases substantially critical current density jc of superconducting compound oxide film surface flatness can't be illustrated now, but complex oxide superconductor of the present invention has crystal anisotropy concerning its resistance, the superconducting compound oxide film that on the film forming face of substrate, forms, the C axle of its crystallization is vertical or for to approach vertical angle with respect to the substrate film forming face, can think to have increased critical current density.Therefore, the most handy MgO monocrystal chip or SrTiO
3{ 001 } face of monocrystal chip is as film forming face.And, can make C axle same substrate parallel with { 110 } face, also can be with the specially appointed direction vertical with the C axle.And, because MgO, SrTiO
3Its coefficient of thermal expansion is approaching with above-mentioned complex oxide superconductor, can not be added to unnecessary stress on the film in the process of heating, cooling, does not worry breakage of thin film applied.
Be described in detail according to above, shown that superconducting thin film according to the present invention and its Jc that compares with existing method manufacturing will height far away.
Below, with embodiment manufacture method according to superconducting thin film complex of the present invention and superconducting wire is described, but technical scope of the present invention is not subjected to any restriction of following disclosed content.
Moreover following embodiment is for above-mentioned Ln
1Ba
2Cu
3O
7-xType I superconductors I and (La
1-xa
x)
2CuO
4Type I superconductors I carries out for the optimum range of determining any one condition in above-mentioned (1)～(4).
In an embodiment, critical temperature Tc is measured by the common method four-terminal method.Critical current density jc is that the resistance of one side determination test batching when Tc is 77.0K increases the magnitude of current on one side, and the magnitude of current during determination test batching resistance is scaled the electric current road and notes through the value of unit are.Also have, according to from the SEM(scanning electron microscopy) photo calculate film surface fineness R
Max
LnBaCuO class superconducting thin film
Embodiment 1
According to top illustrated method of the present invention, make superconducting thin film with the RF magnetron sputtering method, the target that uses is: by the atomic ratio Ln of lanthanide series Ln, the Ba shown in the following table 1, Cu: Ba: Cu is 1: 2.24: 4.35 composite oxides Ln-Ba-Cu-O pottery that constitutes, and target is that diameter is the circle of φ 100mm.Membrance casting condition is identical under the various situations, and its membrance casting condition is so following:
Substrate: MgO(001) face
Atmosphere gas: O
2/ (O
2+ Ar)=20%
Atmosphere air pressure: 0.1Torr
Substrate temperature: 700 ℃
High frequency power: 40W(0.51W/cm
2)
Time: 6 hours
Thickness: 0.88 μ m
(film forming speed 0.35
/ second)
After the film forming, in atmospheric pressure, 900 ℃ temperature, keep after 3 hours, with 5 ℃/minute cooling rates cooling.The critical temperature of resulting superconducting thin film and critical current density are by shown in the table 1.(table 1 is seen the literary composition back)
Moreover for comparing, removing High frequency power is 150W(1.9W/cm
2) in addition, the manufacturing result under the condition that equates fully is also illustrated in the table 1.
The superconducting thin film of making according to the method for the invention described above is compared with Comparative Examples and have been improved critical current significantly.
And, there is several microns crystal grain to exist corresponding to its surface of superconducting compound oxide film with the Comparative Examples of existing method manufacturing, do not observe concavo-convex situation and under SEM, amplify 10,000 times, can infer that it organizes the same ground fine and close with the superconducting compound oxide film of method manufacturing of the present invention everywhere according to film of the present invention surface.
Embodiment 2
The superconducting thin film manufacture method of implementing to narrate above by the RF magnetron sputtering of the present invention, the target that uses is: the Ln-Ba-Cu-O compound oxidate ceramic made from common method raw materials for sintering powder, this material powder be the same Ba of lanthanide series Ln, the Cu shown in the following table 2, be to form at 1: 2.24: 4.35 with atomic ratio Ln: Ba: Cu.Target is that diameter is the plectane of φ 100mm.Membrance casting condition under the various situations is identical, and its membrance casting condition is so following:
Substrate MgO(001) face
700 ℃ of substrate temperatures
Atmosphere gas O
2/ (O
2+ Ar)=20%
Atmosphere air pressure 0.1Torr
High frequency power 40W(0.51W/cm
2)
6 hours time
Thickness 0.88 μ m
(film forming speed 0.35
/ second)
After the film forming, with 900 ℃ temperature at atmospheric O
2The middle maintenance 1 hour, afterwards, cool off with 5 ℃/minute cooling rate.The critical temperature and the critical current density of resulting superconducting thin film are as shown in table 2.
