CN102584204A - Method for preparing yttrium barium copper oxide (YBCO) superconductive composite film - Google Patents
Method for preparing yttrium barium copper oxide (YBCO) superconductive composite film Download PDFInfo
- Publication number
- CN102584204A CN102584204A CN201210030615XA CN201210030615A CN102584204A CN 102584204 A CN102584204 A CN 102584204A CN 201210030615X A CN201210030615X A CN 201210030615XA CN 201210030615 A CN201210030615 A CN 201210030615A CN 102584204 A CN102584204 A CN 102584204A
- Authority
- CN
- China
- Prior art keywords
- ybco
- solution
- temperature
- film
- trifluoroacetic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
Provided is a method for preparing an yttrium barium copper oxide (YBCO) superconductive composite film. Firstly, a precursor solution is prepared, namely yttrium acetate Y(CH3COO)3, barium acetate Ba(CH3COO)2 and cupric acetate Cu(CH3COO)2 are mixed and dissolved in a water solution containing 10-30 mol% of trifluoroacetic acid according to the molar ratio of Y to Ba to Cu being 1 to 2 to 3. The solvent is evaporated in a vacuum mode to obtain gel after even stirring. Carbinol is further added into the gel to be stirred evenly and then the solvent is dried to obtain gel. Afterwards, an appropriate amount of carbinol and terpineol are added into the solution to prepare a solution with 1.5-3.0 mol/L of total ion concentration of metal Y, metal Ba and metal Cu, after even stirring, zirconium acetylacetonate and titanium acetylacetonate which have 10%-15% of total ion molar concentration of metal Y, metal Ba and metal Cu are added into the solution to prepare the precursor solution. After that, the precursor solution is coated on a substrate. A coated film is first subjected to low temperature thermal decomposition at the temperature of 300-500 DEG C to decompose trifluoroacetic acid salt. Finally, the coated film is subjected to high temperature heat treatment at the temperature of 800-880 DEG C and annealing process at the temperature of 450-550 DEG C to form the YBCO superconductive composite film containing nanometer barium titanate and nanometer barium zirconate. The critical current density of the YBCO superconductive composite film reaches 7 MA/ cm<2> (77K, 0T).
Description
Technical field
The present invention relates to a kind of preparation method of s-generation belt material of high temperature superconduct, particularly a kind of preparation method of YBCO superconducting thin film.
Background technology
Superconducting material is because its unique physicals (zero resistance, diamagnetism, tunnel effect etc.) is attracting numerous scientists' concern in the last hundred years always.Advantage such as utilize device such as hyperconductive cable, superconducting transformer, superconduction electricmachine, superconductive current limiter and superconductive energy storage system and the equipment of superconducting material preparation to have that the incomparable volume of conventional products is little, in light weight, efficient is high, energy consumption is low and capacity is big is with a wide range of applications at power domain.For realizing the application of high temperature superconducting materia in the forceful electric power field, the research of superconducting tape is an important directions.Process band to superconducting material, the problem that at first runs into is exactly that high temperature superconducting materia belongs to pottery, thereby can not as metal, have good ductility.Mainly contain based on Bi at present
2Sr
2Ca
2Cu
3O
10(Bi2223) first-generation belt material of high temperature superconduct of system and based on YBa
2Cu
3O
7-x(RE123) s-generation belt material of high temperature superconduct of system is succeeded in developing.Compare with first-generation Bi based high-temperature superconductive strip, s-generation belt material of high temperature superconduct has the ability of the high electric current of load under the upfield, can under higher temperature and magnetic field, use, and be the focus that various countries competitively research and develop in the high-temperature superconductor field.
