Patent Application
20130053249
The present invention refers to obtaining a solution of metal-organic precursors with a maximum fluorine content of 10% using the solution previously described in patent ES2259919 B1 as the starting point. This modification enables carrying out the thermal treatment of superconducting decomposition layers (pyrolysis) and crystal growth in a single stage. In addition, the low fluorine content reduces the risks of toxicity and corrosion.
High temperature superconducting materials have huge potential for use in a wide variety of technologies. However, it is an essential requirement to develop methodologies for obtaining high performance superconductors, particularly those that can transport high electrical currents without losses, including under high magnetic fields. The first high temperature conductors developed were based on BiSrCaCuO-type phases and these were called first generation superconductors (1G). The development of such materials saw a major revolution with the discovery of a new methodology for the preparation of a second generation (2G) of conductors based on REBa2Cu3O7-type materials (REBCO, where RE=rare earth or yttrium), called epitaxial superconductors (or coated conductors).
In recent years, various methodologies have been developed for obtaining epitaxial superconductors based on different multi-layer architectures with high potential in many fields for high current and high temperature applications. Various strategies have been followed for preparing these 2G conductors mainly based on methodologies of vacuum deposition of epitaxial layers on metal substrates. These substrates can have a textured oxide template, deposited by Ion Beam Deposition (IBD) on a polycrystalline substrate or are composed of textured buffer layers, which replicate the texture achieved in substrates via thermomechanical treatments such as the so-called Rolling Assisted Biaxial Texturing (RABiTs). Other interesting approaches are where the textured buffer layer is achieved by Surface Oxidation Epitaxy, SOE) or by deposition by inclined evaporation (Inclined Surface Deposition, ISD).
After these textured substrates have been obtained, deposition of epitaxial oxides is carried out in the form of a multilayer, which acts as a buffer to atomic diffusion and oxidation, and of the REBCO superconducting layer, in which the electric current is transported. In order to prepare these multilayer structures, techniques of vacuum deposition (evaporation, laser ablation, sputtering) or techniques of chemical solution deposition (CSD) based on metal-organic chemical solutions can be used. The latter are particularly interesting due to the possibilities of developing low cost epitaxial superconductors.
The demonstration of the possibility of using trifluoroacetate (TFA) precursors to grow the YBCO superconductor has been widely described as a very important step forward (A. Gupta, R. Jagannathan, E. I. Cooper, E. A. Giess, J. I. Landman, B. W. Hussey, Superconducting oxide films with high transition temperature prepared from metal trifluoroacetate precursors, Appl. Phys. Lett. 52, 1988, 2077; P. C. McIntyre, M. J. Cima, and M. F. Ng, Metalorganic deposition of high-J Ba YCu O thin films from trifluoroacetate precursors onto (100) SrTiO3, J. Appl. Phys. 68, 1990, 4183). These precursors have BaF2, Y2O3 and CuO as final products after the decomposition of the metal-organic precursors and therefore prevent the formation of BaCO3, which enables growing thin YBCO films at lower temperatures. Recently, a new methodology for obtaining anhydrous TFA precursors for obtaining high quality films at the same time as reducing the time required for processing the films and increasing the stability of the precursor solution has been described in patent ES2259919 (B1) and in the international patent application WO 2006/103303.
One of the current objectives is to improve the processes from the environmental point of view, that is, the use of precursor salts and solvents with the smallest possible impact, both from the toxicological and energy points of view. Thus systems have been described for reducing the presence of fluorine in the precursor salts (Dawley, Clem et al. 2001; T. Dawley 2002; Xu, Goyal et al. 2004; Seleznev and Cima 2005), as well as reducing the thermal treatment times using various types of additives (T. Dawley 2002; Dawley, Clem et al. 2004).
The present invention provides a process for obtaining superconducting materials through the use of a solution of metal-organic precursors with lower fluorine content and with stabilising organic additives. The process enables obtaining high quality superconducting materials easily, given that the improvement in the thermal treatment for the preparation of the superconducting layers makes it possible to carry out pyrolysis and crystal growth in a single stage. In addition, the low fluorine content reduces the risks of toxicity. A first aspect of the present invention refers to a process for obtaining a superconducting material comprising deposition from a precursor solution that comprises at least one rare earth or yttrium salt, at least one alkaline earth metal salt and at least one transition metal salt, characterised in that the maximum proportion by weight of fluorine compared to the total weight of the precursor salts is 10%. This implies a reduction in fluorine content of 70% compared to the fluorine content of a standard solution known in the state of the art, which starts from yttrium, barium and copper trifluoroacetates. The minimum fluorine content is that corresponding to the formation of barium fluoride for all the initial barium in the pyrolyzed layer.
In a preferred embodiment, the total concentration of metal ions in the solution is between 0.5 and 2.5 M.