In order to compare, team's film forming speed is 1.5
Table 2 is also expressed Comparative Examples is made situation under the condition that equates fully result outside/second.
Compare with Comparative Examples as above-mentioned visible superconducting thin film made according to the method for the present invention, improved critical current significantly.
And, there is several microns crystal grain to exist corresponding to its surface of superconducting compound oxide film by the Comparative Examples that has the method manufacturing now, and it is made according to the method for the present invention, amplifying 10,000 times under SEM observes under its surperficial situation, can not see concavo-convex phenomenon on its surperficial most of area, its tissue of superconducting compound oxide film that this deducibility goes out with method manufacturing of the present invention is the same.(table 2 is seen the literary composition back)
Embodiment 3
The following embodiment of the invention is to implement the example of the top superconducting thin film manufacture method of being narrated of the present invention by the RF magnetron sputtering.
Employed target is: the Ln-Ba-Cu-O compound oxidate ceramic made from method raw materials for sintering powder commonly used, this material powder is to form at 1: 2.24: 4.35 with the same Ba of lanthanide series Ln, the Cu shown in the following table 3 with atomic ratio Ln: Ba: Cu.Target uses the plectane of diameter as φ 100mm, and the membrance casting condition of various situations is identical, and its membrance casting condition is so following:
Substrate MgO(001) face
700 ℃ of substrate temperatures
Pressure 0.1Torr
Sputter gas O
2(20%)/Ar(80%)
High frequency power 40W(0.51W/cm
2)
6 hours time
Thickness 0.88 μ m
Film forming speed 0.35
/ second
Annealed 900 ℃/3 hours
(with 5 ℃ of branch coolings)
The critical temperature of resulting superconducting thin film, critical current density and surface smoothness are as shown in table 3.
In order to compare, except that film forming speed is 1.5A/ second, with the above-mentioned condition that equates fully under, the result of the manufacturing situation of Comparative Examples also shows in table 3.(table 3 is seen the literary composition back)
As seen by above-mentioned, superconducting thin film according to the present invention is compared with Comparative Examples and has been improved critical current significantly.
And, although on the film surface made from method of the present invention, have only a little little by little (about all surfaces amass 1%) observed several micron-sized rooms, observe under its surperficial situation but under SEM, amplify 10,000 times, can not see concavo-convex phenomenon on most of area on its surface.And the superconducting compound oxide film of the Comparative Examples made from the method beyond the scope of the invention, there is several microns crystal grain mostly in its surface.
Embodiment 4
The superconducting thin film manufacture method of implementing to narrate above by the RF magnetron sputtering of the present invention.Employed target is the Ln-Ba-Cu-O compound oxidate ceramic of making according to common method raw materials for sintering powder, and this material powder is to form at 1: 2.24: 4.35 by the same Ba of lanthanide series Ln, the Cu shown in the following table 4 with atomic ratio Ln: Ba: Cu.Target is that the plectane of φ 100mm is made by diameter.Membrance casting condition is identical under the various situations, and its membrance casting condition is so following:
Substrate MgO(001) face
700 ℃ of substrate temperatures
Atmosphere gas O
2/ (O
2+ Ar)=50%
Atmosphere air pressure 0.1Torr
High frequency power 150W(1.9W/cm
2)
6 hours time
Thickness 0.88 μ m
(film forming speed 0.35
/ second)
After the film forming, with 900 ℃ temperature at atmospheric O
2The middle maintenance 1 hour, afterwards, to cool off with 5 ℃/minute cooling rate, the critical temperature and the critical current density of resulting superconducting thin film are as shown in table 4.
In order to compare, removing film forming speed is 1.5
Beyond/second, the result who makes situation with the condition that equates fully also shows in table 4 as a comparison case.