At present, have at least 5 tame units all to prepare length in the world and surpass 500m, Ic surpasses the band of 250A.Especially the Superpower company of the U.S., it has been prepared and has reached 1311m, and Ic reaches the long band of km level of 250A; American Superconductor Corp. adopts rolling auxiliary biaxial texture base band/metal organic deposit method (RABiTS
TM/ MOD) maximum length of preparation YBCO coating conductor is 520 meters, can adopt 344 methods to cut into and surpass 3000 meters superconducting tape, has stepped major step to batch process.But the cost for preparing the YBCO band now remains 50 times of copper cash, and the performance that must further improve the YBCO coating conductor could satisfy requirement widely.Can the size that improve the critical current density of ybco film and the pinning defective in the film have much relations, and in film, introducing the defective with nanoscale is a difficult problem, and it needs special means.Heavy ion bombardment and the sub-irradiation method of high energy particle are mainly taked in early stage research, in the YBCO monocrystalline, inject particle and can make its Jc improve one to two one magnitude, and these high energy particles comprise heavy ion, electronics, proton, fast neutron etc.But this method has just run into numerous difficulties when relating to practical application, irradiated material has radioactivity, and considers also unworkable from economic angle.Therefore, must seek new approach to improve the critical current density of YBCO coating.The people such as J.L.MacManus-Driscoll of U.S. Los Alamos National Laboratories and Cambridge University then directly mix zirconium white and excessive barium dust in the YBCO ceramic target, adopt pulsed laser deposition (PLD) to obtain containing the BaZrO that is of a size of 10nm according to the processing condition of preparation ybco film
3(BZO) particulate laminated film.Its critical current density all is higher than the critical current density of pure ybco film at whole externally-applied magnetic field, and especially when externally-applied magnetic field was 7T, its critical current density was five times of pure ybco film.Barcelona, ESP university reported that employing trifluoroacetate-metal organic deposit method (TFA-MOD method) has prepared in 2007 on Nature materials contains nanometer BaZrO
3Ybco film.Its critical current density has not only had large increase than the pure ybco film of TFA-MOD method preparation, and its pining force to be issued to peak in the condition of 77K, externally-applied magnetic field 2T be 21GN m
-3, improved 175% than the BZO/YBCO nano compound film of PLD method preparation, improved 60% than performance at the NiTb of 4.2K alloy.The preparation method that the present domestic patent overwhelming majority about the YBCO superconducting film is a ybco film has only Chinese patent CN 101320604A (Granted publication 101320604B) to mention in the YBCO superconducting film and adds SrZrO
3Improve the effect of its critical current density.But the doping SrZrO for preparing in this patent
3Just just increase in High-Field lower critical current density.
Summary of the invention
The objective of the invention is to overcome the more weak shortcoming of YBCO superconducting thin film current capacity of prior art for preparing, a kind of preparation method of effective raising ybco film critical current density is provided.
The present invention contains the ybco film of nano barium phthalate and nanometer barium zirconate through adopting trifluoroacetate-metal organic deposit (TFA-MOD) method preparation.The present invention adds Terpineol 350, titanium acetylacetone and methyl ethyl diketone zirconium in the precursor liquid that contains trifluoroacetic acid yttrium, trifluoroacetic acid barium and trifluoroacetic acid copper.Concentration through the control metals ion; After through low temperature thermal decomposition and high-temperature heat treatment; Prepare the YBCO superconducting thin film that contains nano barium phthalate and nanometer barium zirconate, utilized two kinds of nano particle synergies of nano barium phthalate and nanometer barium zirconate, the flux pinning effect that improves ybco film.
Concrete preparation process order of the present invention is as follows:
(1) according to Y: Ba: Cu=1: 2: 3 mol ratio is Y (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Three kinds of powder are dissolved under room temperature in the deionized water of the trifluoroacetic acid that contains 10-30mol%, wiring solution-forming, and the mol ratio of solute and solvent is 1: 100 in the described solution;
(2) with the described solution of step (1) preparation through magnetic stirrer 1-3h, adopt Rotary Evaporators to steam to desolventize again and obtain gel;
(3) gel that said step (2) is made adds in the methyl alcohol, and the mol ratio of gel described in this step and methyl alcohol is 1: 50; Behind magnetic stirrer 0.5-1.5h, adopt Rotary Evaporators to steam again and desolventize, with impurity such as further removal moisture, obtain purified gel;
(4) gel that said step (3) is made joins in methyl alcohol and the Terpineol 350, the solution that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 1.5-3.0mol/L, and the volume ratio of described methyl alcohol and Terpineol 350 is 1: 1; The solution stirring that will contain said Y, Ba and Cu is even; Add titanium acetylacetone and methyl ethyl diketone zirconium again; Titanium acetylacetone that is added and methyl ethyl diketone zirconium are the 10%-15% of Y, Ba and three kinds of total ion volumetric molar concentrations of metal of Cu in the described Y of containing, Ba and the Cu solution, are prepared into precursor liquid;
(5) precursor liquid of said step (4) being processed adopts spin coating or method of pulling up to be coated on the substrate;
(6) will place the quartzy stove of high-temperature tubular through the substrate after step (5) applies, under 300 ℃ of-500 ℃ of temperature, carry out the low temperature thermal decomposition of 10h, decompose trifluoroacetate; The temperature rise rate of this step is 40 ℃/h;
(7) will pass through the substrate that said step (6) handles and place 750 ℃～-850 ℃ high-temperature heat treatment 2-4h, generate the cubic phase YBCO film that contains nano barium phthalate, nanometer barium zirconate; The heat-up rate of this step is 400 ℃/h;
(8) will pass through the substrate that step (7) handles and place 450 ℃-550 ℃ of temperature, and under the pure oxygen condition to the film thermal treatment 0.5-1.5h that anneals, be prepared into the YBCO superconducting thin film that contains nano barium phthalate and nanometer barium zirconate.
