CN100356484C - La2-xSrxCuO4 ordered nanowire array and method for preparing same - Google Patents
La2-xSrxCuO4 ordered nanowire array and method for preparing same Download PDFInfo
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- CN100356484C CN100356484C CNB2004100648222A CN200410064822A CN100356484C CN 100356484 C CN100356484 C CN 100356484C CN B2004100648222 A CNB2004100648222 A CN B2004100648222A CN 200410064822 A CN200410064822 A CN 200410064822A CN 100356484 C CN100356484 C CN 100356484C
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Abstract
The present invention relates to a La<2-x>Sr<x>CuO4 sequential nanometer liner array and a preparation method thereof, which is characterized in that citrate is used as complex agents, ethylene glycol is used as cross linking agents, a forerunner of La<2-x>Sr<x>CuO4 sol with adjustable viscidity is prepared through effectively controlling the hydrolytic degree of the citrate and the aggregation degree of the ethylene glycol by double heating, the sol is injected in a multiple-hole alumina mould plate with a nanometer hole array obtained by a two-time anode corrosion method under soft vacuum, the multiple-hole alumina mould plate filled with sol solution is obtained, and after the multiple-hole alumina mould plate filled with sol solution is sintered and annealed in pure oxygen, the sequential array composed of polycrystal La<2-x>Sr<x>CuO4 nanometer lines which are arranged in parallel together is obtained; the sequential array comprises the multiple-hole alumina mould plate, the diameter of the sequential array is about from 40 nm to 70 nm, the length of the sequential array can reach the micrometer level, x is from 0.05 to 0.3, and the crystal lattices of the nanometer lines are in orthogonal bottom-centered structures. The method of the present invention is a known simple method for synthesizing the nanometer lines of high temperature superconductive materials at present.
Description
Technical field:
The invention belongs to oxide high-temperature superconductor and preparing technical field thereof, particularly relate to the La of x in the 0.05-0.3 scope
2-xSr
xCuO
4High temperature superconducting materia ordered nano linear array and preparation method thereof.
Background technology:
Germany " Condensed Matter Physics " (Zeitschrift f ü r Physik B-Condensed Matter) reported La-Ba-Cu-O oxide superconductor (Bednorz in 1986, M ü ller Possible high Tc superconductivity in theIa-Ba-Cu-O system), this is found the earliest in history high-temperature superconductor.After this found (the ReBa of Y system again in succession
2Cu
3O
7-δ, 1987); Bi is (Bi
2Sr
2Ca
N-1Cu
nO
2n+4, 1988) and (Tl of Tl system
2Ba
2Ca
N-1Cu
nO
2n+4, 1988) and superconductor.The La-Sr-Cu-O system is the high-temperature superconductor that belongs to a series of with found La-Ba-Cu-O system the earliest, and it is one of maximum system of research at present.The existing method for preparing La-Sr-Cu-O mainly is the ceramic post sintering method, American Chemical Society's " inorganic chemistry " magazine (1989, the 154th page of 28 volume) sol-gel process of the oxalate coprecipitation method of report and Holland's " material wall bulletin " magazine (1999, the 289th page of 38 volume) report.These methods need higher sintering temperature, and product crystal grain is thick, is the powder of irregular shape.Nearest AIP's " physical comment communication " magazine (2004,93 roll up the 087002-1 pages or leaves) reported and utilized laser coating to cooperate the method for ion beam etching to prepare high temperature superconducting materia YBCO nano wire, but this method program complexity, expense costliness are difficult to apply.
One peacekeeping quasi-one-dimensional nanometer material has unique character and is widely studied, and also has a lot of unusual character and application prospects by the oldered array that nano wire is formed.The ordered nano linear array that a lot of alloys, oxide and Ferrite Material arranged at present is being synthesized by success, for example: American Chemical Society's " chemical material " magazine (2003,664 pages of 15 volumes) the Ni-Cu alloy nano linear array of report, the Fe of Germany's " Applied Physics A " magazine (the 1197th page of 78 volume) report
2O
3Nano-wire array, the CoFe of Holland's " Chemical Physics communication " magazine (the 484th page of 379 volume) report
2O
4Nano-wire array.But do not see relevant preparation high temperature superconducting materia La so far
2-xSr
xCuO
4The report of ordered nano linear array.