The rare earth salt preferably comprises at least one element selected from Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu and any of their combinations. More preferably, the salt is of Y, Gd, Eu, Dy and any of their combinations. The counterion of this rare earth or yttrium salt may be monofluoro-carboxylate, difluoro-carboxylate, trifluoroacetate, non-fluorinated carboxylate or combinations of these. Still more preferably, the rare earth or yttrium salt is a trifluoroacetate. The alkaline earth metal in a preferred embodiment is selected from Ba, Sr, Ca and any of their combinations, and in a more preferred embodiment the alkaline earth metal is Ba. In a more preferred embodiment, the salt of the alkaline earth is a non-fluorinated carboxylate.
The salt of the transition metal is preferably of Cu and more preferably the salt of the transition metal is a non-fluorinated carboxylate.
In a preferred embodiment, the solution comprises at least one solvent selected from acetic acid, acetone, acetonitrile, benzene, 1-butanol, 2-butanol, 2-butanone, pentanone, t-butyl alcohol, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, 1,2-dichloroethane, diethyl ether, diethylene glycol, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, dimethyl ether, dimethyl formamide, dimethyl sulfoxide, dioxane, ethanol, ethyl acetate, ethylene glycol, glycerine, heptane, triamide, hexane, methanol, methyl t-butyl ether, dichloromethane, N-methyl-2-pyrrolidone, N-methylpyrrolidone, nitromethane, pentane, petroleum ether, 1-propanol, 2-propanol, pyridine, tetrahydrofuran, toluene, triethylamine, o-xylene, m-xylene, p-xylene and any of their combinations. In a more preferred embodiment the solvent is selected from methanol, ethanol, isopropanol and any of their combinations. It a still more preferred embodiment, the solvent is ethanol.
The solution preferably comprises at least one stabilising additive constituted by carbon chains functionalised with alcohol, amino, ether and carbonyl groups, either alone or in combinations or forming part of polymeric chains. When it is an amino alcohol, it is preferably triethanolamine and when it is a urea, it is preferably N,N-dimethylurea. Still more preferably, the stabilising additive is added to the solution in a proportion of from 2% to 20% by weight.
The reduction in the amount of fluorine present in the standard process brings with it the consequent reduction of toxic and corrosive gases, which facilitates the industrial application of the process.
The presence of additives in the initial solution makes the superconducting tape less susceptible to environmental conditions such as humidity. Consequently, it is stable for longer storage times and the environmental requirements for its deposition are reduced compared to the usually described conditions.
The process of the present invention is characterised in that it preferably comprises the decomposition and crystal growth of the deposited product. Such thermal treatment is carried out in a single stage, more preferably at a temperature of between 70 and 900° C. Still more preferably, this treatment is characterised by being carried out in a controlled atmosphere oven and comprises: a first heating that is carried out in an atmosphere of nitrogen with a water vapour pressure of between 7 and 100 mbar and an oxygen pressure of between 0.1 and 1 mbar to a temperature of between 750 and 820° C.; and a second heating at a temperature of between 300 and 500° C. at an oxygen pressure of 1 bar for a period of time less than 8 h, followed by cooling to room temperature.
The process takes place in a single temperature ramp of 5 to 100° C./min up to the temperature of 750 to 820° C.
In this way, the decomposition or pyrolysis of the starting metal-organic salts and subsequent crystal structure growth that takes place in the superconducting layer takes place in a single stage. This implies a global simplification of the process and a reduction of treatment times for possible large-scale application.
The superconducting material will preferably have a composition of AA′2Cu3O7-x, where A is a rare earth or Y (yttrium), A′ is an alkaline earth and x is between 0 and 1, where more preferably, A is selected from Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu and any of their combinations. Still more preferably, A is yttrium. A′ is more preferably selected from Ba, Sr, Ca and any of their combinations. Still more preferably, A′ is barium.
The superconducting material preferably has the formula YBa2Cu3O7-x, where x is between 0 and 1.
In a preferred embodiment, the solution is deposited on a monocrystalline or biaxial textured substrate and in a more preferred embodiment, the substrate is selected from: a rare earth salt or oxide; an alkaline earth salt or oxide; a transition metal salt or oxide; and any of their combinations. In a yet more preferred embodiment, the substrate is selected from a list comprising monocrystals of SrTiO3, LaAlO3, zirconium, stabilised zirconium (YSZ), MgO, rare earth oxides and biaxially textured metal tapes.
In a second aspect, the present invention refers to a superconducting material obtainable according to the process described above in the present invention.
Preferably, the superconducting material has the formula YBa2Cu3O7. This material is characterised by more preferably having a critical current of between 2 and 4 MA/cm2 at 77 K and in the absence of external magnetic field, that is with the magnetic field produced by the sample itself or the auto-field. In a third aspect, the present invention refers to a solution that comprises at least one rare earth or yttrium salt, at least one alkaline earth metal salt and at least one transition metal salt with a fluorine content in the solution of these salts of less than 10% by weight.