Substrate described in the step (5) is lanthanum aluminate, strontium titanate or magnesium oxide single-crystal substrate.
Compared with prior art, the present invention has following beneficial effect:
The present invention adds Terpineol 350, methyl ethyl diketone zirconium and titanium acetylacetone in traditional precursor liquid that contains trifluoroacetic acid yttrium, trifluoroacetic acid barium and trifluoroacetic acid copper.Through the concentration of control metals ion, after through low temperature thermal decomposition and high temperature sintering, prepared the YBCO superconducting thin film that contains nano barium phthalate and nanometer barium zirconate.These have the barium titanate of nano-scale and the effect that barium zirconate has well played flux pinning, and compare with single nano particle, and the nano-substance of two kinds of different structures can be worked in coordination with the critical current density that improves the YBCO film.Adopting the ybco film critical current density of this method preparation is at null field or at High-Field raising to be arranged all, reaches 7MA/cm in null field lower critical current density
2, improved the current capacity of YBCO thick film greatly, reduced the production cost of coating conductor, widened the range of application of YBCO coating conductor.
Description of drawings
Fig. 1 is the field emission scanning electron microscope picture of the YBCO film of embodiment 1 preparation;
Fig. 2 is the field emission scanning electron microscope picture of the YBCO film of embodiment 2 preparations;
Fig. 3 is the X ray diffracting spectrum of the YBCO film of embodiment 2 preparations;
Fig. 4 is the critical transition temperature curve of the YBCO film of embodiment 3 preparations;
Fig. 5 is the critical current density curve of the YBCO film of embodiment 4 preparations.
The specific embodiment mode
Embodiment 1
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.005mol, 0.01mol and 0.015mol; With wiring solution-forming in the deionized water that is dissolved in the trifluoroacetic acid that contains 10mol% after yttium acetate, NSC 75794 and the venus crystals mixing, wherein the mol ratio of solute and solvent is 1: 100 in the solution;
(2) solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 1h;
(3) methyl alcohol of 1.55mol is added in the gel that said step (2) makes; Behind magnetic stirrer 0.5h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel, wherein the molar ratio of colloidal sol and methyl alcohol is 1: 50;
(4) gel that step (4) is made joins in the mixed solution of 10.3ml methyl alcohol and 10.3ml Terpineol 350, and the volume ratio of described methyl alcohol and Terpineol 350 is 1: 1, the solution that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 1.5mol/L.The methyl alcohol that contains Y, Ba and Cu and the terpineol solution of gained are stirred; Add 0.0015mol titanium acetylacetone and 0.0015mol methyl ethyl diketone zirconium again; The ratio of titanium acetylacetone and methyl ethyl diketone zirconium is 1: 1; The methyl ethyl diketone zirconium that is added be in the described Y of containing, Ba and three kinds of metallic solutions of Cu Y, Ba and three kinds of total ion volumetric molar concentrations of metal of Cu 10%, be prepared into precursor liquid;
(5) precursor liquid that step (4) is made is spin-coated on the strontium titanate monocrystal chip with 1500 rev/mins speed, and the spin coating time is 90s;
(6) will be placed on to send in the quartz boat in the quartzy stove of high-temperature tubular through the coated substrate of step (5) and carry out low temperature thermal decomposition and high-temperature heat treatment, obtain containing the YBCO high temperature superconducting film of nano barium phthalate and nanometer barium zirconate at last.
