CN107342140B - A method of making rare earth barium copper oxide superconducting film - Google Patents
A method of making rare earth barium copper oxide superconducting film Download PDFInfo
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Abstract
The invention discloses a kind of methods for making rare earth barium copper oxide superconducting film.Method includes the following steps: (a) prepares the precursor solution containing rare earth element ion, barium ions, copper ion and solvent；(b) application temperature is controlled by the thermostatic mode not higher than 20 DEG C, controls substrate and precursor solution in same set temperature, precursor solution is coated in substrate and obtains precursor film；(c) precursor film is placed in heat-treatment furnace, rare earth barium copper oxide superconducting film is obtained by thermal decomposition, sintering and oxygenation step.It is in specific steady temperature by controlling application temperature, effectively increases the thickness of film.
Description
Technical field
The present invention relates to a kind of methods for making rare earth barium copper oxide superconducting film and constant temperature dipping system.
Background technique
RE, Ba and Cu oxide (REBa1+xCu3O7-y, wherein RE is rare earth element such as Y, Gd, Sm etc., 0.5≤x≤1,0 < y <
0.5) high temperature superconducting film is the core component of second generation high temperature super conductive conductor (be otherwise known as coating conductor), it is in liquid nitrogen temperature
Spending (77K) has high self-fields critical current density (generally greater than 1MA/cm2), and be suitble to answer under high magnetic field environments
With.The technology for preparing high temperature superconducting film at present mainly includes chemical solution deposition and some vacuum deposition methods, wherein chemical solution
Liquid deposition technique is very beneficial for reducing production cost, and prepare by the technology due to not needing expensive vacuum equipment
High temperature superconducting film there is excellent performance, while the technology stoichiometric ratio is easy to fine-tune, the good, Cheng Xiang at film uniformity
Purity is high, deposition rate are high, very wide to the shape and size range of choice of substrate.Therefore, chemical solution deposition technique is considered
It is one of the core technology of the low cost and high performance second generation high temperature super conductive conductor industrialization preparation of development.
In order to reduce the preparation cost of second generation high temperature super conductive conductor, its industrialization process is promoted, it is super that high temperature can be improved
The critical current of conducting wire is most important.There are mainly two types of modes for the critical current of raising superconductivity wire, first is that improving critical electricity
Current density, second is that improving the thickness of superconducting layer.It is fairly perfect to the research of first way in the world at present, use chemistry
The Jc of the RE, Ba and Cu oxide high-temperature superconducting thin film of solwution method preparation generally can achieve 4MA/cm2Level it is even higher.For
The second way improves film thickness, and existing method mainly has: 1. change the ion concentration of precursor solutions to increase film thickness 2.
Change film rate, additive such as polyethylene glycol (PEG), polyvinyl butyral is added in Lai Zengjia film thickness 3. in precursor solution
(PVB), polyvinylpyrrolidone (PVP) etc..
The method for improving film thickness for existing three kinds, can increase the thickness of film, this side to a certain extent
The introducing of method is conducive to further change the thickness of film, increases and adjusts window.For precursor solution, when changing its concentration,
Its viscosity can also occur to change accordingly, to change the thickness of film in coated film.The coating side of high temperature super conductive conductor
Formula mainly has spin coating, dip-coating, die slot coating, inkjet printing etc., and the coating rate for changing film can vary in the thickness of film
Degree, for example, spin coating can change the rotation speed of spin coating instrument to change film thickness, dip-coating can change the rate of pulling etc. of film
Adjust film thickness.The thickness of film can also be made to exist in addition, adding the viscosity of certain additive change solution in the solution
It changes to a certain extent.It is to be coated at normal temperature that existing precursor solution, which applies membrane process, does not consider control of the temperature to film thickness
Factor processed.
Summary of the invention
The main purpose of the present invention is to provide a kind of method for making rare earth barium copper oxide superconducting film and constant temperature dipping system,
It is in specific steady temperature by controlling application temperature, effectively increases the thickness of film, controllability is good.
