CN110128131A - A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting - Google Patents

A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting Download PDF

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CN110128131A
CN110128131A CN201910529839.7A CN201910529839A CN110128131A CN 110128131 A CN110128131 A CN 110128131A CN 201910529839 A CN201910529839 A CN 201910529839A CN 110128131 A CN110128131 A CN 110128131A
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dysprosium
film
superconducting
oxygen
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刘连
王文涛
霍堡垒
田正健
赵勇
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Southwest Jiaotong University
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Abstract

A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, operation is mainly: mixing micro cobalt ions in the precursor solution of dysprosium barium copper oxygen；The precursor solution solution for mixing micro cobalt ions is coated on substrate, forms dysprosium barium copper oxygen amorphous precursor film after thermal decomposition；For the amorphous precursor film under conditions of 740-750 DEG C, 55-65 minutes or under conditions of 800-805 DEG C, 10-30 minutes, completion is epitaxially grown to phase；It makes annealing treatment to form the dysprosium Ba-Cu-O superconducting film with orthorhombic crystal structure finally by cryogenic oxygen.The dysprosium Ba-Cu-O superconducting film of acquisition has excellent texture, the micro-structure and high critical current densities of smooth densification.The temperature for being epitaxially grown to phase of this method is low or the time is short, and preparation cost is low, preparation efficiency is high, is conducive to the mass production and scale application of dysprosium Ba-Cu-O superconducting material.And its dysprosium Ba-Cu-O superconducting film obtained has excellent texture, the micro-structure and high critical current densities of smooth densification.