Low temperature thermal decomposition is carried out under moistening oxygen condition.Bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed, make that water vapour pressure is 100hPa in the reaction chamber, on average be warming up to 300 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere.The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 160hPa in the reaction chamber; Temperature rise rate with 400 ℃/h rose to 800 ℃ of the highest temperatures before this; Behind 800 ℃ of insulation 2h, directly feed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to 450 ℃ with 100 ℃/h then, insulation 0.5h makes the YBCO oxygen uptake of cubic phase change the YBCO with superconductivity of quadrature phase in 450 ℃ purity oxygen atmosphere, and sample stove under the oxygen atmosphere is chilled to room temperature subsequently.With field emission scanning electron microscope sample has been carried out the surface topography observation, the YBCO thick film surface is smooth, fine and close; And film surface is obviously found out has nano particle, as shown in Figure 1.
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.01mol, 0.02mol and 0.03mol; With wiring solution-forming in the deionized water that is dissolved in the trifluoroacetic acid that contains 20mol% after yttium acetate, NSC 75794 and the venus crystals mixing, wherein the mol ratio of solute and solvent is 1: 100 in the solution;
(2) the said solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 2h;
(3) 3.175mol methyl alcohol is joined in the gel that step (2) makes; Behind magnetic stirrer 1h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel, wherein the molar ratio of colloidal sol and methyl alcohol is 1: 50;
(4) gel that step (3) is made joins in the mixed solution of 15.8ml methyl alcohol and 15.8ml Terpineol 350, and the volume ratio of described methyl alcohol and Terpineol 350 is 1: 1, the solution that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 2.0mol/L.The methyl alcohol that contains Y, Ba and Cu and the terpineol solution of gained are stirred; Add 0.00375mol titanium acetylacetone and 0.00375mol methyl ethyl diketone zirconium again; The ratio of titanium acetylacetone and methyl ethyl diketone zirconium is 1: 1; The titanium acetylacetone that is added is 12.5% of Y in methyl alcohol and the terpineol solution of the described Y of containing, Ba and Cu, Ba and three kinds of total ion volumetric molar concentrations of metal of Cu, is prepared into precursor liquid;
(5) precursor liquid that step (4) is made is spin-coated on the lanthanuma luminate single crystal substrate with 1500 rev/mins speed, and the spin coating time is 90s;
(6) will apply good substrate through step (5) and be placed on to send in the quartz boat in the quartzy stove of tubular type and carry out low temperature thermal decomposition and high-temperature heat treatment, obtain containing the YBCO high temperature superconducting film of nano barium phthalate and nanometer barium zirconate at last.
Low temperature thermal decomposition is carried out under moistening oxygen condition.Bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed, make that water vapour pressure is 130hPa in the reaction chamber, on average be warming up to 400 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere.The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 200hPa in the reaction chamber; Temperature rise rate with 400 ℃/h rose to 825 ℃ of the highest temperatures before this; Behind 825 ℃ of insulation 3h, directly feed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to 500 ℃ with 100 ℃/h then, insulation 1h makes the YBCO oxygen uptake of cubic phase change the YBCO with superconductivity of quadrature phase in 500 ℃ purity oxygen atmosphere, and sample stove under the oxygen atmosphere is chilled to room temperature subsequently.With field emission scanning electron microscope sample has been carried out the surface topography observation, the YBCO thick film surface is smooth, fine and close; And film surface is obviously found out has nano particle, as shown in Figure 2.
With X-ray diffractometer sample has been carried out analysis of components, as shown in Figure 3.Can find out that sample has YBCO (00l) diffraction peak, explain that adulterated Ti and Zr do not destroy the c axle preferrel orientation of YBCO.And except that YBCO (00l) diffraction peak, also have some more weak diffraction peaks in the sample.Through the retrieval of JCPDS card, be 25.493 °, 26.242 °, 31.313 °, 38.654 ° and 55.628 ° at 2 θ and have diffraction peak corresponding BaTi0 respectively
3(004), (103), (104), (006) and (300) diffraction peak is 43.254 ° at 2 θ and has the corresponding BaZrO of d diffraction peak
3(002) diffraction peak, explain that the second of in precursor liquid, adding mills acetone titanium and second and mill the acetone zirconium and generate BaTiO through after the follow-up thermal treatment
3(BTO) and BaZrO
3(BZO).