By as seen above-mentioned, superconducting thin film made according to the method for the present invention is compared with Comparative Examples, improved critical current significantly, and, there is several microns crystal grain to exist corresponding to its surface of superconducting compound oxide film according to the Comparative Examples that has the method manufacturing now, make for method of the present invention, under SEM, amplify 10,000 times and observe, on most of area on its surface, can not see concavo-convex phenomenon.Its tissue of superconducting compound oxide film that this deducibility goes out with method manufacturing of the present invention is the same.(table 4 is seen the literary composition back)
Embodiment 5
The superconducting thin film manufacture method of implementing to narrate above by the RF magnetron sputtering of the present invention.
Employed target is: the Ln-Ba-Cu-O compound oxidate ceramic made from common method raw materials for sintering powder, this material powder is 1: 2.24: 4.35 formation with the same Ba of lanthanide series Ln, the Cu shown in the following table 5 with atomic ratio Ln: Ba: Cu.Target is that the plectane of φ 100mm is made by diameter.Membrance casting condition under the various situations is identical, and its membrance casting condition is so following:
Substrate MgO(001) face
690 ℃ of substrate temperatures
High frequency power 100W(1.27W/cm
2)
6 hours time
Thickness 0.88 μ m
Film forming speed 0.35
/ second
Film forming air pressure 0.15Torr
Film forming gas is formed O
2/ Ar(20/80)
After the film forming, in atmospheric pressure, kept 3 hours, afterwards, cool off with 5 ℃/minute cooling rate with 910 ℃ temperature.The critical temperature and the critical current density of resulting superconducting thin film are as shown in table 5.
In order to compare, removing film forming air pressure and be 0.0008Torr and 0.7Torr and High frequency power is 150W(1.9W/cm
2) outside, with the above-mentioned condition that equates fully under the result of situation of manufacturing also in table 5, show.(table 5 is seen the literary composition back)
Superconducting thin film by the method manufacturing of the present invention of above-mentioned visible usefulness is compared with Comparative Examples, has improved critical current significantly.
And, under SEM, amplifying 10,000 times with its surface of superconducting compound oxide film of method manufacturing of the present invention and observe, its about area more than 98% in surface be can not see concavo-convex phenomenon.But with the superconducting compound oxide film of the Comparative Examples of the method manufacturing beyond the scope of the invention, its surface exists in several microns crystal grain mostly.
Embodiment 6
Be to make the superconducting wire of narrating above of the present invention with the RF magnetron sputtering.
As core is to adopt: carry out the bar that wire drawing becomes diameter 1mm length 150mm with fiber elongation method from the MgO monocrystal rod, carry out sputter while rotate above-mentioned on the substrate frame of RF magnetic controlled tube sputtering apparatus commonly used.
And employed target is: with the made Ln-Ba-Cu-O compound oxidate ceramic of common method raw materials for sintering powder, this material powder is 1: 2.24: 4.35 formation with the same Ba of lanthanide series Ln, the Cu shown in the following table 6 with atomic ratio Ln: Ba: Cu.It is the plectane of φ 100mm that target adopts diameter.Membrance casting condition under the various situations is identical, and its membrance casting condition is so following:
700 ℃ of core heating-up temperatures
Sputtering pressure 0.1Torr
Oxygen ratio O
2(20%)/Ar(80%)
High frequency power 40W(0.51W/cm
2)
6 hours time
Film forming speed 0.30
/ second
Annealed 900 ℃/3 hours
(with 5 ℃ of/minute coolings)
The critical temperature of resulting wire rod, critical current density and surface smoothness are as shown in table 6.
Although the method according to this invention on the surface of formed superconducting compound oxide film on the core, have only a little little by little (about all surfaces 1%) observed several micron-sized rooms, observe under its surperficial situation but under SEM, amplify 10,000 times, on its surperficial most of area, can not see concavo-convex phenomenon.And there is several microns crystal grain mostly in its surface of superconducting compound oxide film of the Comparative Examples of the method manufacturing beyond the method according to this invention scope.(table 6 is seen the literary composition back)
(La
1-xB
x)
2CuO
4Type I superconductors I
Embodiment 7
Be according to the method for narrating above of the present invention, make superconducting thin film with the RF magnetron sputtering method.
