CN104233455B - A kind of method preparing high-temperature superconductor doped crystal - Google Patents
A kind of method preparing high-temperature superconductor doped crystal Download PDFInfo
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- CN104233455B CN104233455B CN201410382418.3A CN201410382418A CN104233455B CN 104233455 B CN104233455 B CN 104233455B CN 201410382418 A CN201410382418 A CN 201410382418A CN 104233455 B CN104233455 B CN 104233455B
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Abstract
The invention discloses a kind of method preparing high-temperature superconductor doped crystal, comprise the following steps：A () is by BaCO3Powder and CuO powder carry out dispensing, wet grinding and sintering, obtain Ba Cu O powder；B Ba Cu O powder is added to the Y that metallic element (M) adulterates by ()2O3It is heated to the first temperature in crucible, and continues to be incubated, obtain M Y Ba Cu O solution, be cooled to second temperature；C () is used YBCO/MgO thin film as seed crystal, be incubated growth 50～100 hours in the M Y Ba Cu O solution of second temperature.The present invention introduces the Y that metallic element (M) adulterates in a creative way2O3Crucible, provides doped chemical and rare earth element simultaneously, has pervasive meaning to preparing high-temperature superconductor doped crystal.
Description
Technical field
The present invention relates to high-temperature superconductive crystal preparing technical field, more particularly, to a kind of preparation of high-temperature superconductor doped crystal
Method.
Background technology
Superconductor more than liquid nitrogen temperature (77K) for the critical temperature is referred to as high-temperature superconductor.More than liquid nitrogen temperature super
The discovery of conductor is so that common physics laboratory possesses the condition carrying out superconducting experiment.At present, high-temperature superconductor includes four
Big class：The Rare Earth of 90K, the hydrargyrum system of the bismuth system of 110K, the thallium system of 125K and 135K.Since REBa2Cu3O7-δ(abbreviation RE-Ba-
Cu-O or REBCO, wherein RE=Y, Sm, Gd, Nd etc.) since high-temperature superconductor is found, just cause the extensive concern of people.
On the one hand, because traditional BCS theory cannot explain the superconducting mechanism of REBCO high-temperature superconductor completely, therefore in world wide
Physicist need high-quality high-temperature superconductive crystal, explore high-temperature superconductor cause；On the other hand, cation substitutes in RE-
Ba-Cu-O system is just attract the concern of more and more people, because the research that the research of this material can be superconducting mechanism carries
For some new opinions, and superconductivity can be improved for practical application.
Top seeded solvent growth is generally considered a kind of preparation method of the REBCO high-temperature superconductive crystal of great potential.
During the seed crystal lifting REBCO HTS single crystals body of top, seed crystal is fixed on slowly molten near saturation in connecting rod
Liquid surface, induces the growth of REBCO superconductive monocrystal as unique forming core point.Growth conditionss due to top seeded solvent growth
Close to equilibrium state, it is used the crystal that the less material of lattice mismatch obtains as seed crystal induced growth to have low defect, Gao Ping
The features such as whole degree, highly crystalline performance.Further, since top seed crystal lifting is carried out under non-vacuum condition, thus this method tool
There is the low advantage of preparation cost.
Shown according to research, in order to obtain large-sized REBCO HTS single crystals body, mainly consider two aspects.One
It is the growth time of crystal, one is the speed of growth of crystal.
In the prior art, in a first aspect, long crystal growth can produce following subject matter：First, molten
Amount in crucible for the liquid can reduce because a certain degree of wellability climbs out of crucible, and this can cause the decline of liquid level to affect crystalline substance
The quality of body；Second, liquid level can because be in hypersaturated state and solute can not consume in time and produce floating material for a long time again,
This is likely to cause the generation of polycrystalline；3rd, the change with crystalline size is big, and the temperature field near liquid level also can become
Change, thus affecting the liquid level temperature of crystal growth.Especially when growing the high-temperature superconductive crystal of metallic element doping, solution system
Complexity make problem more prominent.