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.015mol, 0.03mol and 0.045mol; With wiring solution-forming in the l deionized water that is dissolved in the trifluoroacetic acid that contains 30mol% after yttium acetate, NSC 75794 and the venus crystals mixing, wherein the mol ratio of solute and solvent is 1: 100 in the solution;
(2) solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 3h;
(3) methyl alcohol of 4.875mol is joined in the gel that step (2) makes; Behind magnetic stirrer 1.5h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel, wherein the molar ratio of colloidal sol and methyl alcohol is 1: 5;
(4) gel that step (3) is made joins in the mixed solution of 16.25ml methyl alcohol and 16.25ml Terpineol 350, and the volume ratio of described methyl alcohol and Terpineol 350 is 1: 1, and processing Y, Ba and Cu three metal ion species concentration is the solution of 3.0mol/L.The methyl alcohol that contains Y, Ba and Cu and the terpineol solution of gained are stirred; Add 0.006075mol titanium acetylacetone and 0.006075mol methyl ethyl diketone zirconium again; The ratio of titanium acetylacetone and methyl ethyl diketone zirconium is 1: 1; The methyl ethyl diketone zirconium that is added is 13.5% of Y in methyl alcohol and the terpineol solution of the described Y of containing, Ba and Cu, Ba and three kinds of total ion volumetric molar concentrations of metal of Cu, is prepared into precursor liquid;
(5) speed of above-mentioned precursor liquid with 1500 rev/mins is spin-coated on the lanthanuma luminate single crystal matrix, the spin coating time is 90s;
(6) will apply good sample through step (5) and be placed on to send in the quartz boat in the quartzy stove of tubular type and carry out low temperature thermal decomposition and high-temperature heat treatment, obtain containing the YBCO high temperature superconducting film of nano barium phthalate and nanometer barium zirconate at last.
Low temperature thermal decomposition is carried out under moistening oxygen condition.Bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed, make that water vapour pressure is 160hPa in the reaction chamber, on average be warming up to 500 ℃ from room temperature, and then stove is chilled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere.The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 240hPa in the reaction chamber; Temperature rise rate with 400 ℃/h rose to 850 ℃ of the highest temperatures before this; Behind 850 ℃ of insulation 4h, directly feed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to 550 ℃ with 100 ℃/h then, insulation 1.5h makes the YBCO oxygen uptake of cubic phase change the YBCO with superconductivity of quadrature phase in 550 ℃ purity oxygen atmosphere, and sample stove under the oxygen atmosphere is cooled to room temperature subsequently.
Fig. 4 is the curve of the critical transition temperature of pure ybco film and YBCO/ (BZO BTO) laminated film.As can be seen from the figure, these two sample critical transition temperatures are more or less the same, and are about 90K, explain that mixing ybco film inner nanometer BZO and nanometer BTO does not destroy its supraconductivity.The suiperconducting transition width that can see YBCO/ (BZO BTO) laminated film from the amplification picture of temperature transition curve shows that also less than 1K it has good supraconductivity.
Embodiment 4
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.01mol, 0.02mol and 0.03mol; With wiring solution-forming in the deionized water that is dissolved in the trifluoroacetic acid that contains 20mol% after yttium acetate, NSC 75794 and the venus crystals mixing, wherein the mol ratio of solute and solvent is 1: 100 in the solution;
(2) the said solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 2h;
(3) 3.175mol methyl alcohol is joined in the gel that step (2) makes; Behind magnetic stirrer 1h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel, wherein the molar ratio of colloidal sol and methyl alcohol is 1: 5;
(4) gel that step (3) is made joins in the mixed solution of 15.8ml methyl alcohol and 15.8ml Terpineol 350, and the volume ratio of described methyl alcohol and Terpineol 350 is 1: 1, the solution that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 2.0mol/L.The methyl alcohol that contains Y, Ba and Cu and the terpineol solution of gained are stirred; Add 0.0045mol titanium acetylacetone and 0.0045mol methyl ethyl diketone zirconium again; The ratio of titanium acetylacetone and methyl ethyl diketone zirconium is 1: 1; The titanium acetylacetone that is added is 15% of Y in methyl alcohol and the terpineol solution of the described Y of containing, Ba and Cu, Ba and three kinds of total ion volumetric molar concentrations of metal of Cu, is prepared into precursor liquid;
(5) precursor liquid that step (4) is made is coated on the magnesium oxide single-crystal substrate with 5 millimeters/minute pull rate;
(6) will apply good substrate through step (5) and be placed on to send in the quartz boat in the quartzy stove of tubular type and carry out low temperature thermal decomposition and high-temperature heat treatment, obtain containing the YBCO high temperature superconducting film of nano barium phthalate and nanometer barium zirconate at last.
