CN101752035B - Method for preparing high temperature superconducting thin film by chemical process - Google Patents
Method for preparing high temperature superconducting thin film by chemical process Download PDFInfo
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- CN101752035B CN101752035B CN2008102399608A CN200810239960A CN101752035B CN 101752035 B CN101752035 B CN 101752035B CN 2008102399608 A CN2008102399608 A CN 2008102399608A CN 200810239960 A CN200810239960 A CN 200810239960A CN 101752035 B CN101752035 B CN 101752035B
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Abstract
The invention provides a method for preparing high temperature superconducting thin film by chemical process. The method comprises the following steps: firstly preparing a precursor solution, by mixing Y(CH3COO)3, RE(CH3COO)3, Ba(CH3COO)2 and Cu(CH3COO)2 with ratio of (Y+RE) to Ba to Cu equaling to 1:2:3 (wherein RE is Nd, Sm, Eu, Gd and Dy) and dissolving in 20-30 mol percent aqueous trifluoroacetic acid solution; stirring to be uniform, performing vacuum drying by evaporation to the solvent to obtain gel; then adding methanol, stirring to be uniform, performing drying by evaporation to the solvent to obtain gel; then adding proper amount of methanol to prepare the precursor solution with the total concentration of metal ions of Y, RE, Ba and Cu being 0.8-3.0mol/L; then coating the precursor solution on a substrate; performing low temperature heat treatment at 400-410 DEG C to the coated thin film to decompose trifluoroacetic acid salt; and finally performing high temperature heat treatment at 800-850 DEG C and annealing process at 490-510 DEG C to form YBCO thin film doped with rare-earth element.
Description
Technical field
The present invention relates to a kind of chemical solution preparation method of high-temperature superconducting thin film, particularly utilize yttrium barium copper oxide (YBCO) film of the organic method of trifluoroacetate-metal (TFA-MOD) preparation doped with rare-earth elements.
Background technology
Superconductor can be prepared into different forms according to the difference of application: film material, bulk, wire rod (band).For superconducting thin film, in current topmost high-temperature superconductor system, BiSrCaCuO (BSCCO), TlBa
2The T of CaCuO (TBCCO) and HgBaCaCuO (HBCCO) system
C(inversion temperature) is though higher (Tc 〉=110K), because the growth in situ progress of BSCCO, TBCCO and HBCCO high-temperature superconducting thin film is slow, at present, the BSCCO of Tc 〉=110K, TBCCO and HBCCO superconducting thin film still mainly adopt the post-processing approach preparation.The high-temperature superconducting thin film of post-processing approach preparation is generally polycrystal film, and Jc is lower, and the surface is also more coarse, can not satisfy the requirement of making the high-temperature superconductor electronic device.YBa
2Cu
3O
7-x(YBCO) lower (T of though Tc
C=90K), but the microwave surface resistance Rs of ybco film can be used for designing high performance passive microwave device, for example filter, resonator, delay line etc. than the little several magnitude of common metal material.And the research of the growth in situ of ybco film makes significant progress, can adopt the high-quality ybco film of several different methods growth in situ.Comprising that pulsed laser deposition (PLD), sputtering method (Sputtering), polynary coevaporation method (Co-evaporation), Metalorganic Chemical Vapor Deposition (MOCVD) wait in these physics and method chemistry, trifluoroacetate-metal organic deposit (TFA-MOD) method has numerous advantages.The first, the solution coatings technology can satisfy industrial width and length requirement to coating.The second, need use vacuum system to compare with magnetron sputtering, metal organic chemical vapor deposition and pulsed laser deposition with expensive equipment, metal organic deposit cost is low, the deposition rate height.The 3rd, composition is controlled easily, can accurately control metal group member's proportioning.Therefore, the TFA-MOD legal system is equipped with the concern that ybco film has caused domestic and international scientist in recent years.