For second aspect, the technical scheme of prior art is mainly：First, grown in pure oxygen environment；Pure oxygen
Atmosphere can improve dissolubility in Ba-Cu-O solvent for the RE element such that it is able to improve the speed of growth of crystal, but this
Method operates comparatively laborious and compared to air atmosphere, cost is also higher.Second, precursor aqueous solution increases by second
Rare earth element, such as Sm or Nd etc..Although but this method Sm or Nd have higher dissolubility, SmBCO or NdBCO than Y
The speed of growth of monocrystal is also fast compared with YBCO, but this does not solve the problems, such as the fast-growth of YBCO crystal；In addition, in Y-
Introduce Sm or Nd element in Ba-Cu-O solution and can also improve the speed of growth, but the sample obtaining has mixing of Sm or Nd element
Miscellaneous, eventually affect the lattice structure of YBCO monocrystal.Similarly, when metallic element enters into Y-Ba-Cu-O solution, changing
While becoming lattice structure, it is not improved the speed of growth.
The preparation of the high-temperature superconductive crystal that metallic element (M) adulterates in the past, typically selects the oxide of institute's doping metals
Crucible, also adds powdery Y while adding Ba-Cu-O cosolvent2O3；Or select Y2O3Crucible, helps adding Ba-Cu-O
Also the oxide of powdery doping metals is added while solvent.On the one hand, no matter being any method, all make solution state
Controlling becomes considerably complicated, is unfavorable for that doped crystal long-time stable grows；On the other hand, former approach is unfavorable on a large scale
Inside provide rare earth element, later approach is unfavorable for interior offer metallic element simultaneously on a large scale, thus the speed of growth is subject to simultaneously
Certain suppression.
Therefore, those skilled in the art is devoted to seeking a kind of side not only having extended growth time but also having improved the speed of growth
Method, is used for preparing high-temperature superconductor doped crystal.
Content of the invention
In view of the drawbacks described above of prior art, the technical problem to be solved is to overcome crystal in traditional method
Growth time and the technological deficiency of speed of growth control aspect and a kind of method preparing high-temperature superconductor doped crystal is provided.
For achieving the above object, the invention provides a kind of method preparing high-temperature superconductor doped crystal it is characterised in that
The method comprising the steps of：
A. by BaCO3Powder and CuO powder carry out dispensing, obtain BaCO3+ CuO powder；
B. the BaCO to described step a gained3+ CuO powder carries out pretreatment；
C. sinter the BaCO that described step b obtains3+ CuO powder, prepared Ba-Cu-O powder；
D. the Ba-Cu-O powder of described step c gained is added to the Y of element M doping2O3It is heated to the first temperature in crucible
Degree, and continue to be incubated, obtain M-Y-Ba-Cu-O solution；
E. the M-Y-Ba-Cu-O solution of described step d gained is cooled to second temperature；
F. it is used YBCO/MgO thin film as seed crystal, the surface of described YBCO/MgO thin film seed is contacted through described step
M-Y-Ba-Cu-O solution after e process, using the YBCO crystal of top seed crystal lifting technique growth elements M doping.
Preferably, in step a：Described BaCO3The mol ratio of Ba and Cu in+CuO powder is 0.4～0.7.
Preferably, in step, described in b, pretreatment includes following operation：
I. to described BaCO3+ CuO powder carries out wet grinding to obtain BaCO3+ CuO slurry, the wet grinding time is 2～4 hours；
Ii. the BaCO described in baking operation i3+ CuO slurry.
It is further preferred that when carrying out described wet grinding in above-mentioned operation i, in described BaCO3The liquid adding in+CuO powder
Body is dehydrated alcohol or water.
Preferably, in described step c：Described sintering is to be incubated 40～50 hours at 890～910 DEG C.
Preferably, in described step d：Described first temperature is 15～25 DEG C of more than the Peritectic Temperature of YBCO；Described insulation
Time be 30～40 hours.
Preferably, in described step e：The speed of described cooling is 1～2 DEG C/min；Described second temperature is the bag of YBCO
5～15 DEG C below brilliant temperature.
Preferably, the parameter of the technique of top seed crystal lifting described in step f is：Rotary speed is 80～120rpm, lifting
Speed is 0.03～0.30mm/h, and growth time is 50～100 hours.
Preferably, described element M is metallic element.
Present invention also offers the YBCO crystal of doped chemical M prepared according to the method described above.
