JP2008204958A - Oxide superconductor and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxide superconductor, which includes c-axis oriented particles at a high rate when a thick film is formed on a substrate and shows high characteristics, capable of adjusting a lattice constant of a mixed superconductor film obtained by mixing raw material solution of a plurality of Ln system superconductors. <P>SOLUTION: The oxide superconductor, in which main components are represented by a general expression LnBa<SB>2</SB>Cu<SB>3</SB>O<SB>7-x</SB>(here, Ln is two elements or more selected from a group of Gd, Tb, Dy, Ho, Er, Tm, and Y, and a content of each element is 10 to 90 mol%), includes fluorine with a molar ratio of 10<SP>-2</SP>to 10<SP>-6</SP>of copper. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an oxide superconductor and a method for manufacturing the same.

  High critical current oxide superconducting materials that have recently been put into practical use are expected to be usefully applied to fusion reactors, magnetic levitation trains, accelerators, magnetic diagnostic equipment (MRI), and some of them have already been put into practical use. Has been made.

Oxide superconductors mainly include bismuth-based and yttrium-based (hereinafter referred to as Y-based) superconductors, but Y-based superconductors with good magnetic field characteristics have attracted much attention as materials that are close to practical use. ing. The Y-based superconductor is an oxide represented by YBa ₂ Cu ₃ O _7-x , and an oxide having a structure in which yttrium is substituted with a partial element of the lanthanoid group is also a superconductor excellent in magnetic field characteristics. It is known. As the lanthanoid group elements, lanthanum, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and the like are known.

  Examples of the method for producing the Y-based superconductor include a pulse laser deposition (PLD) method, a liquid phase growth deposition (LPE) method, an electron beam (EB) method, and a metal organic matter deposition (MOD) method. Among these, the non-vacuum and low-cost MOD method has been in the spotlight in recent years, and is actively researched mainly in the United States and Japan. Among the MOD methods, the MOD method using trifluoroacetic acid (hereinafter referred to as TFA-MOD method) has recently been reported to be able to produce a superconductor having high characteristics.

  In the MOD method, a gel film is obtained by applying and drying a chemical solution onto a single crystal substrate by spin coating or dip coating, and the gel film is subjected to two normal pressures of calcination and main firing. In this method, a superconductor is obtained by heat treatment and oxygen annealing. In this method, the organic substance in the precursor is decomposed into an oxide during calcination performed at 400 to 500 ° C., and a biaxially oriented structure of the oxide layer is formed during the main calcination performed at 700 to 900 ° C.

  In the MOD method, microcrystals are formed after calcination, and a disorderly oriented structure is formed starting from the microcrystals during main calcination, and the influence becomes particularly large when the film thickness is 100 nm or more. In this method, in order to obtain a good orientation structure, rapid heating and quenching are performed in a very short time so that oxides after pyrolysis grow in the film after calcination and fine crystals are not formed. Becomes important. This rapid heating / cooling is performed by putting a sample in and out of an electric furnace, but it is difficult to obtain a uniform film because the degree of heating differs between the central portion and the end portion. For this reason, this method requires a large electric furnace capable of precise temperature control, and it is difficult to obtain a high-performance superconductor with good reproducibility due to the presence of a different phase.

The TFA-MOD method using trifluoroacetate has been developed as a method for improving the MOD method so that the microcrystals in the calcined film do not affect the heat-treated structure after the main calcination. The TFA-MOD method was first reported by Gupta et al. In 1988, but at that time, it was considered that the purity of the solution was low due to the influence of the starting materials, and as with other MOD methods, it showed very remarkable characteristics and reproducibility. There wasn't. Thereafter, the TFA-MOD method was improved by McIntyre et al., And the superconducting critical current value (J _c ) at 77 K, 0 T exceeded 1 MA / cm ² .

  Although the TFA-MOD method is a MOD method, fine crystals in the calcined film do not affect the orientation after the main baking. According to the TEM observation, there are many nanocrystallites in the cross section of the calcined film, but it was confirmed that all of them disappeared after the firing and a biaxially oriented structure was formed with good reproducibility. (Non-Patent Document 1). Therefore, unlike the normal MOD method, carbon that is harmful to the superconducting properties can be almost completely removed by calcination for 10 hours or more, and a superconductor having high properties can be obtained with good reproducibility (non-patented). Reference 2). Initially, the growth mechanism during firing was unclear, but recently it was revealed that a pseudo liquid phase network was formed as a result of the inclusion of fluorine, and microcrystals in the calcined film were eliminated. As a result, it has been clarified in principle that the TFA-MOD method exhibits reproducibility and high characteristics not found in the normal MOD method (Non-patent Document 3). One of the characteristics of the TFA-MOD method is that a trace amount of fluorine remains in the film because the chemical equilibrium reaction is deeply involved in the growth by the formed pseudo liquid phase network. However, it has also been clarified that this small amount of residual fluorine does not deteriorate the superconducting properties.