To achieve the above object, the invention adopts the following technical scheme:
A method of making rare earth barium copper oxide superconducting film, comprising the following steps:
(a) precursor solution containing rare earth element ion, barium ions, copper ion and solvent is prepared；
(b) application temperature is controlled by the thermostatic mode not higher than 20 DEG C, controls substrate and precursor solution in same setting
Precursor solution is coated in substrate and obtains precursor film by temperature；
(c) precursor film is placed in heat-treatment furnace, rare earth barium copper oxide superconducting is obtained by thermal decomposition, sintering and oxygenation step
Film.
Further:
In step (b), the set temperature is constant temperature not higher than 10 DEG C, preferably no greater than 0 DEG C.
The thermostatic mode includes water bath with thermostatic control, constant temperature oil bath or constant temperature humidity chamber.
The coating method of the precursor solution includes spin coating, dip-coating, die slot coating or spraying printing.
In step (c), it is rapidly heated and rises to 300-650 DEG C and keep the temperature the thermal decomposition of completion in 0-60 minutes, continue to rise to
700-825 DEG C and the sintering of completion in 20-250 minutes is kept the temperature, then 400-500 DEG C will be cooled to and keep the temperature 0-240 minutes and be oxygenated.
Step (c) includes:
Thermal decomposition the stage, with 1-1500 DEG C/min of heating rate by the furnace temperature of precursor film present position rise to for
300-650 DEG C and keep the temperature 0-60 minutes, should during use 0.1-3 liters/min of high purity oxygen gas stream as thermally decomposing atmosphere, and
Increase being passed through for water vapour at 100 DEG C or so；
In sintering stage, oxygen-nitrogen mixture and water vapour are passed through in heat-treatment furnace, gas flow is 0.1-3 liters/min,
The furnace temperature of precursor film present position is risen to as 730-825 DEG C with 10-100 DEG C/min of heating rate and keeps the temperature 20-250 points
Clock；
In the oxygenation stage, the furnace temperature of precursor film present position is down to 400-500 DEG C, 0-240 minutes is kept the temperature, was cooling down
Heat-treating atmosphere is switched to dry high purity oxygen gas in journey, is finally cooled to room temperature precursor film.
The rare earth element ion, barium ions, copper ion molar ratio are 1:(1+x): 3, wherein 0.5≤x≤1；Before described
The total concentration for driving GOLD FROM PLATING SOLUTION category element is 0.5-3mol/L；It is 1%-50%'s that mass fraction is added in the precursor solution
Polymeric additive, for the polymeric additive molecular weight within the scope of 50-50000, the polymeric additive includes PEG
(polyethylene glycol), PVA (polyvinyl alcohol), PVB (polyvinyl butyral), PVC (polyvinyl chloride), PAA (polyacrylic acid), PET
(polyethylene terephthalate), PE (polyethylene), PP (polypropylene), PC (polycarbonate), PMMA (poly-methyl methacrylate
Ester), PVP (polyvinylpyrrolidone), PAM (polyacrylamide), PEO (polyethylene glycol oxide), PPG (polyether polyol), PPO
It is one of (polyphenylene oxide) or a variety of.
It is a kind of for coating the constant temperature dipping system of rare earth barium copper oxide superconducting film, including water-bath groove body, heat conducting pipe and leaching
Container, the upper end opening of the water-bath groove body and the heat conducting pipe are applied, the heat conducting pipe is arranged in such a way that lower end seals
The bottom of the water-bath groove body forms water-bath media in the water-bath groove body, outside the heat conducting pipe and holds sky
Between, the top that the water-bath media hold space is provided with insulating barrier, and the immersion container is placed on the interior of the heat conducting pipe
Portion, the immersion container hold space not higher than the water-bath media, and the water-bath groove body will be described by the heat conducting pipe
The heat of water-bath media is transmitted to the immersion container, and the temperature for controlling the solution in the immersion container is not higher than 30 DEG C
Constant temperature.
Further:
The internal diameter of the heat conducting pipe is greater than the outer diameter of the immersion container in the heat conducting pipe and the immersion container
Form interval region, it is preferable that the top of the interval region is provided with insulating barrier.
The heat conducting pipe is the closed copper pipe in lower end.