Description

A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting
Technical field
The present invention relates to be related to a kind of method for promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting.
Background technique
Dysprosium barium copper oxygen (DyBCO, DyBa2Cu3O7-δ) coating conductor is in transmission cable, transformer, magnet, superconducting magnetic energy storage Equal fields have a wide range of applications potentiality.German coating conductor manufacturer THEVA is using reaction electron beam coevaporation (RCE) side The dysprosium barium copper oxygen coating conductor that method is prepared in inclined substrate successfully breaches thickness effect, and critical current is more than 1000A/cm.
Compared to expensive vacuum method, deposition of metal organic (MOD) method is as a kind of DyBCO coating conductor for preparing Chemical method has low in cost, easily operated advantage, is more suitable for large-scale industrial production.Trifluoroacetate metal has It is a kind of typical deposition of metal organic method that machine object, which deposits (TFA-MOD) method, and this method can be prepared with good texture With high critical current densities (Jc) dysprosium Ba-Cu-O superconducting film, be extensively studied at present and be applied to industrial production. But the characteristics of due to this method itself, it is difficult to avoid generating poisonous gas HF at phase heat treatment stages, this not only has environment It is potentially hazardous, while arranging designing and manufacturing for fluorine facility and also increasing the preparation cost of dysprosium Ba-Cu-O film, constrain TFA- The further development of MOD method.In contrast to this, floride-free deposition of metal organic (FF-MOD) method has preparation process relatively simple The single, feature fast and environmental-friendly at phase velocity, is persistently concerned by people in recent years.But this method prepares texture The sintering temperature of DyBCO film is generally at 800 DEG C or so, and sintering time is generally at 60 minutes or more.So for a long time, high-temperature Sintering heat treatment, on the one hand will cause the elements diffusion between coating conductor dielectric layer and DyBCO superconducting layer, leads to superconductivity It can deteriorate.On the other hand also cause its preparation cost height, preparation efficiency low.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting.The preparation of this method It is at low cost, preparation efficiency is high, and the performance of dysprosium Ba-Cu-O superconducting film obtained is good, and critical current density is big.
The technical scheme adopted by the invention for realizing the object of the invention is a kind of promotion dysprosium Ba-Cu-O superconducting film epitaxial growth Method, the steps include:
A, prepared by precursor solution: by acetic acid dysprosium or acetylacetone,2,4-pentanedione dysprosium, barium acetate or acetylacetone barium, copper acetate or levulinic Ketone copper and cobalt acetate or acetylacetone cobalt, by dysprosium: barium: copper: oxygen: the stoichiometric ratio 1:2:3-X:X, 0.0008≤X of cobalt≤ 0.05 ratio, is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the b membrane substrate walked is subjected to decomposition heat treatment and obtains amorphous precursor film；
D, it is epitaxially grown to phase:
By amorphous precursor film at 740-750 DEG C, it is epitaxially grown to phase 55-65 minutes and obtains in dry argon oxygen gas mixture atmosphere The dysprosium barium copper oxygen phase film of texture.
Alternatively, being epitaxially grown to phase 10-30 points in dry argon oxygen gas mixture atmosphere by amorphous precursor film at 800-805 DEG C Clock obtains the dysprosium barium copper oxygen phase film of texture；
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment in oxygen atmosphere, obtains having orthogonal The dysprosium Ba-Cu-O superconducting film of crystal structure.
Compared with prior art, the beneficial effects of the present invention are:
One, the method for the present invention is mixed with micro Co ion in precursor solution.It has been found that stoichiometric ratio is 0.0008-0.05 Co ion doping, can be effectively facilitated the epitaxial growth of DyBCO precursor film crystal grain, be embodied in two sides Face:
On the one hand the temperature of grain nucleation in DyBCO precursor film during phase can be reduced into so that DyBCO film can compared with Start and complete epitaxial growth at a temperature of low, to significantly reduce the texture temperature of film, improves the property of dysprosium barium copper oxygen film Energy.Experiment shows to can be prepared by using the method for the present invention in 750 DEG C of low temperature close in 77K temperature and zero magnetic field lower critical electric current Degree is up to 3.0MA/cm2DyBCO film.
On the other hand, the speed of DyBCO precursor film grain nucleation and growth can be accelerated, so that DyBCO film epitaxial growth Time shorten；While the texture time for significantly shortening film, the performance of dysprosium barium copper oxygen film is improved.Experiment shows to use The method of the present invention is heat-treated 30 minutes at 805 DEG C and can be prepared by being up in 77K temperature and zero magnetic field lower critical current density 4.0MA/cm2DyBCO film.
Two, since the doping of Co ion is substantially reduced the texture temperature of DyBCO film or shortens the texture time, and then reduce The harmful element of dielectric layer improves the performance of DyBCO coating conductor to DyBCO superconduction membrane diffusion.
Three, the method for the present invention significantly reduces the temperature of epitaxial growth or has been obviously shortened the time of epitaxial growth, has What effect reduced DyBCO high temperature superconducting film is epitaxially grown to phase cost, reduces the preparation cost of dysprosium Ba-Cu-O superconducting film, improves The preparation efficiency of dysprosium Ba-Cu-O superconducting film, is conducive to the scale application of dysprosium Ba-Cu-O superconducting material.