Low temperature thermal decomposition is carried out under moistening oxygen condition.Bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed, make that water vapour pressure is 130hPa in the reaction chamber, on average be warming up to 400 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere.The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 200hPa in the reaction chamber; Temperature rise rate with 400 ℃/h rose to 880 ℃ of the highest temperatures before this; Behind 880 ℃ of insulation 3h, directly feed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to 500 ℃ with 100 ℃/h then, insulation 1h makes the YBCO oxygen uptake of cubic phase change the YBCO with superconductivity of quadrature phase in 500 ℃ purity oxygen atmosphere, and sample stove under the oxygen atmosphere is chilled to room temperature subsequently.
Fig. 5 is the graphic representation of the critical current density of pure ybco film, YBCO/BTO, YBCO/ (BZO BTO) laminated film.As can be seen from Figure 5, compare with the YBCO/BTO laminated film with pure ybco film, the critical current density of YBCO/ (BTO BZO) laminated film is all to be significantly improved at null field or under High-Field.After the match outer at liquid nitrogen temperature, 1T, the critical current density of YBCO/ (BTO BZO) is 2 * 10
6A/cm
2, and pure ybco film is merely 4 * 10
5A/cm
2, the former is 5 times of the latter approximately.Show nanometer BaTiO
3And BaZrO
3Effectively play the effect of collaborative flux pinning in ybco film inside, and then improved its superconductivity.
Claims (3)
1. the preparation method of a YBCO superconduction laminated film is characterized in that, described preparation method adds Terpineol 350, methyl ethyl diketone zirconium and titanium acetylacetone in the precursor liquid that contains trifluoroacetic acid yttrium, trifluoroacetic acid barium and trifluoroacetic acid copper; Concentration through the control metals ion; Through low temperature thermal decomposition and high-temperature heat treatment; Preparation contains the YBCO superconducting thin film of nano barium phthalate and nanometer barium zirconate, utilizes two kinds of nano particle synergies of nano barium phthalate and nanometer barium zirconate, the flux pinning effect that improves ybco film.
2. the preparation method of a kind of YBCO superconduction laminated film as claimed in claim 1 is characterized in that described preparation method comprises the steps:
(1) according to Y: Ba: Cu=1: 2: 3 mol ratio is Y (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Mix, under room temperature, be dissolved in the deionized water of the trifluoroacetic acid that contains 10-30mol%, be made into the solution of trifluoroacetate, the mol ratio of solute and solvent is 1: 100 in the said trifluoroacetic acid salts solution;
(2) with the trifluoroacetic acid salts solution of step (1) preparation through magnetic stirrer 1-3h, adopt Rotary Evaporators to steam to desolventize again and obtain gel;
(3) gel that said step (2) is made adds in the methyl alcohol; The gel in this step and the mol ratio of methyl alcohol are 1: 50, behind magnetic stirrer 0.5-1.5h, adopt Rotary Evaporators to steam again and desolventize; With impurity such as further removal moisture, obtain purified gel;
(4) gel that said step (3) is made joins in methyl alcohol and the Terpineol 350, the solution that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 1.5-3.0mol/L, and the volume ratio of described methyl alcohol and Terpineol 350 is 1: 1; The solution stirring that will contain described Y, Ba and Cu is even; Add methyl ethyl diketone zirconium and titanium acetylacetone again; Methyl ethyl diketone zirconium that is added and titanium acetylacetone are the 10%-15% of Y, Ba and three kinds of total ion volumetric molar concentrations of metal of Cu in the described Y of containing, Ba and the Cu solution, are prepared into precursor liquid;
(5) the said precursor liquid of above-mentioned steps (4) being processed adopts spin coating or method of pulling up to be coated on the substrate;
(6) will place the quartzy stove of high-temperature tubular through the substrate after step (5) applies, under 300 ℃ of-500 ℃ of temperature, carry out the low temperature thermal decomposition of 10h, decompose trifluoroacetate; The temperature rise rate of this step is 40 ℃/h;
(7) will pass through the substrate that step (6) handles and place 800 ℃-880 ℃ high-temperature heat treatment 2-4h, generate the cubic phase YBCO film that contains nano barium phthalate, nanometer barium zirconate; The heat-up rate of this step is 400 ℃/h;
(8) will pass through substrate that step (7) handles and place under 450 ℃-550 ℃ and the pure oxygen condition, be prepared into the YBCO superconducting thin film that contains nano barium phthalate and nanometer barium zirconate the film thermal treatment 0.5-1.5h that anneals.