Along with the scope of application of going deep into and enlarging it to ybco film research, also must manage in high-temperature superconductor, to introduce strong flux pinning center, overcome the hot activation flux creep that causes owing to weak flux pinning ability under the high temperature, phenomenons such as magnetic flux rheology, improve the flux pinning ability of high-temperature superconductor, thereby further improve the critical current density (Jc) under its magnetic field.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing high performance high-temperature superconducting thin film cheaply.
For achieving the above object, the invention provides a kind of method of preparing high temperature superconducting thin film by chemical process, comprise the steps:
First step, according to (Y+RE): Ba: Cu=1: 2: 3 molar ratio is Y (CH
3COO)
3, RE (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Mix, room temperature is dissolved in wiring solution-forming in the deionized water that contains the equivalent trifluoroacetic acid, and wherein, RE is one or more among Nd, Sm, Eu, Gd or the Dy, RE (CH
3COO)
3Account for Y (CH
3COO)
3Molar content be 1-10%;
Second step, after above-mentioned solution stirred, vacuum evaporating solvent obtained gel;
Third step adds methyl alcohol with above-mentioned gel, and making Y, RE, Ba and Cu metal ion total concentration is the solution of 0.8-3.0mol/L, stirs, and is prepared into precursor liquid;
The 4th step adopts spin coating with above-mentioned precursor liquid or the method that lifts is coated on the substrate; Preferred employing sol evenning machine is coated on the substrate with 3000 rev/mins-6000 rev/mins speed;
The 5th step is carried out about 10 hours heat treatment under 400 ℃～410 ℃ conditions, to decompose trifluoroacetate;
The 6th step is at the cubic phase ybco film of 800 ℃～850 ℃ insulations generation in 3-4 hour doped with rare-earth elements;
The 7th step is incubated annealing heat treatment in 0.5-1.5 hour to film under 490 ℃～510 ℃ and pure oxygen condition, be prepared into the YBCO high-temperature superconducting thin film of doped with rare-earth elements.
The method of above-mentioned preparing high temperature superconducting thin film by chemical process wherein, also can be included in before carrying out third step operation and adds in the gel after methyl alcohol makes it dissolving, removed solvent under reduced pressure to remove the purification step of impurity such as moisture.
The method of above-mentioned preparing high temperature superconducting thin film by chemical process, wherein, the trifluoroacetic acid deionized water solution concentration described in the first step can be 20～30 moles of %.
The method of above-mentioned preparing high temperature superconducting thin film by chemical process, wherein, the mixing time in second step is preferably 1-5 hour.
The method of above-mentioned preparing high temperature superconducting thin film by chemical process, wherein, the substrate in the 4th step can be lanthanum aluminate, strontium titanates or magnesium oxide single-crystal matrix.
The method of above-mentioned preparing high temperature superconducting thin film by chemical process, wherein, the 5th step is preferably carried out under moistening oxygen condition, and the vapour pressure in the reative cell is 100hPa-170hPa.
The method of above-mentioned preparing high temperature superconducting thin film by chemical process, wherein, the 6th step is preferably carried out under moistening oxygen and argon gas condition, feeds the argon gas that 500～1000ml/min contains 500～1000ppm oxygen in reative cell, and the vapour pressure in the reative cell is 100hPa-170hPa.
Beneficial effect of the present invention is: method of the present invention can prepare high performance YBCO high-temperature superconducting thin film.Because the acetate that the present invention uses when the preparation precursor liquid removes Y (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Also added the acetate RE (CH that contains Nd, Sm, Eu, Gd or Dy rare earth element outward,
3COO)
3After containing the precursor liquid process low temperature thermal decomposition and high temperature sintering of rare earth element, in ybco film, mixed the RE of nano-scale
2O
3, the RE of these nano-scales
2O
3And RE
2O
3And the defective that forms between the ybco film has well played the effect of flux pinning, has improved the critical current density (J of ybco film greatly
C).Widened the application of YBCO superconducting thin film under externally-applied magnetic field.