Three, the method for the present invention is in whole preparation process, not fluorine-containing equal pollutants in all raw materials, to environment without dirt Dye；And all raw materials are cheap and easily-available, low manufacture cost；The ratio of Co doping is easy to control and adjusts, and is also beneficial to dysprosium barium copper The industrialized production of oxygen superconductive tape material.
Further detailed description is made to the present invention with reference to the accompanying drawings and detailed description.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of dysprosium barium copper oxygen film made from embodiment 1；
Fig. 2 is the stereoscan photograph of dysprosium barium copper oxygen film made from embodiment 1；
Fig. 3 is the X ray diffracting spectrum of dysprosium barium copper oxygen film made from embodiment 4；
Fig. 4 is the stereoscan photograph of the dysprosium barium copper oxygen film of Co ion doping made from embodiment 4.
In Fig. 1 and Fig. 3, ordinate is diffracted intensity (Intensity), and unit is arbitrary unit (a.u.)；Abscissa is 2 θ of the angle of diffraction, unit are degree (deg)
Specific embodiment:
Embodiment 1
A kind of specific embodiment of the invention are as follows: a method of promote the film epitaxial growth of dysprosium Ba-Cu-O superconducting, step Suddenly it is:
A, prepared by precursor solution: by acetic acid dysprosium, barium acetate, copper acetate and cobalt acetate, by dysprosium: barium: copper: the stoichiometry of cobalt Ratio than 1:2:2.9992:0.0008, is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the membrane substrate of b step is subjected to thermal decomposition process and obtains amorphous precursor film；
The concrete operations of thermal decomposition process are: membrane substrate are placed in tube furnace, under argon atmosphere protection, with 1 DEG C/min rises to 150 DEG C from room temperature；Then it is passed through dew point into furnace and is 15 DEG C of water vapour, while being passed through argon gas and forming humidity Argon atmosphere, be warming up to 450 DEG C with 0.5 DEG C/min, keep the temperature 1 hour；It is natural then again in dry argon atmosphere It is cooled to room temperature.
D, it is epitaxially grown to phase:
By amorphous precursor film at 750 DEG C, it is epitaxially grown in dry argon oxygen gas mixture atmosphere phase 55 minutes and obtains texture Dysprosium barium copper oxygen phase film.
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment, obtains that there is orthorhombic crystal structure Dysprosium Ba-Cu-O superconducting film.
The specific method of annealing is: the dysprosium barium copper oxygen phase film of texture is protected in 350 DEG C of dry oxygen atmospheres Temperature 3 hours, then cools to room temperature.
Test shows that critical current density of the dysprosium Ba-Cu-O superconducting film made from this example under 77K temperature, zero magnetic field is 3.0MA/cm2。
Fig. 1 is the X ray diffracting spectrum of dysprosium barium copper oxygen film made from this example.The chart it is bright at 750 DEG C at phase, Co ion is mixed The texture of miscellaneous superconducting film is good, without other miscellaneous phases.
Fig. 2 is the stereoscan photograph of dysprosium barium copper oxygen film made from this example.The chart it is bright at 750 DEG C at phase, Co ion is mixed Miscellaneous film surface is smooth, fine and close, and typical c-axis texture features are presented.
Embodiment 2
A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, the steps include:
A, prepared by precursor solution: by acetylacetone,2,4-pentanedione dysprosium, acetylacetone barium, acetylacetone copper and acetylacetone cobalt, by dysprosium: Barium: the ratio of the stoichiometric ratio 1:2:2.998:0.02 of cobalt is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the membrane substrate of b step is subjected to thermal decomposition process and obtains amorphous precursor film；
The concrete operations of thermal decomposition process are: membrane substrate are placed in tube furnace, under argon atmosphere protection, with 3 DEG C/min rises to 120 DEG C from room temperature；Then it is passed through dew point into furnace and is 20 DEG C of water vapour, while being passed through argon gas and forming humidity Argon atmosphere, be warming up to 480 DEG C with 1.5 DEG C/min, keep the temperature 0.5 hour；Then again in dry argon atmosphere, from So it is cooled to room temperature.
D, it is epitaxially grown to phase:
By amorphous precursor film at 740 DEG C, phase is epitaxially grown to 65 minutes in dry argon oxygen gas mixture atmosphere, obtains texture Dysprosium barium copper oxygen phase film.
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment, obtains that there is orthorhombic crystal structure Dysprosium Ba-Cu-O superconducting film.
The specific method of annealing is: the dysprosium barium copper oxygen phase film of texture is protected in 400 DEG C of dry oxygen atmospheres Temperature 1 hour, then cools to room temperature.
Test shows that critical current density of the dysprosium Ba-Cu-O superconducting film made from this example under 77K temperature, zero magnetic field is 1.0MA/cm2。
Embodiment 3
A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, the steps include:
A, prepared by precursor solution: by acetic acid dysprosium, barium acetate, copper acetate and cobalt acetate, by dysprosium: barium: copper: the stoichiometry of cobalt Ratio than 1:2:2.95:0.05, is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the membrane substrate of b step is subjected to thermal decomposition process and obtains amorphous precursor film；
The concrete operations of thermal decomposition process are: membrane substrate are placed in tube furnace, under argon atmosphere protection, with 5 DEG C/min rises to 100 DEG C from room temperature；Then it is passed through dew point into furnace and is 10 DEG C of water vapour, while being passed through argon gas and forming humidity Argon atmosphere, be warming up to 500 DEG C with 0.25 DEG C/min, keep the temperature 2 hours；Then again in dry argon atmosphere, from So it is cooled to room temperature.
D, it is epitaxially grown to phase:
By amorphous precursor film at 745 DEG C, phase is epitaxially grown to 60 minutes in dry argon oxygen gas mixture atmosphere, obtains texture Dysprosium barium copper oxygen phase film.