Compared to prior art, the advanced point of the present invention is embodied in：
Present invention employs a kind of pervasive crucible, crucible mixes corresponding metallic element M, obtain metallic element M and mix
Miscellaneous high-temperature superconductive crystal：Doped chemical and solute are provided by crucible simultaneously, have both avoided the pollution of impurity element, in turn simplify
The environmental aspect of solution system.On the one hand, the state of solution is easily controlled such that it is able to make growth time effectively extend；Separately
On the one hand, doped chemical is uniformly distributed in crucible, can continually provide Y element and M element such that it is able to a certain degree
The upper raising speed of growth, successfully prepares high-temperature superconductor doped chemical crystal.
Below with reference to specific embodiment, the invention will be further described, to be fully understood from the purpose of the present invention, spy
Seek peace effect.
Specific embodiment
Embodiment 1
A kind of method preparing high-temperature superconductor doped crystal, comprises the following steps：
(1) take BaCO3Powder and CuO powder carry out dispensing, obtain BaCO3+ CuO powder, BaCO3In+CuO powder
The mol ratio of Ba and Cu is 0.6 or 0.7.
(2) BaCO that step (1) is obtained3+ CuO powder carries out pretreatment, and pretreatment includes：
A, in BaCO3Dehydrated alcohol is added to carry out wet grinding in+CuO powder, the wet grinding time is set as 3 hours, obtains BaCO3+
CuO slurry.
B, drying BaCO3+ CuO slurry.
(3) sintering step (2 obtain) BaCO3+ CuO powder.By BaCO3+ CuO powder is incubated 48 hours at 900 DEG C, is formed
Uniform Ba-Cu-O powder.
(4) the Ba-Cu-O powder obtaining step (3) is added to the Y of Mg doping2O3It is heated to 1017 DEG C (i.e. in crucible
More than the Peritectic Temperature of YBCO 12 DEG C), and then it is incubated 40 hours.Thus, Ba-Cu-O powder uniform melt, obtains Mg-Y-
Ba-Cu-O solution.
(5) the Mg-Y-Ba-Cu-O solution that step (4) obtains is cooled to 997 DEG C (i.e. with the cooldown rate of 1 DEG C/min
8 DEG C below the Peritectic Temperature of YBCO).
(6) the YBCO/MgO thin film that a size of 3mm × 3mm is used as seed crystal, by the surface of YBCO/MgO thin film seed
Contact Mg-Y-Ba-Cu-O solution, grows the YBCO crystal of Mg doping using top seed crystal lifting technique.Wherein, top seed crystal carries
The parameter of drawing process is：The rotary speed of seed crystal is 100rpm, and pull rate is 0.05mm/h, and growth time is 80 hours.
Embodiment 2
A kind of method preparing high-temperature superconductor doped crystal, comprises the following steps：
(1) take BaCO3Powder and CuO powder carry out dispensing, obtain BaCO3+ CuO powder, BaCO3In+CuO powder
The mol ratio of Ba and Cu is 0.4.
(2) BaCO that step (1) is obtained3+ CuO powder carries out pretreatment, and pretreatment includes：
A, in BaCO3Dehydrated alcohol is added to carry out wet grinding in+CuO powder, the wet grinding time is set as 2 hours, obtains BaCO3+
CuO slurry.
B, drying BaCO3+ CuO slurry.
(3) BaCO that sintering step (2) obtains3+ CuO powder.By BaCO3+ CuO powder is incubated 50 hours at 890 DEG C, shape
Uniformly Ba-Cu-O powder.
(4) the Ba-Cu-O powder obtaining step (3) is added to the Y of Fe doping2O3It is heated to 1020 DEG C (i.e. in crucible
More than the Peritectic Temperature of YBCO 15 DEG C), and then it is incubated 35 hours.Thus, Ba-Cu-O powder uniform melt, obtains Fe-Y-
Ba-Cu-O solution.
(5) the Fe-Y-Ba-Cu-O solution that step (4) obtains is cooled to 990 DEG C (i.e. with the cooldown rate of 1.5 DEG C/min
15 DEG C below the Peritectic Temperature of YBCO).
(6) the YBCO/MgO thin film that a size of 3mm × 3mm is used as seed crystal, by the surface of YBCO/MgO thin film seed
Contact Fe-Y-Ba-Cu-O solution, grows the YBCO crystal of Fe doping using top seed crystal lifting technique.Wherein, top seed crystal carries
The parameter of drawing process is：The rotary speed of seed crystal is 80rpm, and pull rate is 0.03mm/h, and growth time is 70 hours.