Summary of the invention:
The present invention proposes a kind of high temperature superconducting materia La
2-xSr
xCuO
4Ordered nano linear array and preparation method thereof.
La of the present invention
2-xSr
xCuO
4The preparation method of ordered nano linear array is characterized in that, this x chooses in the scope of 0.05-0.3, according to La
2-xSr
xCuO
4Composition, get raw material La
2O
3, CuO and SrCO
3, make La: Sr: the ratio of Cu molal quantity is 2-x: x: 1; Preparation aqueous citric acid solution, the molal quantity that makes the citric acid that contains in this solution of 1L be take by weighing the CuO molal quantity 300-600 doubly; Measure the part of this citric acid solution, the citric acid total amount that makes wherein to be comprised is 6 times that the front takes by weighing the CuO molal quantity, adds SrCO then
3Add again and use HNO
3Dissolving La
2O
3Cu (the NO that obtains with CuO
3)
2And La (NO
3)
3Mixed solution, the molal quantity that comprises Cu element and La element to this mixed solution of 1L be respectively take by weighing CuO 100 times and 100 (2-x) doubly, stir and obtain blue mixed solution, the ethylene glycol that adds three times of this blue solution volumes, be heated to solution and become green, regulate PH=6-7 with ethylenediamine then, heat again until system and become the brown sol solution; Purity is not less than 99.9% aluminium flake and is not less than 10 in vacuum degree
-3Pa, temperature are 400-600 ℃ of annealing after 4-7 hour, and the electrolysis tank that places the oxalic acid electrolyte that 0.3 M is housed makes the one side of aluminium flake contact with electrolyte as anode, and another side does not contact with electrolyte, corrodes 4-6 hour at 30-45V, 0-5 ℃; Aluminium flake after this corrosion is placed in the mixed acid solution of being made up of 6wt% phosphoric acid and 1.5wt% chromic acid, soaked 5-8 hour at 40-60 ℃, then this aluminium flake is placed in the anode of the electrolysis tank that 0.3M oxalic acid electrolyte is housed, the one side that makes this aluminium flake be corroded contacts with electrolyte, another side does not contact with electrolyte, carries out corroding the second time 18-24 hour at 30-45V, 0-5 ℃; CuCl with energy and aluminium generation displacement reaction
2Or SnCl
2Solution is removed the remaining aluminium lamination of the side that does not contact with electrolyte; To face down except that this of intact aluminium, and make template swim in 1-5 hour through hole on the 3-8wt% phosphoric acid solution; Porous alumina formwork behind the through hole is placed above-mentioned sol solution, be evacuated to and be not less than 10
-1Pa; The porous alumina formwork of colloidal sol that taken out this filling in air, 600 ℃-700 ℃ insulations 8-10 hour, obtains being included in the La in the template
2-xSr
xCuO
4The ordered nano linear array; Through the pure oxygen atmosphere annealing in process, promptly obtain La again
2-xSr
xCuO
4The ordered nano linear array.
The present invention adopts the La of method for preparing
2-xSr
xCuO
4The ordered nano linear array, be characterised in that its be contained in the aperture be in the porous alumina formwork of 40-70nm, be arranged parallel to each other together, x is at the polycrystalline La of 0.05-0.3 scope
2-xSr
xCuO
4The oldered array that nano wire is formed, lattice is the core structure of just telling somebody what one's real intentions are.