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment, obtains that there is orthorhombic crystal structure Dysprosium Ba-Cu-O superconducting film.
The specific method of annealing is: the dysprosium barium copper oxygen phase film of texture is protected in 500 DEG C of dry oxygen atmospheres Temperature 5 hours, then cools to room temperature.
Test shows that critical current density of the dysprosium Ba-Cu-O superconducting film made from this example under 77K temperature, zero magnetic field is 1.2MA/cm2。
Embodiment 4
A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, the steps include:
A, prepared by precursor solution: by acetic acid dysprosium, barium acetate, copper acetate and cobalt acetate, by dysprosium: barium: copper: the stoichiometry of cobalt Ratio than 1:2:2.9992:0.0008, is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the membrane substrate of b step is subjected to thermal decomposition process and obtains amorphous precursor film；
The concrete operations of thermal decomposition process are: membrane substrate are placed in tube furnace, under argon atmosphere protection, with 5 DEG C/min rises to 100 DEG C from room temperature；Then it is passed through dew point into furnace and is 10 DEG C of water vapour, while being passed through argon gas and forming humidity Argon atmosphere, be warming up to 500 DEG C with 0.25 DEG C/min, keep the temperature 2 hours；Then again in dry argon atmosphere, from So it is cooled to room temperature.
D, it is epitaxially grown to phase:
By amorphous precursor film at 805 DEG C, phase is epitaxially grown to 30 minutes in dry argon oxygen gas mixture atmosphere, obtains texture Dysprosium barium copper oxygen phase film.
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment, obtains that there is orthorhombic crystal structure Dysprosium Ba-Cu-O superconducting film.
The specific method of annealing is: the dysprosium barium copper oxygen phase film of texture is protected in 500 DEG C of dry oxygen atmospheres Temperature 5 hours, then cools to room temperature.
Test shows that critical current density of the dysprosium Ba-Cu-O superconducting film made from this example under 77K temperature, zero magnetic field is 4.0MA/cm2。
Fig. 3 is the X ray diffracting spectrum of dysprosium barium copper oxygen film made from this example.The chart it is bright at 805 DEG C at phase 30 minutes, Co The superconducting film of ion doping is all c-axis texture, without other miscellaneous phases.
Fig. 4 is the stereoscan photograph of dysprosium barium copper oxygen film made from this example.The chart it is bright at 805 DEG C at phase 30 minutes, Co The hole of the film surface of ion doping is small, smooth, fine and close, and typical c-axis texture features are presented.
Embodiment 5
A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, the steps include:
A, prepared by precursor solution: by acetic acid dysprosium, barium acetate, copper acetate and cobalt acetate, by dysprosium: barium: copper: the stoichiometry of cobalt Ratio than 1:2:2.98:0.02, is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the membrane substrate of b step is subjected to thermal decomposition process and obtains amorphous precursor film；
The concrete operations of thermal decomposition process are: membrane substrate are placed in tube furnace, under argon atmosphere protection, with 4 DEG C/min rises to 150 DEG C from room temperature；Then it is passed through dew point into furnace and is 20 DEG C of water vapour, while being passed through argon gas and forming humidity Argon atmosphere, be warming up to 450 DEG C with 1.5 DEG C/min, keep the temperature 0.5 hour；Then again in dry argon atmosphere, from So it is cooled to room temperature.
D, it is epitaxially grown to phase:
By amorphous precursor film at 800 DEG C, phase is epitaxially grown to 20 minutes in dry argon oxygen gas mixture atmosphere, obtains texture Dysprosium barium copper oxygen phase film.
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment, obtains that there is orthorhombic crystal structure Dysprosium Ba-Cu-O superconducting film.
The specific method of annealing is: the dysprosium barium copper oxygen phase film of texture is protected in 450 DEG C of dry oxygen atmospheres Temperature 4 hours, then cools to room temperature.
Test shows that critical current density of the dysprosium Ba-Cu-O superconducting film made from this example under 77K temperature, zero magnetic field is 1.8MA/cm2。
Embodiment 6
A method of promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, the steps include:
A, prepared by precursor solution: by acetylacetone,2,4-pentanedione dysprosium, acetylacetone barium, acetylacetone copper and acetylacetone cobalt, by dysprosium: Barium: copper: the ratio of the stoichiometric ratio 1:2:2.95:0.05 of cobalt is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the membrane substrate of b step is subjected to thermal decomposition process and obtains amorphous precursor film；
The concrete operations of thermal decomposition process are: membrane substrate are placed in tube furnace, under argon atmosphere protection, with 1 DEG C/min rises to 130 DEG C from room temperature；Then it is passed through dew point into furnace and is 15 DEG C of water vapour, while being passed through argon gas and forming humidity Argon atmosphere, be warming up to 450 DEG C with 1 DEG C/min, keep the temperature 1 hour；It is naturally cold then again in dry argon atmosphere But to room temperature.
D, it is epitaxially grown to phase:
By amorphous precursor film at 803 DEG C, phase is epitaxially grown to 10 minutes in dry argon oxygen gas mixture atmosphere, obtains texture Dysprosium barium copper oxygen phase film.
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment, obtains that there is orthorhombic crystal structure Dysprosium Ba-Cu-O superconducting film.
The specific method of annealing is: the dysprosium barium copper oxygen phase film of texture is protected in 350 DEG C of dry oxygen atmospheres Temperature 1 hour, then cools to room temperature.
Test shows that critical current density of the dysprosium Ba-Cu-O superconducting film made from this example under 77K temperature, zero magnetic field is 1.5MA/cm2。