Beneficial effects of the present invention:
The present invention prepares high temperature superconducting film traditional handicraft for chemical solution deposition technique and proposes improvement, by being not higher than
20 DEG C of thermostatic mode controls application temperature, controls substrate and precursor solution in same set temperature, precursor solution is coated on
Precursor film, the thickness of Lai Zengjia film are obtained in substrate.Inventor changes precursor solution temperature when the study found that coating precursor film
Degree, not only can control every rheological parameter of precursor solution (including Newtonian fluid, non-newtonian fluid etc.), such as viscosity, bend
Intensity, consistency index, flow behavior index, density etc. are taken, moreover, if with the thermostatic mode control coating temperature not higher than 20 DEG C
Degree, relative to being coated under room temperature, can also effectively increase the thickness of film, so as to obtain the film compared with high critical current,
And controllability is strong.
Detailed description of the invention
Fig. 1 is the preparation process flow of the embodiment of the present invention；
Fig. 2 is the improvement water bath device overall effect figure of the embodiment of the present invention；
Fig. 3 is the improvement water bath device top view of the embodiment of the present invention；
Fig. 4 is the improvement water bath device sectional view of the embodiment of the present invention；
Fig. 5 is scanning electron microscope (SEM) measured film thickness result of present example 1；
Fig. 6 is scanning electron microscope (SEM) image of 10 DEG C of film cross sections in present example 1；
Fig. 7 is scanning electron microscope (SEM) measured film thickness result of present example 2；
Fig. 8 is scanning electron microscope (SEM) image of 10 DEG C of film cross sections in present example 2.
Specific embodiment
It elaborates below to embodiments of the present invention.It is emphasized that following the description is only exemplary,
The range and its application being not intended to be limiting of the invention.
Refering to fig. 1, in one embodiment, a method of making rare earth barium copper oxide superconducting film, comprising the following steps:
(a) precursor solution containing rare earth element ion, barium ions, copper ion and solvent is prepared；
(b) application temperature is controlled by the thermostatic mode not higher than 20 DEG C, controls substrate and precursor solution in same setting
Precursor solution is coated in substrate and obtains precursor film by temperature；
(c) precursor film is placed in heat-treatment furnace, rare earth barium copper oxide superconducting is obtained by thermal decomposition, sintering and oxygenation step
Film.
In a preferred embodiment, in step (b), the set temperature is constant temperature not higher than 10 DEG C, preferably no greater than 0
℃。
The thermostatic mode includes water bath with thermostatic control, constant temperature oil bath or constant temperature humidity chamber.
The coating method of the precursor solution includes spin coating, dip-coating, die slot coating or spraying printing.
Refering to fig. 1, in a preferred embodiment, it in step (c), is rapidly heated and rises to 300-650 DEG C and keep the temperature 0-60 minutes
Thermal decomposition is completed, continue to rise to 700-825 DEG C and keeps the temperature the sintering of completion in 20-250 minutes, then 400-500 DEG C will be cooled to
And it keeps the temperature 0-240 minutes and is oxygenated.
Refering to fig. 1, in more preferred embodiment, step (c) includes:
Thermal decomposition the stage, with 1-1500 DEG C/min of heating rate by the furnace temperature of precursor film present position rise to for
300-650 DEG C and keep the temperature 0-60 minutes, should during use 0.1-3 liters/min of high purity oxygen gas stream as thermally decomposing atmosphere, and
Increase being passed through for water vapour at 100 DEG C or so；
In sintering stage, oxygen-nitrogen mixture and water vapour are passed through in heat-treatment furnace, gas flow is 0.1-3 liters/min,
The furnace temperature of precursor film present position is risen to as 730-825 DEG C with 10-100 DEG C/min of heating rate and keeps the temperature 20-250 points
Clock；
In the oxygenation stage, the furnace temperature of precursor film present position is down to 400-500 DEG C, 0-240 minutes is kept the temperature, was cooling down
Heat-treating atmosphere is switched to dry high purity oxygen gas in journey, is finally cooled to room temperature precursor film.
In a preferred embodiment, the rare earth element ion, barium ions, copper ion molar ratio are 1:(1+x): 3, wherein
0.5≤x≤1；The total concentration of metallic element is 0.5-3mol/L in the precursor solution；Quality is added in the precursor solution
Score is the polymeric additive of 1%-50%, and the polymeric additive molecular weight is within the scope of 50-50000, the polymerization
Object additive includes PEG (polyethylene glycol), PVA (polyvinyl alcohol), PVB (polyvinyl butyral), PVC (polyvinyl chloride), PAA
(polyacrylic acid), PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene), PC (polycarbonate), PMMA
(polymethyl methacrylate), PVP (polyvinylpyrrolidone), PAM (polyacrylamide), PEO (polyethylene glycol oxide), PPG are (poly-
Ethoxylated polyhydric alcohol), one of PPO (polyphenylene oxide) or a variety of.