The x scope is chosen between 0.05-0.3 among the present invention, is based on La
2-xSr
xCuO
4The superconductivity compositing range of system is 0.05＜x＜0.32.For example " high-temperature superconductor basic research " (noon in week is vertical, Liang Weiyao, the 20th page of 11 row, Shanghai science tech publishing house) book is pointed out, for La
2-xSr
xCuO
4The superconductivity compositing range of system is 0.05＜x＜0.32.
Method among the present invention is utilized the complexing agent of citric acid as complexing nitrate, and ethylene glycol is as crosslinking agent, and expense is cheap, and is simple to operate, the colloidal sol stable homogeneous that obtains; Adopt the method for post bake to control the hydrolysis of citrate and the polymerization rate of ethylene glycol, controlled the process of colloidal sol to gel, can be by changing the viscosity of controlling the precursor sol thing heating time, be used to pour into the porous alumina formwork in different apertures, the nano wire of preparation different-diameter; Traditional colloidal sol preparation method adopts metallorganic more, the expense costliness, complicated operation can not effectively be controlled the process of colloidal sol to gel again, can not get the controlled precursor sol thing of viscosity, the precursor sol thing that makes conventional method obtain is unsuitable for being filled into porous alumina formwork and prepares nano wire; Be generally more than 900 ℃ and compare with traditional solid reaction process, coprecipitation synthesis temperature, the precursor sol thing in the inventive method is the mixed uniformly system of molecular level, greatly reduces the activation energy of reaction, makes the inventive method synthesize La
2-xSr
xCuO
4Temperature be reduced to 600-700 ℃; Traditional solid reaction process can only prepare micron-sized, unordered granular powder, and constraint has obtained one dimension ordered nano linear array as hard template to cooperate porous alumina formwork in the inventive method.The method is the method for the at present known in the world synthesizing high temperature superconductor nano wire than cheap and simple.
La among the present invention
2-xSr
xCuO
4Be that the polycrystalline compounds of x one of in the 0.05-0.3 scope constitutes, diameter is 40nm-70nm, together nano-wire array is arranged parallel to each other, this is the one-dimensional nano line array of the La-Sr-Cu-O system that successfully is synthesized first in the world, the superconducting characteristic that it has, help further understanding the origin of high-temperature superconductor, for developing in the future high sensitivity infra-red detection device, use the very-high speed computer of Josephson's joint, high-resolution superconducting quantum interference device (SQUID) (SQUID) provide the material support.
Description of drawings:
Fig. 1 is La
2-xSr
xCuO
4The preparation process schematic diagram of nano-wire array.
Fig. 2 is the surface topography map of JSM-6700F field emission scanning electron microscope (FE-SEM) observation porous alumina formwork
Fig. 3 is La
1.85Sr
0.15CuO
4The copper target x-ray diffraction pattern of nano-wire array and porous alumina formwork.
Fig. 4 is the La after the partial oxidation aluminum alloy pattern plate is removed in the observation of JSM-6700F field emission scanning electron microscope
1.85Sr
0.15CuO
4The little multiple cross-section morphology figure of nano-wire array.
Fig. 5 is the La after the partial oxidation aluminum alloy pattern plate is removed in the observation of JSM-6700F field emission scanning electron microscope
1.85Sr
0.15CuO
4The field emission scanning electron microscope figure that amplify the part of nano-wire array.
Fig. 6 is the La after whole templates are removed in H-800 transmission electron microscope (TEM) observation
1.85Sr
0.15CuO
4The TEM figure of nano wire.
Fig. 7 is the single La that the H-800 transmission electron microscopy observation arrives
1.85Sr
0.15CuO
4The pattern picture of nano wire and corresponding selected area electron diffraction pattern thereof.
Fig. 8 is the single La that JEOL-2010 high resolution transmission electron microscopy (HRTEM) observes Fig. 7
1.85Sr
0.15CuO
4The pairing lattice fringe picture of nano wire.
Fig. 9 is the single La of Fig. 7 of being done on the JEOL-2010 high resolution transmission electron microscopy
1.85Sr
0.15CuO
4The electronic energy spectrum of nano wire (EDS).