Claims (3)

1. a kind of method for promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting, the steps include:
A, prepared by precursor solution: by acetic acid dysprosium or acetylacetone,2,4-pentanedione dysprosium, barium acetate or acetylacetone barium, copper acetate or acetylacetone copper With cobalt acetate or acetylacetone cobalt, by dysprosium: barium: copper: the stoichiometric ratio 1:2:3-X:X of cobalt, the ratio of 0.0008≤X≤0.05 Example, is dissolved in propionic acid, obtains precursor solution；
B, by the precursor solution of a step coated on substrate, film coating and drying: is formed on substrate after dry；
C, the preparation of amorphous precursor film: the b membrane substrate walked is subjected to decomposition heat treatment and obtains amorphous precursor film；
D, it is epitaxially grown to phase:
By amorphous precursor film at 740-750 DEG C, it is epitaxially grown in dry argon oxygen gas mixture atmosphere phase 55-65 minutes and obtains texture Dysprosium barium copper oxygen phase film；
Alternatively, being epitaxially grown to phase by amorphous precursor film at 800-805 DEG C 10-30 minutes in dry argon oxygen gas mixture atmosphere, obtaining To the dysprosium barium copper oxygen phase film of texture；
E, it makes annealing treatment: the dysprosium barium copper oxygen of the texture of d step mutually being made annealing treatment in oxygen atmosphere, is obtained with orthorhombic crystal The dysprosium Ba-Cu-O superconducting film of structure.
2. a kind of method for promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting as described in claim 1, it is characterised in that: described The concrete operations of the thermal decomposition process of c step are: membrane substrate being placed in tube furnace, under argon atmosphere protection, with 1-5 DEG C/min from room temperature rises to 100-150 DEG C；Then it is passed through dew point into furnace and is 10-20 DEG C of water vapour, while being passed through argon gas shape At moist argon atmosphere, it is warming up to 450-500 DEG C with 0.25-1.5 DEG C/min, keeps the temperature 0.5-2 hours；Then again dry In dry argon atmosphere, cooled to room temperature.
3. a kind of method for promoting the film epitaxial growth of dysprosium Ba-Cu-O superconducting as described in claim 1, it is characterised in that: described The specific method of the annealing of e step is: by the dysprosium barium copper oxygen phase film of texture, in 350-500 DEG C of dry oxygen atmosphere Heat preservation 1-5 hours, then cools to room temperature.
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Citations (1)

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CN102424575A (en) * 2011-09-13 2012-04-25 西南交通大学 Preparation method of Co-doped GdBCO superconducting film

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CN102424575A (en) * 2011-09-13 2012-04-25 西南交通大学 Preparation method of Co-doped GdBCO superconducting film

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