Refering to Fig. 2 to Fig. 4, in one embodiment, a kind of constant temperature dip-coating for coating rare earth barium copper oxide superconducting film is set
It is standby, including water-bath groove body 2, heat conducting pipe 5 and immersion container 4, the upper end opening of the water-bath groove body 2 and the heat conducting pipe 5,
The bottom of the water-bath groove body 2 is arranged in such a way that lower end seals in the heat conducting pipe 5, in the water-bath groove body 2,
The external water-bath media that formed of the heat conducting pipe 5 hold space, and the top that the water-bath media hold space is provided with insulation gear
Plate 1, the immersion container 4 are placed on the inside of the heat conducting pipe 5, and the immersion container 4 is held not higher than the water-bath media
The heat of the water-bath media is transmitted to the immersion container 4 by the heat conducting pipe 5 by space, the water-bath groove body 2, control
The temperature of the solution in the immersion container 4 is made as the constant temperature not higher than 20 DEG C.Water-bath media can be water, mixture of ice and water,
And other liquid or solidliquid mixture etc..
Refering to Fig. 2 to Fig. 4, in a preferred embodiment, the internal diameter of the heat conducting pipe 5 is greater than the outer diameter of the immersion container 4
To form interval region in the heat conducting pipe 5 and the immersion container 4.It is highly preferred that the top of the interval region is arranged
There is insulating barrier.Insulating barrier plays heat preservation and prevents the moisture of water-bath from entering in immersion container 4.It is highly preferred that described thermally conductive
Pipe is the closed copper pipe in lower end.
In embodiment, platinum sensor can be used and heater controls bath temperature, pulling machine presss from both sides during lifting
It holds substrate and immerses precursor solution, lifting film is then carried out under certain speed.
The constant temperature dipping system can control dip-coating bottle temperature close to bath temperature, keep the temperature uniformity of lifting process.It adopts
With the constant temperature dipping system of preferred embodiment, it on the one hand can guarantee the consistency for lifting temperature in range, on the other hand be insulated
Pollution of the moisture that baffle/retaining ring can also prevent to solution.
Refering to fig. 1, in a specific embodiment, the technique for making rare earth barium copper oxide superconducting film comprises the following processes:
(1) according to 1:(1+x): 3 metal cation molar ratio (wherein 0.5≤x≤1), by rare earth metal, barium and copper
Salt is weighed and is put into container, reduces its water content as far as possible by the methods of toasting or rotating.Rare earth metal can use one
Kind rare earth element or the form of several rare earth element combination, selectable rare earth element include yttrium (Y), gadolinium (Gd), samarium
(Sm), neodymium (Nd), europium (Eu), dysprosium (Dy), holmium (Ho), erbium (Er) etc..Workable salt include trifluoroacetate, acetate,
Nitrate, carbonate, hydrochloride, acrylates, naphthenate etc..
(2) acids solvent or alcohols solvent (such as methanol) or water equal solvent or combinations thereof are added, and is mixed into polymer addition
Agent, using the method for magnetic agitation and standing, preparation obtains uniform and stable precursor solution.Polymeric additive can use
PEG (polyethylene glycol), PVA (polyvinyl alcohol), PVB (polyvinyl butyral), PVC (polyvinyl chloride), PAA (polyacrylic acid),
PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene), PC (polycarbonate), PMMA (polymethyl
Sour methyl esters), PVP (polyvinylpyrrolidone), PAM (polyacrylamide), PEO (polyethylene glycol oxide), PPG (polyether polyol),
PPO (polyphenylene oxide) etc.；Mass fraction of the molecular weight of polymeric additive within the scope of 50-50000, in precursor solution preparation
For 1%-50%.The total concentration of metallic element is 0.5-3mol/L in precursor solution.