Figure 10 goes up measured our prepared La in superconducting quantum interference device (SQUID) (SQUID)
1.85Sr
0.15CuO
4The magnetic susceptibility of nano-wire array and the curve relation figure of temperature.
Figure 11 is La
1.88Sr
0.12CuO
4The copper target x-ray diffraction pattern of nano-wire array and porous alumina formwork
Figure 12 is the La after the whole templates of removing of H-800 transmission electron microscopy observation
1.88Sr
0.12CuO
4A large amount of nano wire TEM figure.
Figure 13 is the La after the partial oxidation aluminum alloy pattern plate is removed in the observation of JSM-6700F field emission scanning electron microscope
1.88Sr
0.12CuO
4The section field emission scanning electron microscope figure of nano-wire array.
Embodiment:
Embodiment 1:La
1.85Sr
0.15CuO
4The preparation of ordered nano linear array
Prepare required sol solution with sol-gel process: according to compound L a
1.85Sr
0.15CuO
4Composition, take by weighing 1.507g (4.625 * 10 respectively
-3Mol) La
2O
3, 0.1105g (7.485 * 10
-4Mol) SrCO
3, 0.3978g (5.000 * 10
-3Mol) CuO; La wherein
2O
3With CuO HNO
3Obtain La (NO after the dissolving
3)
3And Cu (NO
3)
2Mixed solution 10ml; With 6.304g (3.000 * 10
-2Mol) citric acid is dissolved in and obtains the lemon aqueous acid in the 10ml distilled water, the SrCO that takes by weighing previously
3Add wherein and stir simultaneously, treat SrCO
3Add the La (NO that obtains previously again after the dissolving fully
3)
3And Cu (NO
3)
2Mixed solution, continue to stir and to obtain even one stable transparent blue solution in ten minutes; In this blue solution of 20ml, add the stirring that 60ml ethylene glycol does not stop, the mixing material that obtains is heated to green, treat to obtain navy blue clear solution with ethylenediamine adjusting PH=6 behind its cool to room temperature, in fact the ethylene glycol that adds in the experiment can be mixed liquor volume 2-6 doubly, but it is best to add the effect that ethylene glycol obtains by 3 times of volumes; This solution is continued heating 20-40 minute, just can obtain testing the sol solution of required brownish black stable homogeneous, the colloidal sol of looking more heating time is thickness more.This method adopts the secondary anode etch to prepare porous alumina formwork, and it is the necessary condition of synthesis of nano linear array, can use purity to be not less than 99.9% aluminium flake, and the high more effect of purity is good more; Adopting 99.999% aluminium flake in the present embodiment, is 10 in vacuum degree
-3Pa, 500 ℃ of annealing of temperature 5 hours, to remove mechanical stress, then aluminium flake be placed on oxalic acid electrolyte is housed electrolysis tank as anode, electrolyte employing concentration can at the oxalic acid of 0.15-0.4M, it is best that wherein concentration 0.3M obtains the order of porous alumina formwork hole, so present embodiment adopts the oxalic acid of 0.3M; Make aluminium flake simultaneously contact electrolyte, establish it for the x face, another side contact with electrolyte, establishes it and is the y face, corrodes 5 hours 40V, 0 ℃, and the voltage of use is big more, and the hole diameter of the alumina formwork that obtains is big more.Aluminium flake after this corrosion is immersed in 60 ℃ the mixed acid solution of forming by phosphoric acid and chromic acid after 5 hours, the concentration of phosphoric acid and chromic acid is that 6wt% and 1.5wt% are effective, other concentration range 6 ± 1wt% and 1.5 ± 1wt% with interior can, under same condition, carried out corroding the second time 24 hours, and also only allowed the x face contact specifically with electrolyte.Behind anticaustic, the structure of the multiaperture pellumina that forms on metal aluminium flake surface is divided into three layers: the superiors are aluminum oxide porous layers, be hexagon solid matter column distribution between its construction unit each other, the hole occupies the centre position of construction unit in order, axial and its Surface Vertical in hole; The bottom of hole is fine and close alumina barrier layer; It then is the metal aluminium lamination that does not have oxidation.For obtaining the bilateral alumina formwork, need remove aluminium lamination and alumina barrier layer respectively, present embodiment adopts saturated CuCl
2Solution is removed remaining aluminium lamination; Then template there is one of barrier layer to face down, template is swum on the phosphoric acid solution corroded 1-1.5 hour, it is best that phosphoric acid concentration is generally the 5wt% effect, other concentration range 5 ± 1wt% with interior can, to remove the barrier layer of hole root, this process is called " through hole ", has so just obtained required bilateral porous alumina formwork.This porous alumina formwork is immersed in the wide-mouth bottle that fills a certain amount of above-mentioned sol solution, then wide-mouth bottle is evacuated, air in this process in the template hole can be drawn out of and cause forming a negative pressure, and sol solution will enter the hole of porous alumina formwork under the effect of pressure.