Test batching is: respectively La: the ratio of components of Ba: Cu is that 1.8: 0.2: 1 composite oxides sintered body is made for target and is the ratio of components of La: Sr: Cu that 1.8: 0.2: 1 composite oxides sintered body is made for target.Also have, it is the roundel of φ 100mm that target adopts diameter.
Substrate MgO(001) face
O
2/（O
2+Ar）20%
Pressure 0.1Torr
700 ℃ of substrate temperatures
High frequency power 40W(0.51W/cm
2)
6 hours time
Thickness 0.88 μ m
(film forming speed 0.35A/ second)
After the film forming, with 900 ℃ temperature (O in atmospheric pressure
2Dividing potential drop is about 0.2Torr) kept 3 hours, afterwards, with 5 ℃/minute cooling rate cooling.
In order to compare, use identical target respectively, be 150W(1.9W/cm except only adding electric power
2) outside, made the superconducting compound oxide film with the condition that equates fully.
Its result always is shown in table 7.(table 7 is seen the literary composition back)
Embodiment 8
The superconducting thin film manufacture method of implementing to narrate above by the RF magnetron sputtering of the present invention.Target adopts respectively: with the atomic ratio La of common method sintering La, Ba, Cu: Ba: Cu is the La-Ba-Cu-O composite oxides sintered body that the material powder that forms at 1.8: 0.2: 1 is made, and utilizes the atomic ratio La of common method sintering La, Sr, Cu: Sr: Cu is the La-Ba-Cu-O composite oxides sintered body that the material powder that forms at 1.8: 0.2: 1 is made.Target is that diameter is the plectane of φ 100.The membrance casting condition of various situations is identical, and its membrance casting condition is so following:
Substrate MgO(001) face
O
2/（O
2+Ar）20%
700 ℃ of substrate temperatures
Pressure 0.1Torr
High frequency power 40W(0.51W/cm
2)
6 hours time
Thickness 0.88 μ m
(film forming speed 0.35
/ second)
After the film forming, with 900 ℃ temperature at atmospheric O
2The middle maintenance one hour, afterwards, cool off with 5 ℃/minute cooling rate.
In order to compare, except film forming speed under the situation of identical target is 1.5
Outside/second, under the condition that equates fully, make the superconducting compound oxide film.
Resulting summary sheet as a result is shown in the table 8.(table 8 is seen the literary composition back)
Embodiment 9
Following embodiments of the invention are superconducting thin film manufacture methods of the present invention of implementing to narrate above by the RF magnetron sputtering.
Used target is: with the composite oxides sintered body that method raw materials for sintering powder commonly used is made, this material powder is 1.8: 0.2: 1 formations with the same La of element a, the Cu that represent La or Sr with atomic ratio La: a: Cu.Target adopts the plectane of diameter phi 100mm.The membrance casting condition of various situations is identical, and its membrance casting condition is so following:
Substrate MgO(001) face
700 ℃ of cardinal temperatures
Pressure 0.1Torr
Sputter gas O
2(20%)/Ar(80%)
High frequency power 40W(0.51W/cm
2)
6 hours time
Thickness 0.88 μ m
Film forming speed 0.35
/ second
Annealed 900 ℃/3 hours
(with 5 ℃ of/minute coolings)
And film forming speed is 1.5 in that other membrance casting condition is identical corresponding to various targets
Make Comparative Examples under the condition of/second.
Its result is illustrated in the table 9.(table 9 is seen the literary composition back)
As seen by above-mentioned, superconducting thin film according to the present invention is compared with Comparative Examples and has been improved critical current significantly.
And, although on the film surface that the method according to this invention is made, have only a little little by little (about all surfaces amass 1%) observed several micron-sized rooms, but amplifying 10,000 times under SEM observes under its surperficial situation, can not see concavo-convex phenomenon on most of area on its surface, and there is several microns crystal grain in its surface mostly in the superconducting compound oxide film of the Comparative Examples by the method manufacturing beyond the inventive method scope.