(3) substrate is cleaned in methanol equal solvent using ultrasonic method, substrate is the oxide with biaxial texture, such as aluminium
Sour lanthanum, strontium titanates, cerium oxide, magnesia or yttria-stabilized zirconia etc. can use monocrystal chip, can also be using in gold
Belong to the sull with biaxial texture prepared in base band.
(4) precursor solution is placed under constant temperature, the thermostatic mode is water bath with thermostatic control, constant temperature oil bath, constant temperature and humidity
Chamber etc..After temperature and setting value balance, the modes such as printing are coated with or sprayed using spin coating, dip-coating, die slot, are uniformly applied
It covers and precursor film is formed on the substrate.Preferably, application temperature is lower than 20 DEG C.
(5) will precursor film be placed in heat-treatment furnace in start the thermal decomposition stage, with 1-1500 DEG C/min of heating rate will before
The furnace temperature for driving membrane sample present position rises to as 300-650 DEG C and keeps the temperature 0-60 minutes.0.1-3 liters/min should be used in the process
High purity oxygen gas stream as thermal decomposition atmosphere, and increase water vapour at 100 DEG C or so and be passed through.
(6) during the sintering process, be passed through oxygen-nitrogen mixture and water vapour in heat-treatment furnace, gas flow be 0.1-3 liter/
Minute.The furnace temperature of forerunner's membrane sample present position is risen to as 730-825 DEG C and kept the temperature with 10-100 DEG C/min of heating rate
20-250 minutes.
(7) in the oxygenation stage, the furnace temperature of forerunner's membrane sample present position is down to 400-500 DEG C, keeps the temperature 0-240 minutes,
Heat-treating atmosphere is switched to dry high purity oxygen gas in temperature-fall period.Finally, closing heat-treatment furnace heating power, make sample
Cool to room temperature with the furnace.
(8) range of last superconducting thin film thickness obtained is at 100 nanometers to 10 microns.
The method that the control application temperature of the embodiment of the present invention adjusts rare earth barium copper oxide superconducting film thickness can also cooperate it
One or more being used cooperatively of his method (such as adjusting concentration, spin coating revolving speed, the dip-coating rate of pulling or using additive), can
To increase film thickness, suitably so as to obtain the film compared with high critical current on the basis of certain critical current density.
Example 1
Preparation flow is as shown in Figure 1, first, in accordance with 1:(1+x): 3 metal cation molar ratio (wherein 0.5≤x≤1),
It by four acetate hydrate yttriums, barium acetate, copper acetate dihydrate, is dissolved in deionized water by the way of stirring, and added wherein
Enter trifluoroacetic acid.By the process of 2 rotary evaporations, finally in methyl alcohol by above-mentioned dissolving metal salts, obtain clear,
Navy blue predecessor, concentration 1.5mol/L.
By the way of improving water-bath, respectively 0 DEG C, 10 DEG C, 20 DEG C and 30 DEG C at a temperature of carry out dip-coating, before above-mentioned
It drives solution and is coated to LaAlO3In (lanthanum aluminate) single crystal substrates, places into and carry out rapid thermal treatment in tube furnace, it is available
YBCO precursor thin film.With Hitachi Su8010 scanning electron microscope observation film sections thickness, each sample takes 5 values to eliminate and misses
Difference.The dip-coating under 0 DEG C, 10 DEG C, 20 DEG C, 30 ° of different steady temperatures, film thickness be respectively 265nm, 227nm, 222nm,
158nm。
Fig. 5 shows scanning electron microscope (SEM) measured film thickness result of example 1.Fig. 6 is shown in example 1
Scanning electron microscope (SEM) image of 10 DEG C of film cross sections.
Example 2
By a kind of preparation solution methods of embodiment, compound concentration is the predecessor of 1.8mol/L, and then predecessor is added
Mass fraction is 25% polyethylene glycol 2000 (PEG2000), obtains modified predecessor after dissolution is sufficiently stirred and stands.