The preparation process of present embodiment sample can be described with the schematic diagram of accompanying drawing 1: for the loose structure of nano aperture array is arranged, its enlarged diagram d shows and is parallel to each other between its hole empty template a, is the orderly arrangement of 6 side Mi Dui before priming by vacuum; Through vacuumizing processing, the precursor sol thing injection empty template a that had before prepared, obtain being filled with the template b of colloidal sol, its enlarged diagram e is presented in the hole of porous alumina formwork and is filled with the precursor sol thing; The template b that will fill up sol solution then insulation annealing in air, under 600 ℃ the condition just obtained being filled with La after 10 hours
1.85Sr
0.15CuO
4The template c of nano wire; Be filled with the La that generates by the reaction of precursor sol thing in the hole of its enlarged diagram f demonstration porous alumina formwork
1.85Sr
0.15CuO
4Nano wire.
Resulting template sample can be used for X-ray diffraction analysis after milled processed, through can be used for transmission electron microscope, field emission scanning electron microscope and high resolution transmission electron microscopy analysis after the 2M NaOH solution-treated.
The porous alumina formwork (AAO) that above-mentioned employing two-step electrochemical etch is prepared is done the field emission scanning electron microscope observation, photo as shown in Figure 2, from Fig. 2 photo as can be seen: the prepared AAO aperture of present embodiment evenly (50 ± 5nm) and be the symmetrical orderly arrangement of six sides substantially.
La to above-mentioned preparation
1.85Sr
0.15CuO
4The X-ray diffraction analysis of nano-wire array sample obtains Fig. 3, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; Diffraction maximums all among Fig. 3 can change into (113), (200), (220), (004) by quadrature base-centered lattice structure index ... with the JCPDS in the international standard powder X-ray RD diffraction card, 86-1691 is consistent, and the diffraction bag of angle of diffraction between the 20-40 degree is the amorphous diffraction bag of porous alumina formwork among the figure.So owing to be that the LSCO sample that a kind of structure of anoxic burns out under general air atmosphere all can show a kind of anoxic structure among the used AAO in the present embodiment, the result of Fig. 3 can indexing to La
1.85Sr
0.15CuO
3.8Be exactly a kind of anoxic structure, just can obtain not that the LSCO nano wire of anoxic is La if under pure oxygen atmosphere, do annealing in process
1.85Sr
0.15CuO
4Nano wire.
For the nano-wire array for preparing in the present embodiment field emission scanning electron microscope analysis of profiling, the electromicroscopic photograph that obtains such as Fig. 4, shown in Figure 5, the filling rate of its nano wire is very high as can be seen, line is very full, the length of nano wire is determined by template used thickness, reach micron dimension, and the substantially parallel orderly array of lining up between the nano wire.Shown diameter homogeneous, surface clean, the fine and close nano wire of photo Fig. 6 of this and transmission electron microscope is corresponding.