In a preferred embodiment, these salts also include a stabilising additive such as those described above.
A fourth aspect of the present invention refers to the use of the solution for obtaining a superconducting material.
Throughout the description and the claims, the use of the word “comprise” and its variants is not intended to exclude other technical characteristics, additives, components or steps. For experts in the subject, other purposes, advantages and characteristics of the invention will follow in part from the description and in part from the practice of the invention. The following examples and figures are provided for illustration purposes and are not intended as limitations of the present invention.
The invention is illustrated below by some tests carried out by the inventors illustrating the specificity and effectiveness of the process for obtaining superconducting materials through the use of a solution of metal-organic precursors with lower fluorine content.
A solution was prepared of 50 ml Y trifluoroacetate, Ba 2,4-pentanedionate and Cu acetate with a total metal concentration of 1.5 M (ratio Y:Ba:Cu of 1:2:3). This was done by weighing 5.35 g (1.25×10−2 moles) of Y(TFA)3, 10.59 g (2.5×10−2 moles) of Ba(acac)2 and 6.81 g (1.75×10−2 moles) of Cu(AcO)2 that had been previously dried for 16 hours in an oven at 70° C. in a vacuum. The salts were dissolved in 20 ml methanol and 10 mL (7.5×10−2 moles) of triethanolamine (TEA) were added over the mixture, adjusting the final volume to 50 mL with methanol.
This solution was deposited by the spin coating technique on a monocrystalline substrate of LaAlO3 of dimensions 5×5 mm, thickness 0.5 mm and orientation (100). Next, thermal treatment was carried out to achieve the formation of the YBa2Cu3O7 phase. This was performed in an oven where a rapid temperature rise (25° C./min) was applied until reaching temperatures in the range of 790-815° C. This temperature was maintained for 180 minutes (the last 30 minutes in the dry) and then a descending ramp was applied at a rate of 2.5° C./min until reaching room temperature. In this case, the O2 pressure was 0.2 mbar and of water pressure was 7 mbar. The gas flow was that permitted by the mass flow controller used (Bronkhorst High-Tech) for making the mixture, with a range of 0.012 to 0.6 l/min for N2 and of between 0.006 and 0.03 l/min for O2. Oxygenation of this sample was carried out using the same dry atmosphere without removing the sample from the oven. The temperature was raised to 450° C., the carrier gas was changed to dry O2 at 1 bar pressure and this temperature was maintained for a time of 90 minutes. Next, a descending temperature ramp was performed at 300° C./h until reaching room temperature. The resulting layer was approximately 275 nm in thickness.
The sample was characterised by X-ray diffraction, SEM images and measurement of the critical current at 77 K and of the auto field (Jc=3.6×106 A/cm2). For reference values, the dependence of the critical current as a function of magnetic field applied perpendicularly to the substrate at 65 K was measured. It was found that Jc=0.45×106 A/cm2 at 65 K and H=1 T.
A vial with a septum-type cap was filled with 6.60 g N,N-dimethylurea (7.5×10−2 moles) and over this were added 20 ml of the YBCO solution in methanol prepared as in example 1. The mixture was stirred at room temperature and filtered through a 0.45 μm filter. The mixture thus prepared was preserved in an atmosphere of Ar.
This solution of Y, Ba and Cu salts, containing 20% of N,N-dimethylurea, was deposited on a LaO substrate under the same conditions indicated in Example 1. Thermal treatment of the deposited sample was carried out as described in Example 1 to result in the formation of the YBa2Cu3O7 phase. The resulting layer was 200 nm in thickness. The sample was characterised by scanning electron microscope and by X-ray diffraction (
The same process as described in Example 1 was followed except that ethanol was used as a solvent.
This solution of Y, Ba and Cu salts containing 20% of TEA was deposited on a LaO substrate under the same conditions as indicated in Example 1. Thermal treatment of the deposited sample was carried out as described in Example 1 to result in the formation of the YBa2Cu3O7 phase. The resulting layer was 200 nm in thickness. The sample was characterised by scanning electron microscope and by X-ray diffraction (
The same process as described in Example 2 was followed and ethanol was used as a solvent.
This solution of Y, Ba and Cu salts containing 20% of TEA was deposited on a LaO substrate under the same conditions as indicated in Example 1. Thermal treatment of the deposited sample was carried out as described in Example 1 to result in the formation of the YBa2Cu3O7 phase. The resulting layer was 200 nm in thickness. The sample was characterised by scanning electron microscope and by X-ray diffraction (
| Number | Date | Country | Kind |
|---|---|---|---|
| P 200931114 | Dec 2009 | ES | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/ES2010/070798 | 12/3/2010 | WO | 00 | 10/12/2012 |