By the way of improving water-bath temperature control, respectively 0 DEG C, 10 DEG C, 20 DEG C and 30 DEG C at a temperature of carry out dip-coating, use immersion technique
Above-mentioned precursor solution is coated to LaAlO3In (lanthanum aluminate) single crystal substrates, places into and carry out rapid thermal treatment in tube furnace, it can
To obtain YBCO precursor thin film.With Hitachi Su8010 scanning electron microscope observation film sections thickness, each sample takes 5 values to disappear
Except error.The dip-coating under 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C of different steady temperatures, film thickness be divided into 548nm, 493nm,
384nm、329nm。
Fig. 7 shows scanning electron microscope (SEM) measured film thickness result of example 2.Fig. 8 is shown in example 2
Scanning electron microscope (SEM) image of 10 DEG C of film cross sections.
The above content is combine it is specific/further detailed description of the invention for preferred embodiment, cannot recognize
Fixed specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs,
Without departing from the inventive concept of the premise, some replacements or modifications can also be made to the embodiment that these have been described,
And these substitutions or variant all shall be regarded as belonging to protection scope of the present invention.
Claims (8)
1. a kind of method for making rare earth barium copper oxide superconducting film, which comprises the following steps:
(a) precursor solution containing rare earth element ion, barium ions, copper ion and solvent is prepared；
(b) application temperature is controlled by the thermostatic mode not higher than 20 DEG C, controls substrate and precursor solution in same set temperature,
Precursor solution is coated in substrate and obtains precursor film；
(c) precursor film is placed in heat-treatment furnace, rare earth barium copper oxide superconducting film is obtained by thermal decomposition, sintering and oxygenation step.
2. the method according to claim 1, wherein the set temperature is not higher than 10 DEG C in step (b)
Constant temperature.
3. according to the method described in claim 1, it is characterized by: the set temperature is not higher than 0 DEG C in step (b)
Constant temperature.
4. according to the method described in claim 1, it is characterized by: the thermostatic mode include water bath with thermostatic control, constant temperature oil bath or
Constant temperature humidity chamber.
5. according to the method described in claim 1, it is characterized by: the coating method of the precursor solution include spin coating, dip-coating,
Die slot coating or spraying printing.
6. method according to any one of claims 1 to 5, which is characterized in that in step (c), be rapidly heated and rise to 300-
650 DEG C and the thermal decomposition of completion in 0-60 minutes is kept the temperature, continues to rise to 700-825 DEG C and keep the temperature completion in 20-250 minutes being sintered,
It will be cooled to 400-500 DEG C again and keep the temperature 0-240 minutes and be oxygenated.
7. according to the method described in claim 6, it is characterized in that, step (c) includes:
In the thermal decomposition stage, the furnace temperature of precursor film present position is risen to as 300-650 with 1-1500 DEG C/min of heating rate
DEG C and keep the temperature 0-60 minutes, should during use 0.1-3 liters/min of high purity oxygen gas stream as atmosphere is thermally decomposed, and at 100 DEG C
Left and right increases being passed through for water vapour；
In sintering stage, oxygen-nitrogen mixture and water vapour are passed through in heat-treatment furnace, gas flow is 0.1-3 liters/min, with
The furnace temperature of precursor film present position is risen to as 730-825 DEG C and keeps the temperature 20-250 minutes by 10-100 DEG C/min of heating rate；
In the oxygenation stage, the furnace temperature of precursor film present position is down to 400-500 DEG C, 0-240 minutes are kept the temperature, in temperature-fall period
Heat-treating atmosphere is switched to dry high purity oxygen gas, is finally cooled to room temperature precursor film.
8. method according to any one of claims 1 to 5, which is characterized in that the rare earth element ion, barium ions, copper
Ion molar ratio is 1:(1+x): 3, wherein 0.5≤x≤1；The total concentration of metallic element is 0.5- in the precursor solution
3mol/L；The polymeric additive for being 1%-50% added with mass fraction in the precursor solution, the polymeric additive
For molecular weight within the scope of 50-50000, the polymeric additive includes PEG (polyethylene glycol), PVA (polyvinyl alcohol), PVB (poly-
Vinyl butyral), PVC (polyvinyl chloride), PAA (polyacrylic acid), PET (polyethylene terephthalate), PE (poly- second
Alkene), PP (polypropylene), PC (polycarbonate), PMMA (polymethyl methacrylate), PVP (polyvinylpyrrolidone), PAM it is (poly-
Acrylamide), PEO (polyethylene glycol oxide), PPG (polyether polyol), one of PPO (polyphenylene oxide) or a variety of.
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