Analysis on high-resolution-ration transmission electric-lens can provide pattern picture and selected area electron diffraction (SAED) pattern and the EDS analysis of the single nano-wire of being done, thereby determines the crystal structure characteristic of nano wire.Fig. 7, Fig. 8 and Fig. 9 have provided the result that high resolution electron microscopy is analyzed.As can be seen from Figure 7, the crystallization situation of the nano wire of present embodiment preparation is fine, and the nano wire that has all presents single crystal characteristics.
Fig. 8 is the lattice fringe picture of single nano-wire among the Fig. 7 that does on high-resolution-ration transmission electric-lens, can see the lattice fringe that wherein has 2 kinds of cycles, fringe spacing be respectively 0.2886nm and 0.2164nm corresponding respectively { 113} family of crystal planes and { 122} family of crystal planes, this is corresponding with the SAED among Fig. 7, consistent with the result of the XRD figure of Fig. 3, the polycrystalline that sample that present embodiment is prepared is made up of the fine single crystal grain of crystallization is described.
The electronic energy spectrum (EDS) of single nano-wire among Fig. 7 that Fig. 9 is on high-resolution-ration transmission electric-lens to be done, the different energy levels of elements such as La, Sr, Cu are being represented at peak among the figure respectively, and the area at each peak and ratio just corresponding the mole ratio of corresponding element in the nano wire, the area sum that integration is calculated each peak of La is S
1, each peak area sum of Sr is S
2, find S
1: S
21.85: 0.15 (must use copper mesh owing to doing when high-resolution is tested for Cu, so the area at the EDS peak of Cu can not reflect the real content of the Cu in the nano wire) these nominal components with this nano wire of ≈ are consistent.
The sample that obtained in 20 hours through annealing in process in 700 ℃ of pure oxygen atmospheres is done the magnetic measurement analysis, Figure 10 is the curve of the magnetic susceptibility of the sample that obtains on superconducting quantum interference device (SQUID) (SQUID) for temperature, can see that sample has shown diamagnetism in temperature less than 30 K, " Superconductor Physics " book (Zhang Liyuan, Zhang Jinlong, the 7th page, the Electronic Industry Press) mentions the diamagnetism that the surperficial bucking current that is looped around around the high-temperature superconductor has caused whole system, this is one of characteristic of having of high temperature superconducting materia, the result of the Magnetic Measurement in the present embodiment reveals diamagnetic characteristic at 4.2K-30K scope diagram of system, this moment, the bucking current of system was set up, and superconductor is at T
CBelow do not have resistance, bucking current can exist always, so the sample among this embodiment all will show diamagnetic characteristic in temperature less than 30K.
Measurement result and the literature search of XRD, TEM, FE-SEM, HRTEM, SQUID show: adopting the preparation-obtained nano-wire array of the inventive method, is the high temperature superconducting materia La that successfully is synthesized with present simpler method
1.85Sr
0.15CuO
4Nanometer line ordered array, it has filled up the blank in this field, this La
1.85Sr
0.15CuO
4The superconducting characteristic that has can play certain impetus for the mechanism of understanding high-temperature superconductor with for exploitation, the utilization of nano-device.