Embodiment 10
Be to make superconducting thin film of the present invention by the RF magnetron sputtering, used target is: the composite oxides sintered body made from common method raw materials for sintering powder, this material powder is to constitute at 1.8: 0.2: 1 by La and Sr or Ba and Cu with atomic ratio La: a: Cu.Target is that diameter is the plectane of φ 100mm.The membrance casting condition of various situations is identical, and its membrance casting condition is as following:
Substrate MgO(001) face
O
2/（O
2+Ar）50%
700 ℃ of substrate temperatures
Pressure 0.1Torr
High frequency power 150W(1.9W/cm
2)
6 hours time
Thickness 0.88 μ m
(film forming speed 0.35
/ second)
After the film forming, at 900 ℃ atmospheric O
2The middle maintenance, cooled off with 5 ℃/minute cooling rate after one hour.
In order to contrast, removing film forming speed is 1.5
Beyond/second, under the condition that equates fully, make the superconducting compound oxide film.
Gained is the result all show at table 10.(table 10 is seen the literary composition back)
There is several microns crystal grain in its surface for superconducting compound oxide film with the Comparative Examples that has the method manufacturing now, and make by method of the present invention, under SEM, amplify 10,000 times and observe under its surperficial situation, on its surperficial most of area, can not see concavo-convex phenomenon.Can infer that its tissue of superconducting compound oxide film with method manufacturing of the present invention is the same.
Embodiment 11
Be to make superconducting thin film of the present invention by the RF magnetron sputtering.Employed target is to adopt the composite oxides sintered body make with common method raw materials for sintering powder, and material powder is to be 1.8: 0.2: 1 formations by La, the element a that represents Ba or Sr and Cu with atomic ratio La: a: Cu.Target is that diameter is the plectane of φ 100mm, and the membrance casting condition of various situations is identical, and its membrance casting condition is so following:
Substrate MgO(001) face
690 ℃ of substrate temperatures
High frequency power 100W(1.27W/cm
2)
6 hours time
Thickness 0.88 μ m
Film forming speed 0.35
/ second
Film forming air pressure 0.15Torr
Film forming gas constitutes O
2/ Ar(20: 80)
After the film forming, kept in atmospheric pressure 3 hours with 910 ℃ temperature, afterwards, cool off with 5 ℃/minute cooling rate, its result is represented by table 11.
In order to compare, except that film forming air pressure is 0.0008Torr and 0.7Torr, with above-mentioned identical condition under make the superconducting compound oxide film, result in this case is also illustrated in the table 11.
Under SEM, amplify the superconducting compound oxide film surface that 10,000 times of observations are made with method of the present invention, can not see concavo-convex phenomenon on about area more than 98% on its surface.But, have several microns crystal grain mostly with its surface of superconducting compound oxide film of the Comparative Examples of the method manufacturing outside the scope of the invention.(table 11 is seen the literary composition back)
LnBaCuO class superconducting thin film
Embodiment 12
Be to make superconducting thin film according to the manufacture method of narrating above of the present invention.Employed target is: is the composite oxides Ln-Ba-Cu-O pottery that constitutes at 1: 2.24: 4.35 by the lanthanide series Ln shown in the following table 12 and Ba, Cu with atomic ratio Ln: Ba: Cu, and target is that diameter is the plectane of φ 100mm.The membrance casting condition of various situations is identical, and its membrance casting condition is as following:
Substrate MgO(001) face
700 ℃ of substrate temperatures
Pressure 0.01～0.1Torr
High frequency power 40W(0.51W/cm
2)
6 hours time
Thickness 0.8 μ m
After the film forming, with 900 ℃ temperature at atmospheric O
2The middle maintenance one hour, afterwards, cool off with 5 ℃/minute cooling rate.
In order to compare, removing High frequency power is 150W(1.9W/cm
2) outside, under the condition that equates fully, making the superconducting compound oxide film that contains Ho, the result of this situation also is illustrated in the table 12.(table 12 is seen the literary composition back)
As seen by above-mentioned, superconducting thin film made according to the method for the present invention is compared with Comparative Examples, has improved critical current density significantly.There is several microns crystal grain for its surface of superconducting compound oxide film with the Comparative Examples that has the method manufacturing now, and make with the inventive method, under SEM, amplify 10,000 times and observe its surface, can not see concavo-convex phenomenon, can infer out, be same fine and close with its tissue of superconducting compound oxide film of method manufacturing of the present invention.