3. the preparation method of a kind of YBCO superconduction laminated film as claimed in claim 2 is characterized in that, substrate described in the described step (5) is lanthanum aluminate, strontium titanate or magnesium oxide single-crystal substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210030615XA CN102584204A (en) | 2012-02-12 | 2012-02-12 | Method for preparing yttrium barium copper oxide (YBCO) superconductive composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210030615XA CN102584204A (en) | 2012-02-12 | 2012-02-12 | Method for preparing yttrium barium copper oxide (YBCO) superconductive composite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102584204A true CN102584204A (en) | 2012-07-18 |
Family
ID=46473544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210030615XA Pending CN102584204A (en) | 2012-02-12 | 2012-02-12 | Method for preparing yttrium barium copper oxide (YBCO) superconductive composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102584204A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103352212A (en) * | 2013-07-09 | 2013-10-16 | 东北大学 | Method for preparing YBCO (yttrium barium copper oxide) film by taking ethanol as solvent through low-fluorine MOD (metal organic deposition) method |
| CN103680759A (en) * | 2012-08-31 | 2014-03-26 | 株式会社东芝 | Method for producing oxide superconductor, and oxide superconductor |
| CN106374030A (en) * | 2016-11-10 | 2017-02-01 | 中国科学院电工研究所 | YBCO superconductive composite thin film preparation method |
| CN106904945A (en) * | 2017-03-23 | 2017-06-30 | 江苏大学 | A kind of BST/MgO flexures electric laminated film of parallel-connection structure and preparation method thereof |
| CN108007895A (en) * | 2017-12-08 | 2018-05-08 | 北京鼎臣世纪超导科技有限公司 | A kind of method of checking R EBCO superconducting films precursor liquid quality |
| CN111533551A (en) * | 2020-05-08 | 2020-08-14 | 中国科学院电工研究所 | YBCO superconducting film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258618A (en) * | 2004-10-01 | 2008-09-03 | 美国超导公司 | Thick superconductor films with improved performance |
| CN101694789A (en) * | 2009-10-16 | 2010-04-14 | 北京工业大学 | Ti-doped YBCO film preparation process |
| CN102173820A (en) * | 2011-02-21 | 2011-09-07 | 中国科学院电工研究所 | Preparation method of YBa2Cu3O7-x(YBCO) high-temperature superconductive thick film |
| CN102255041A (en) * | 2011-07-13 | 2011-11-23 | 中国科学院电工研究所 | Preparation method of YBCO (Yttrium Barium Copper Oxide) superconducting thin film |
-
2012
- 2012-02-12 CN CN201210030615XA patent/CN102584204A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258618A (en) * | 2004-10-01 | 2008-09-03 | 美国超导公司 | Thick superconductor films with improved performance |
| CN101694789A (en) * | 2009-10-16 | 2010-04-14 | 北京工业大学 | Ti-doped YBCO film preparation process |
| CN102173820A (en) * | 2011-02-21 | 2011-09-07 | 中国科学院电工研究所 | Preparation method of YBa2Cu3O7-x(YBCO) high-temperature superconductive thick film |
| CN102255041A (en) * | 2011-07-13 | 2011-11-23 | 中国科学院电工研究所 | Preparation method of YBCO (Yttrium Barium Copper Oxide) superconducting thin film |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680759A (en) * | 2012-08-31 | 2014-03-26 | 株式会社东芝 | Method for producing oxide superconductor, and oxide superconductor |
| CN103352212A (en) * | 2013-07-09 | 2013-10-16 | 东北大学 | Method for preparing YBCO (yttrium barium copper oxide) film by taking ethanol as solvent through low-fluorine MOD (metal organic deposition) method |