Embodiment 2:La
1.88Sr
0.12CuO
4The preparation of ordered nano linear array
At first prepare required sol solution: according to compound L a with sol-gel process
1.88Sr
0.12CuO
4Composition, take by weighing 1.531g (4.7 * 10 respectively
-3Mol) La
2O
3, 0.08858 g (6.0 * 10
-4Mol) SrCO
3, 0.3978g (5.0 * 10
-3Mol) CuO; La wherein
2O
3With CuO HNO
3Obtain La (NO after the dissolving
3)
3And Cu (NO
3)
2Mixed solution 10ml; Take by weighing 6.304g (3.0 * 10 then
-2Mol) citric acid also is dissolved in the 20ml distilled water and obtains citric acid solution, the SrCO that takes by weighing previously
3Add wherein and stir simultaneously, treat SrCO
3Add the La (NO that obtains previously again after the dissolving fully
3)
3And Cu (NO
3)
2Mixed solution stirs and obtained even one stable transparent blue solution in ten minutes; In this solution of 20ml, add 60ml ethylene glycol and do not stop to stir, this mixing material is heated to liquid color becomes green, treat to regulate the navy blue clear solution that PH=7 can obtain with ethylenediamine behind its cool to room temperature; This solution is continued heating 20-40 minute, just can obtain testing the sol solution of required brownish black stable homogeneous, the colloidal sol of looking more heating time is thickness more.Adopt the secondary anode etch to prepare porous alumina formwork, this step is identical with embodiment's 1, and the aluminium of resulting template bottom is with the SnCl of 1 M
2Solution is removed.By priming by vacuum the precursor sol thing of having prepared, insert bilateral porous alumina formwork by the hole, again the template that is filled with colloidal sol in air 700 ℃ the insulation 8 hours, can be used for projection electron microscope and field emission scanning electron microscope analysis after the last resulting sample treatment, sample 800 ℃ of annealing in process in pure oxygen atmosphere were made X-ray diffraction analysis after 24 hours.
Prepared sample is done X-ray diffraction analysis (XRD), the result as shown in figure 11, abscissa is an angle of diffraction, ordinate is relative diffracted intensity.Most peak is consistent with the peak on the powder diffraction XRD standard card JCPDS-85-1919 card on the figure, also has the little assorted peak of a spot of intensity owing to annealing in process rear oxidation aluminum alloy pattern plate generation crystallization is brought.The compound L a that shows the gained of above-mentioned preparation
1.88Sr
0.12CuO
4.09Nano-wire array is a pure phase, and to be that annealing time is long in the purity oxygen bring unnecessary oxygen, can be by changing the annealing time control oxygen content in pure oxygen.
Sample is analysis result such as Figure 12 and shown in Figure 13 of transmission electron microscope and field emission scanning electron microscope, as seen from the figure, the filling rate of the nanowire diameter homogeneous that present embodiment prepares, surface clean, compact nanometer line is near 100%, the length of line is determined by template used thickness, reach micron dimension, the substantially parallel orderly array of lining up between the nano wire.
Above-mentioned illustrated result shows that present embodiment adopts the method for collosol and gel and porous alumina formwork combination, and insulation is 10 hours in air, under 600 ℃ the condition, and synthetic sample is the La of pure phase
1.88Sr
0.12CuO
4-δ. nano-wire array.
The La of x between 0.05-0.3
2-xSr
xCuO
4Other components all can adopt operating procedure same as described above to implement.