Table 1
Ln critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Examples Ho 82.0 850
Comparative Examples Tm 82.0 850
Comparative Examples Lu 82.0 845
Ho 82.1 2.0 * 10 of the present invention
6
Er 86.0 2.5 * 10 of the present invention
6
Y 81.0 1.5 * 10 of the present invention
6
Dy 83.2 2.5 * 10 of the present invention
6
Gd 81.0 1.7 * 10 of the present invention
6
Eu 80.6 1.2 * 10 of the present invention
6
Sm 80.4 1.0 * 10 of the present invention
6
Yb 80.2 1.0 * 10 of the present invention
6
Nd 80.8 1.2 * 10 of the present invention
6
La 79.0 0.8 * 10 of the present invention
6
Tm 82.1 1.8 * 10 of the present invention
6
Lu 80.4 1.0 * 10 of the present invention
6
Table 2
Ln critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Examples Ho 82.0 850
Comparative Examples Tm 82.0 850
Comparative Examples Lu 82.0 840
Ho 82.2 1.9 * 10 of the present invention
6
Er 87.1 2.8 * 10 of the present invention
6
Y 80.5 1.4 * 10 of the present invention
6
Dy 83.1 2.6 * 10 of the present invention
6
Gd 81.2 1.8 * 10 of the present invention
6
Eu 80.5 1.1 * 10 of the present invention
6
Sm 80.0 0.9 * 10 of the present invention
6
Yb 80.0 0.9 * 10 of the present invention
6
Nd 80.4 1.1 * 10 of the present invention
6
La 79.3 0.8 * 10 of the present invention
6
Tm 82.2 1.5 * 10 of the present invention
6
Lu 80.5 1.0 * 10 of the present invention
6
Table 3
Ln critical temperature critical current density surface smoothness
Tc（K） Jc（A/cm
2） Rmax（μm）
Comparative Examples Ho 82.0 850 0.07
Comparative Examples Tm 83.0 860 0.06
Comparative Examples Lu 81.0 840 0.08
Ho 82.0 2.0 * 10 of the present invention
60.001
Er 87.3 3.0 * 10 of the present invention
60.002
Y 80.9 1.5 * 10 of the present invention
60.002
Dy 83.0 2.5 * 10 of the present invention
60.002
Gd 81.4 1.8 * 10 of the present invention
60.001
Eu 80.4 1.0 * 10 of the present invention
60.002
Sm 80.4 1.0 * 10 of the present invention
60.001
Yb 80.0 0.9 * 10 of the present invention
60.002
Nd 80.5 1.1 * 10 of the present invention
60.002
La 79.0 0.8 * 10 of the present invention
60.001
Tm 82.4 1.9 * 10 of the present invention
60.003
Lu 79.0 0.9 * 10 of the present invention
60.002
Table 4
Ln critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Example H o 81.9 800
Comparative example Tm 82.1 810
Comparative example Lu 81.9 790
Ho 82.6 2.2 * 10 of the present invention
6
Er 87.0 2.8 * 10 of the present invention
6
Y 81.0 1.5 * 10 of the present invention
6
Dy 82.7 2.4 * 10 of the present invention
6
Gd 81.5 1.8 * 10 of the present invention
6
Eu 80.2 1.0 * 10 of the present invention
6
Sm 80.4 1.0 * 10 of the present invention
6
Yb 80.0 0.9 * 10 of the present invention
6
Nd 80.4 1.0 * 10 of the present invention
6
La 79.5 0.9 * 10 of the present invention
6
Tm 81.0 1.2 * 10 of the present invention
6
Lu 79.5 0.8 * 10 of the present invention
6
Table 5
Ln critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Examples 1 (1) Ho 81.0 450
Comparative Examples 1 Tm 81.0 450
Comparative Examples 1 Lu 81.4 460
Comparative Examples 2 (2) Ho 81.0 450
Comparative Examples 2 Tm 81.0 870
Comparative Examples 2 Lu 81.8 910
Ho 82.0 1.9 * 10 of the present invention
6