| CN103352212B (en) * | 2013-07-09 | 2015-06-17 | 东北大学 | Method for preparing YBCO (yttrium barium copper oxide) film by taking ethanol as solvent through low-fluorine MOD (metal organic deposition) method |
| CN106374030A (en) * | 2016-11-10 | 2017-02-01 | 中国科学院电工研究所 | YBCO superconductive composite thin film preparation method |
| CN106904945A (en) * | 2017-03-23 | 2017-06-30 | 江苏大学 | A kind of BST/MgO flexures electric laminated film of parallel-connection structure and preparation method thereof |
| CN108007895A (en) * | 2017-12-08 | 2018-05-08 | 北京鼎臣世纪超导科技有限公司 | A kind of method of checking R EBCO superconducting films precursor liquid quality |
| CN111533551A (en) * | 2020-05-08 | 2020-08-14 | 中国科学院电工研究所 | YBCO superconducting film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rahman et al. | A review on cuprate based superconducting materials including characteristics and applications | |
| CN102584204A (en) | Method for preparing yttrium barium copper oxide (YBCO) superconductive composite film | |
| CN102255041B (en) | Preparation method of YBCO (Yttrium Barium Copper Oxide) superconducting thin film | |
| CN102931338B (en) | A kind of YBCO superconducting film with multi-layer compound structure and preparation method thereof | |
| CN102731083B (en) | Method for preparing yttrium-barium-copper-oxygen high-temperature superconducting film | |
| CN103102162A (en) | Method for preparing element doping yttrium, gadolinium, barium, copper and oxygen high-temperature superconducting film | |
| CN101916619B (en) | Nano particle doped REBCO film and preparation method thereof | |
| CN102173820B (en) | Preparation method of YBa2Cu3O7-x(YBCO) high-temperature superconductive thick film | |
| CN101747031B (en) | High-temperature superconducting nanometer composite film and method for preparing same | |
| CN101694789B (en) | Ti-doped YBCO film preparation process | |
| CN104446435B (en) | The preparation method of Ag doping terres rares barium copper oxygen conductor of high-temperature superconductor coat material | |
| CN101746807A (en) | Method for increasing thickness of YBCO film prepared through TFA-MOD method | |
| CN202871869U (en) | YBCO superconducting film having multilayered composite structure | |
| Li et al. | Microstructures Property and Improved J c of Eu-Doped YBa 2 Cu 3.6 O 7− δ Thin Films by Trifluoroacetate Metal Organic Deposition Process | |
| Hong et al. | Thermal decomposition of precursor of SmBiO3 buffer layer for YBCO high-temperature superconducting tape | |
| US11328846B2 (en) | Oxide superconductor and method for manufacturing the same | |
| CN102751044A (en) | Preparation method of yttrium barium copper oxide (YBCO) coating conductor | |
| CN102690114B (en) | Method for preparing YBCO superconducting composite film | |
| CN103280520B (en) | Preparation method of YBCO (yttrium barium copper oxide) superconductivity composite film | |
| CN103274682B (en) | Preparation method of high-temperature superconductive film | |
| CN103641467A (en) | Method for preparing a high-temperature superconductive nanometer composite film | |
| Wong-Ng et al. | Subsolidus phase relationships of the BaO–Y2O3–CuOx system under carbonate-free conditions at pO2= 100 Pa and at pO2= 21 kPa | |
| Ye et al. | Enhanced flux pinning in YBCO+ YSZ composite films grown by TFA-MOD method | |
| CN106374030A (en) | YBCO superconductive composite thin film preparation method | |
| Li et al. | Microstructures Property and Improved J of Eu-Doped YBaCuO Thin Films by Trifluoroacetate Metal Organic Deposition Process. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120718 |