Description of drawings
The critical current density test picture of the ybco film that Fig. 1 obtains for embodiment 1;
The critical current density test picture of the ybco film that Fig. 2 obtains for comparative example 1.
Embodiment
Embodiment 1
Press (Y+Sm): Ba: Cu=1: 2: 3 molar ratio is Y (CH
3COO)
3, Sm (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Mix, wherein Sm (CH
3COO)
3Account for Y (CH
3COO)
3Molar content be 5%, room temperature is dissolved in wiring solution-forming in the deionized water that contains the equivalent trifluoroacetic acid fully, the concentration of trifluoroacetic acid is 25 moles of % in the deionized water.
The solution of preparation stirs on magnetic stirrer and improved the solution uniformity in 2 hours, solution is drained gel into blueness with the Rotary Evaporators vacuum then, adding the methyl alcohol stirring more all dissolves gel, drain gel with the Rotary Evaporators vacuum once more subsequently into blueness, add methyl alcohol at last once more, making Y, Sm, Ba and Cu metal ion total concentration is the precursor liquid of 1.5mol/L.
The precursor liquid for preparing is spin-coated on LaAlO with 3000 rev/mins
3On the monocrystalline matrix, spin coating 90 seconds.
The sample that coating is good is placed on to send in the quartz boat in the quartzy stove of tubular type and carries out Low Temperature Heat Treatment and high-temperature heat treatment.
Low Temperature Heat Treatment is to carry out under the moistening oxygen condition, be through the vial that distilled water is housed steam to be brought the oxygen of 500ml/min into reative cell, make that vapour pressure is 160hPa in the reative cell, on average be warming up to 400 ℃ with the heating rate of 40 ℃/h from room temperature, stove is chilled to room temperature then.The purpose of Low Temperature Heat Treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges harmful residual substance.The whole resolving time is about 10h.
High-temperature heat treatment is to carry out at moistening oxygen and argon gas condition, the argon gas mist that 500ml/min is contained 500ppm oxygen is brought steam into reative cell through the vial that distilled water is housed, make that vapour pressure is 190hPa in the reative cell, heating rate with 400 ℃/h rose to the highest temperature before this, be generally 800～850 ℃, present embodiment is 830 ℃.Directly feed the argon gas mist that contains 500ppm oxygen after 2 hours 830 ℃ of insulations, be cooled to 500 ℃ with 100 ℃/h then, insulation made the YBCO oxygen uptake of cubic phase change the YBCO with superconductivity of quadrature phase in 1.5 hours in 500 ℃ purity oxygen atmosphere, and sample stove under the oxygen atmosphere is chilled to room temperature subsequently.With Lepi-system prepared ybco film has been carried out the test of critical current density, as shown in Figure 1.
Since rare earth element nd, Eu, and Gd or Dy and Sm have close character, adopt the method for embodiment 1 can prepare the ybco film that mixes above-mentioned metal oxide equally.
Comparative example 1
Remove Y (CH
3COO)
3, Sm (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Change (CH into Y
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Outside, all the other all are same as embodiment 1.The critical current density test picture of the pure ybco film that comparative example 1 obtains as shown in Figure 2.
Scheme more as can be seen by Fig. 1 and these two of Fig. 2, the critical current density of the YBCO high-temperature superconducting thin film of the doping Sm of embodiment 1 preparation reaches 5.0MA/cm
2, obviously than the critical current density (3.8MA/cm of the pure ybco film of comparative example 1 preparation
2) height.