Er 87.0 2.8 * 10 of the present invention
6
Y 81.0 1.9 * 10 of the present invention
6
Dy 83.0 2.5 * 10 of the present invention
6
Gd 81.0 1.7 * 10 of the present invention
6
Eu 80.2 1.0 * 10 of the present invention
6
Sm 80.5 1.1 * 10 of the present invention
6
Yb 80.0 0.9 * 10 of the present invention
6
Nd 80.5 1.1 * 10 of the present invention
6
La 79.2 0.8 * 10 of the present invention
6
Tm 81.8 1.7 * 10 of the present invention
6
Lu 79.2 0.9 * 10 of the present invention
6
Annotate: (1) air pressure=0.0008Torr
High frequency power=150W(1.9W/cm
2)
(2) air pressure=0.7Torr
High frequency power=150W(1.9W/cm
2)
Table 6
Embodiment Ln critical temperature critical current density surface smoothness
Tc（K） Jc（A/cm
2） Rmax
1 Ho 82.0 2.0×10
60.008
2 Er 88.1 2.0×10
60.009
3 Y 81.0 2.0×10
60.010
4 Dy 84.0 1.8×10
60.022
5 Gd 77.1 0.1×10
60.012
6 Eu 78.1 0.5×10
60.008
7 Sm 79.2 0.6×10
60.032
8 Yb 75.1 0.3×10
60.031
9 Nd 72.3 0.1×10
60.042
10 La 78.2 0.5×10
60.012
Table 7
α critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Examples Ba 28 500
Comparative Examples Sr 38 1000
Ba 28 1 * 10 of the present invention
5
Sr 38 1 * 10 of the present invention
6
Table 8
α critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Examples Ba 28 70
Comparative Examples Sr 38 150
Ba 28 1 * 10 of the present invention
5
Sr 38 1 * 10 of the present invention
6
Table 12
Ln critical temperature critical current density
Tc（K） Jc（A/cm
2）
Comparative Examples Ho 82.0 850
Ho 82.1 2.1 * 10 of the present invention
6
Er 88.2 2.0 * 10 of the present invention
6
Y 81.6 2.2 * 10 of the present invention
6
Dy 84.5 1.9 * 10 of the present invention
6
Gd 77.8 0.1 * 10 of the present invention
6
Eu 78.4 0.7 * 10 of the present invention
6
Sm 80.1 0.9 * 10 of the present invention
6
Yb 77.2 0.6 * 10 of the present invention
6
Nd 77.5 0.3 * 10 of the present invention
6
La 78.3 0.4 * 10 of the present invention
6
Claims (12)
1, a kind of superconducting wire that is made of core and superconducting thin film, wherein said core is by Pt, Ag, Au, MgO, SrTiO
3Or ZrO
2, Pt alloy, Ag alloy, Au alloy composition, in fact wherein said superconducting thin film is made up of a kind of composite oxides of selecting from following one group, this group comprises:
A) by general formula Ln
1Ba
2Cu
3O
7-δThe composite oxides of expression, wherein Ln represents the lanthanide series that at least one is selected from the group that Ln, La, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Yb, Tm and Lu form, and δ is a number that satisfies the scope of 0≤δ＜1;
B) by general formula (La
1-xa
x)
2CuO
4The composite oxides of expression, wherein a represents Ba or Sr;
And described superconducting wire further comprises by MgO, SrTiO
3Perhaps ZrO
2The ceramic film made of a kind of monocrystalline, described monocrystalline is deposited on the described core by sputtering method, the essential part on wherein said superconducting thin film surface is smooth, the surface smoothness R of wherein said superconducting thin film
Max(datum length=1000 μ m) is less than 0.2 μ m.
2, superconducting wire according to claim 1, wherein said ceramic surface have [001] face or [110] face.