As can be seen here, employ a kind of pervasive crucible in embodiments of the invention, be intended to obtain the height of certain metallic element M doping
Temp. superconductive crystal is it is only necessary to mix corresponding metallic element in crucible.The advantage of this method is doped chemical and solute
There is provided by crucible simultaneously, both avoided the pollution of impurity element, in turn simplify the environmental aspect of solution system.On the one hand, solution
State be easily controlled such that it is able to make growth time effectively extend；On the other hand, doped chemical is uniformly distributed in crucible
In, can continually provide Y element and M element such that it is able to improve the speed of growth to a certain extent, successfully prepare high temperature and surpass
Lead doped chemical crystal.
The preferred embodiment of the present invention described in detail above.It should be appreciated that those of ordinary skill in the art is no
Need creative work just can make many modifications and variations according to the design of the present invention.Therefore, all technology in the art
It is available that personnel pass through logical analysis, reasoning, or a limited experiment under this invention's idea on the basis of existing technology
Technical scheme, all should be in the protection domain being defined in the patent claims.
Claims (8)
1. a kind of method preparing high-temperature superconductor doped crystal is it is characterised in that the method comprising the steps of：
A. by BaCO3Powder and CuO powder carry out dispensing, obtain BaCO3+ CuO powder；
B. the BaCO to described step a gained3+ CuO powder carries out pretreatment；
C. sinter the BaCO that described step b obtains3+ CuO powder, prepared Ba-Cu-O powder；
D. the Ba-Cu-O powder of described step c gained is added to the Y of element M g doping2O3It is heated to the first temperature in crucible,
And continue to be incubated, obtain Mg-Y-Ba-Cu-O solution；
E. the Mg-Y-Ba-Cu-O solution of described step d gained is cooled to second temperature；
F. it is used YBCO/MgO thin film as seed crystal, the surface of described YBCO/MgO thin film seed is contacted at through described step e
Mg-Y-Ba-Cu-O solution after reason, using the YBCO crystal of top seed crystal lifting technique growth elements Mg doping.
2. a kind of method preparing high-temperature superconductor doped crystal as claimed in claim 1 is it is characterised in that in described step a：
Described BaCO3The mol ratio of Ba and Cu in+CuO powder is 0.4～0.7.
3. a kind of method preparing high-temperature superconductor doped crystal as claimed in claim 1 is it is characterised in that institute in b in step
State pretreatment and include following operation：
I. to described BaCO3+ CuO powder carries out wet grinding to obtain BaCO3+ CuO slurry, the wet grinding time is 2～4 hours；
Ii. the BaCO described in baking operation i3+ CuO slurry.
4. a kind of method preparing high-temperature superconductor doped crystal as claimed in claim 3 is it is characterised in that in described operation i
In when carrying out described wet grinding, in described BaCO3The liquid adding in+CuO powder is dehydrated alcohol or water.
5. a kind of method preparing high-temperature superconductor doped crystal as claimed in claim 1 is it is characterised in that in described step c：
Described sintering is to be incubated 40～50 hours at 890～910 DEG C.
6. a kind of method being used for as claimed in claim 1 preparing high-temperature superconductor doped crystal is it is characterised in that described step d
In：Described first temperature is 15～25 DEG C of more than the Peritectic Temperature of YBCO；The time of described insulation is 30～40 hours.
7. a kind of method being used for as claimed in claim 1 preparing high-temperature superconductor doped crystal is it is characterised in that described step e
In：The speed of described cooling is 1～2 DEG C/min；Described second temperature is 5～15 DEG C of below the Peritectic Temperature of YBCO.
8. a kind of method being used for as claimed in claim 1 preparing high-temperature superconductor doped crystal is it is characterised in that institute in step f
The parameter stating top seed crystal lifting technique is：Rotary speed is 80～120rpm, and pull rate is 0.03～0.30mm/h, growth
Time is 50～100 hours.
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