Claims (6)
1. the method for a preparing high temperature superconducting thin film by chemical process is characterized in that, comprises the steps:
First step, according to (Y+RE): Ba: Cu=1: 2: 3 molar ratio is Y (CH
3COO)
3, RE (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Mix, room temperature is dissolved in wiring solution-forming in the deionized water that contains the equivalent trifluoroacetic acid, and wherein, RE is one or more among Nd, Sm, Eu, Gd or the Dy, RE (CH
3COO)
3Account for Y (CH
3COO)
3Molar content be 1-10%;
Second step, after above-mentioned solution stirred, vacuum evaporating solvent obtained gel;
Third step adds methyl alcohol with above-mentioned gel, and making Y, RE, Ba and Cu metal ion total concentration is the solution of 0.8-3.0mol/L, stirs, and is prepared into precursor liquid;
The 4th step adopts spin coating or method of pulling up to be coated on the substrate above-mentioned precursor liquid;
The 5th step is carried out 10 hours heat treatment under 400 ℃～410 ℃ conditions, to decompose trifluoroacetate;
The 6th step is at the cubic phase ybco film of 800 ℃～850 ℃ insulations generation in 3-4 hour doped with rare-earth elements;
The 7th step is incubated annealing heat treatment in 0.5-1.5 hour to film under 490 ℃～510 ℃ and pure oxygen condition, be prepared into the YBCO high-temperature superconducting thin film of doped with rare-earth elements.
2. the method for preparing high temperature superconducting thin film by chemical process as claimed in claim 1 is characterized in that, the deionized water solution concentration of trifluoroacetic acid described in the described first step is 20～30 moles of %.
3. the method for preparing high temperature superconducting thin film by chemical process as claimed in claim 1 is characterized in that, mixing time is 1-5 hour described in described second step.
4. the method for preparing high temperature superconducting thin film by chemical process as claimed in claim 1 is characterized in that, substrate described in described the 4th step is lanthanum aluminate, strontium titanates or magnesium oxide single-crystal matrix.
5. the method for preparing high temperature superconducting thin film by chemical process as claimed in claim 1 is characterized in that, described the 5th step is to carry out under moistening oxygen condition, and the vapour pressure in the reative cell is 100hPa-170hPa.
6. the method for preparing high temperature superconducting thin film by chemical process as claimed in claim 1, it is characterized in that, described the 6th step is to carry out under moistening oxygen and argon gas condition, feed 500～1000ml/min and contain the argon gas of 500～1000ppm oxygen in reative cell, the vapour pressure in the reative cell is 100hPa-190hPa.
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| CN101752035B true CN101752035B (en) | 2011-10-19 |
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| CN102173820B (en) * | 2011-02-21 | 2013-07-03 | 中国科学院电工研究所 | Preparation method of YBa2Cu3O7-x(YBCO) high-temperature superconductive thick film |
| CN102491740A (en) * | 2011-11-28 | 2012-06-13 | 西北有色金属研究院 | Yttrium barium copper oxide superconducting thin film mixed with samarium and manufacture method thereof |
| CN103073280A (en) * | 2013-01-30 | 2013-05-01 | 江苏天诚线缆集团有限公司 | Preparation method of patterned YBCO high-temperature superconducting thin film |
| CN107459055B (en) * | 2017-09-11 | 2019-03-05 | 西北有色金属研究院 | A kind of method that nanoparticle induction epitaxial growth prepares ybco film |
| CN107893219A (en) * | 2017-11-09 | 2018-04-10 | 南京邮电大学 | A kind of yttrium barium copper oxide superconducting layer of gadolinium samarium doping and preparation method thereof |
| CN108963067B (en) * | 2018-07-27 | 2022-04-29 | 武汉工程大学 | ReBa2Cu3O7-xMethod for preparing pinning layer on superconducting film |
-
2008
- 2008-12-16 CN CN2008102399608A patent/CN101752035B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| 丁发柱等.TFA-MOD制备YCBO带材工艺研究进展.《稀有金属》.2008,第32卷(第1期),94-100. * |
| 丁发柱等.TFA-MOD法制备YCBO薄膜的研究.《第十二届中国有色金属学会材料科学与合金加工学术研讨会文集》.2007,197-202. * |
| 张莉.YBCO掺杂效应研究.《兰州理工大学学报》.2004,第30卷(第1期),130-133. * |
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