Claims (2)
1, a kind of La
2-xSr
xCuO
4The preparation method of ordered nano linear array is characterized in that, this x chooses in the scope of 0.05-0.3, according to La
2-xSr
xCuO
4Composition, get raw material La
2O
3, CuO and SrCO
3, make La: Sr: the ratio of Cu molal quantity is 2-x: x: 1; Preparation aqueous citric acid solution, the molal quantity that makes the citric acid that contains in this solution of 1L be take by weighing the CuO molal quantity 300-600 doubly; Measure the part of this citric acid solution, the citric acid total amount that makes wherein to be comprised is 6 times that the front takes by weighing the CuO molal quantity, adds SrCO then
3Add again and use HNO
3Dissolving La
2O
3Cu (the NO that obtains with CuO
3)
2And La (NO
3)
3Mixed solution, this mixed solution of 1L comprises Cu
2+And La
3+Molal quantity be respectively take by weighing CuO 100 times and 100 (2-x) doubly, stirring obtains blue mixed solution, adds the ethylene glycol of three times of this blue solution volumes, is heated to solution and becomes green, regulate PH=6-7 with ethylenediamine then, heat again until system and become the brown sol solution; Purity is not less than 99.9% aluminium flake and is not less than 10 in vacuum degree
-3Pa, temperature are 400-600 ℃ of annealing after 4-7 hour, and the electrolysis tank that places the oxalic acid electrolyte that 0.3M is housed makes the one side of aluminium flake contact with electrolyte as anode, and another side does not contact with electrolyte, corrodes 4-6 hour at 30-45V, 0-5 ℃; Aluminium flake after this corrosion is placed in the mixed acid solution of being made up of 6wt% phosphoric acid and 1.5wt% chromic acid, soaked 5-8 hour at 40-60 ℃, then this aluminium flake is placed in the anode of the electrolysis tank that 0.3M oxalic acid electrolyte is housed, the one side that makes this aluminium flake be corroded contacts with electrolyte, another side does not contact with electrolyte, carries out corroding the second time 18-24 hour at 30-45V, 0-5 ℃; CuCl with energy and aluminium generation displacement reaction
2Or SnCl
2Solution is removed the remaining aluminium lamination of the side that does not contact with electrolyte; To face down except that this of intact aluminium, and make template swim in 1-5 hour through hole on the 3-8wt% phosphoric acid solution; Porous alumina formwork behind the through hole is placed above-mentioned sol solution, be evacuated to and be not less than 10
-1Pa; The porous alumina formwork of colloidal sol that taken out this filling in air, 600 ℃-700 ℃ insulations 8-10 hour, obtains being included in the La in the template
2-xSr
xCuO
4The ordered nano linear array; Through the pure oxygen atmosphere annealing in process, promptly obtain La again
2-xSr
xCuO
4The ordered nano linear array.
2, adopt the La of claim 1 preparation method preparation
2-xSr
xCuO
4The ordered nano linear array, be characterised in that its be contained in the aperture be in the porous alumina formwork of 40-70nm, be arranged parallel to each other together, x is at the polycrystalline La of 0.05-0.3 scope
2-xSr
xCuO
4The oldered array that nano wire is formed, lattice is the core structure of just telling somebody what one's real intentions are.
Priority Applications (1)
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| WO2012003639A1 (en) * | 2010-07-08 | 2012-01-12 | Tian, Duoxian | Superconducting material and manufacturing method thereof |
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| CN87107765A (en) * | 1987-01-12 | 1988-08-10 | 休斯顿大学公园大学 | Superconductivity of tetragonal planar compound systems |
| US4921834A (en) * | 1987-01-30 | 1990-05-01 | Hitachi, Ltd. | Flux method of growing oxide superconductors |
| CN1059349A (en) * | 1987-05-08 | 1992-03-11 | 富士通株式会社 | A kind of coating that is used to form superconducting ceramic film |
| US5252543A (en) * | 1987-12-20 | 1993-10-12 | Sumitomo Electric Industries, Ltd. | Superconducting thin film and wire on a smooth substrate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN87107765A (en) * | 1987-01-12 | 1988-08-10 | 休斯顿大学公园大学 | Superconductivity of tetragonal planar compound systems |
| US4921834A (en) * | 1987-01-30 | 1990-05-01 | Hitachi, Ltd. | Flux method of growing oxide superconductors |
| CN1059349A (en) * | 1987-05-08 | 1992-03-11 | 富士通株式会社 | A kind of coating that is used to form superconducting ceramic film |
| US5252543A (en) * | 1987-12-20 | 1993-10-12 | Sumitomo Electric Industries, Ltd. | Superconducting thin film and wire on a smooth substrate |
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| La-Sr-Cu-O体系的半导体-金属转变和超导电性 喻道奇等.低温物理学报，第9卷第4期 1987 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012003639A1 (en) * | 2010-07-08 | 2012-01-12 | Tian, Duoxian | Superconducting material and manufacturing method thereof |
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