3, a kind of manufacturing comprises the method for the superconducting wire of core and ultrathin membrane, and wherein said core is by Pt, Ag, Au, MgO, SrTiO
3Or ZrO
2, Pt alloy, Ag alloy, Au alloy make, in fact wherein said superconducting thin film is made of a kind of composite oxides of selecting from following one group, this group comprises:
A) by general formula Ln
1Ba
2Cu
3O
7-δThe composite oxides of expression, wherein Ln represents the lanthanide series that at least one is selected from the group that La, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Yb, Tm and Lu form, and δ is a number that satisfies the scope of 0≤δ＜1;
B) by general formula (La
1-xa
x)
2CuO
4The composite oxides of expression, wherein a represents Ba or Sr;
And described superconducting wire further comprises by MgO, SrTiO
3Perhaps ZrO
2The ceramic film made of monocrystalline, described monocrystalline is deposited on the described core by sputtering method, the essential part on wherein said superconducting thin film surface is smooth, wherein said superconducting thin film surface smoothness R
Max(datum length=1000 μ m) is less than 0.2 μ m.It is characterized in that: sputter is to finish under such operating condition, promptly by control deposition rate within the scope of 0.05 to 1 dust/second, in the mist of gas pressure from 0.001 to 0.5 torr, inert gas and oxygen the ratio of oxygen in 5 to 95% scope and high frequency power from 0.064 to 2.55W/cm
2, and make the essential part on the final described superconducting thin film surface that obtains become smooth.
4, method according to claim 3 is characterized in that described ceramic surface has [001] face or [110] face.
5, method according to claim 3 is characterized in that heated substrate in the described sputter stage.
6, method according to claim 5 is characterized in that described substrate is heated to the temperature of from 200 to 950 ℃ of scopes.
7, method according to claim 6 is characterized in that described substrate is heated to the temperature of from 500 to 920 ℃ of scopes.
8,, it is characterized in that described sputter is a magnetron sputtering according to each described method in the claim 3 to 6.
9, according to each described method in the claim 3 to 6, it is characterized in that in oxygen-containing atmosphere, the film after the film forming further being heat-treated.
10, method according to claim 9 is characterized in that described heat treatment carries out in 800 to 960 ℃ temperature range.
11, method according to claim 9 is characterized in that film after the above-mentioned heat treatment is to cool off at leisure less than 10 ℃/minute cooldown rate.
12, according to the method for claim 9, it is characterized in that described heat treatment is to carry out under 0.1 to 10 air pressure in partial pressure of oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92102035A CN1024859C (en) | 1987-12-20 | 1992-03-25 | Composite oxides superconductive wire rod and their manufacture method |
Applications Claiming Priority (21)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP322380/87 | 1987-12-20 | ||
| JP62322380A JP2544759B2 (en) | 1987-12-20 | 1987-12-20 | How to make a superconducting thin film |
| JP324706/87 | 1987-12-22 | ||
| JP324709/87 | 1987-12-22 | ||
| JP324702/87 | 1987-12-22 | ||
| JP324704/87 | 1987-12-22 | ||
| JP324710/87 | 1987-12-22 | ||
| JP324705/87 | 1987-12-22 | ||
| JP324703/87 | 1987-12-22 | ||
| JP324701/87 | 1987-12-22 | ||
| JP324708/87 | 1987-12-22 | ||
| JP324707/87 | 1987-12-22 | ||
| JP332304/87 | 1987-12-29 | ||
| JP012335/88 | 1988-01-22 | ||
| JP012332/88 | 1988-01-22 | ||
| JP012334/88 | 1988-01-22 | ||
| JP63012335A JPH0829938B2 (en) | 1988-01-22 | 1988-01-22 | Composite oxide superconducting thin film and method for producing the same |
| JP012331/88 | 1988-01-22 | ||
| JP012333/88 | 1988-01-22 | ||
| CN88109261A CN1021175C (en) | 1987-12-20 | 1988-12-19 | Composite oxide superconductive film |
| CN92102035A CN1024859C (en) | 1987-12-20 | 1992-03-25 | Composite oxides superconductive wire rod and their manufacture method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88109261A Division CN1021175C (en) | 1987-12-20 | 1988-12-19 | Composite oxide superconductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1067524A CN1067524A (en) | 1992-12-30 |
| CN1024859C true CN1024859C (en) | 1994-06-01 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92102035A Expired - Fee Related CN1024859C (en) | 1987-12-20 | 1992-03-25 | Composite oxides superconductive wire rod and their manufacture method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024859C (en) |
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1992
- 1992-03-25 CN CN92102035A patent/CN1024859C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1067524A (en) | 1992-12-30 |
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