It is considered that the reduction in the number of a / b-axis oriented particles contributes to the high characteristics and surprising reproducibility in Y-based superconductor film formation by the TFA-MOD method. The a / b-axis oriented particles are c-axis oriented particles in which the superconducting current flows in a direction parallel to the substrate surface, and the superconducting current flows mainly in the direction perpendicular to the substrate surface. This causes the superconducting current in the direction, that is, the superconducting property, to be significantly reduced. At present, the following three points are considered as the causes of the formation of the a / b axis oriented particles. That is,
(1) The main firing conditions (oxygen partial pressure and temperature) are not optimal.
(2) Impurities are present in the solution.
(3) The lattice constant of c-axis oriented particles does not match the lattice constant of the single crystal substrate,
It is a factor.

  Regarding (1), Hammond and Bormann have reported that there are optimum conditions that do not depend on the superconductor fabrication method (Non-Patent Document 4). According to this, the optimum firing temperature decreases by about 25 ° C. every time the oxygen partial pressure during firing is reduced by half. The optimum firing conditions for the MOD method and the TFA-MOD method are the same as those for the PLD method.

  Regarding (2), it is experimentally known that the ratio of c-axis oriented particles increases and the superconducting properties are improved by reducing the amount of impurities. It has also been disclosed that the characteristics are dramatically improved (Patent Document 1).

  With regard to (3), the superconductor should have a-, b-, and c-axis lengths inherent to the substance, but when a thin film is formed on a single crystal substrate, it is adjusted to the lattice constant of the substrate. It is considered that the epitaxial growth occurs in such a distorted state. In general, the thickness of the superconductor obtained by this method is 0.1 to 10 μm, whereas the thickness of the single crystal substrate is about 0.4 to 1.0 mm, which is about 1000 times as thick. This is because the superconducting film grows while being distorted when the lattice constants of the thin film and the substrate are different. It is considered that a lattice constant almost the same as the lattice constant of the single crystal substrate is observed immediately above the substrate. When a very thin film of about 0.1 μm is formed and phase identification is performed by XRD, the value is close to the lattice constant of the substrate. Is observed. However, as the film thickness increases, it is considered that the superconductor approaches the inherent lattice constant. Whether a / b-axis oriented particles or c-axis oriented particles are easily formed is determined by the lattice constant of the single crystal substrate.

Here, when a TFA-MOD method is used to form a YBCO superconductor film having a thickness of 150 to 300 nm on four types of single crystal substrates of LaAlO ₃ , NdGdO ₃ , SrTiO ₃ , and CeO ₂ / YSZ, XRD measurement is performed. The peak intensity ratio of the a / b axis oriented particles in FIG. 4 is always weaker in the order of NdGdO ₃ , LaAlO ₃ , SrTiO ₃ , CeO ₂ / YSZ, regardless of the film thickness. That is, when a CeO ₂ / YSZ substrate is used, a superconducting film having the highest J _c value is obtained, and a characteristic of 11 MA / cm ² (77K, 0T) is obtained with a thickness of 0.22 μm (Non-patent Document 1). In order to increase the c-axis orientation ratio, it is desirable to change the lattice constant inherent to the substrate or the superconductor, but it is not possible to continuously change the lattice constant of the substrate. This is because the number of substances that can be used as a single crystal substrate is limited, and the lattice constant thereof is also a jump value.

  Therefore, it is desired to improve the c-axis oriented particle ratio by adjusting the axial length of the superconductor. As described above, a specific Ln group element can be substituted at the Y position of the YBCO superconductor. With regard to Ln group elements, lanthanoid contraction in which the ionic radius contracts with the atomic number is observed, and at present, it is difficult to measure the a, b, and c axis lengths of each Ln-based superconductor. The axial length of the body is considered to be different. It is expected to produce a superconductor in which c-axis oriented particles can be easily obtained by mixing two or more types of Ln-based superconductors depending on the substrate.

  As described above, La, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and the like are known as the Ln group element that represents a superconductor by replacing Y. However, some of these Ln group elements are difficult to apply the TFA-MOD method. In the case of La, Nd, and Sm with a small atomic number, if an attempt is made to prepare a trifluoroacetate methanol solution, an esterification reaction occurs and the salt is easily decomposed. If purification is performed under conditions where the esterification reaction does not occur, a large amount of impurities As a result, good superconducting properties cannot be obtained. In the case of Yb having a large atomic number, it has been found that the solubility is extremely low and a solution capable of obtaining a practical film thickness cannot be prepared.

As for other Gd, Tb, Dy, Ho, Er, and Tm, a high-purity methanol solution can be prepared by a SIG (Solvent-Into-Gel) method as in the case of Y trifluoroacetate (non-patent literature). 5, Patent Document 1), a single superconductor is obtained. The critical current density (J _c ) of these superconductors is practically high (3-4 MA / cm ² (77K, 0T)) (Non-Patent Documents 6 and 7). Compared to the J _c value of 7 MA / cm ² (77K, 0T), it is about half the value. It was expected that by mixing each Ln-based solution, a superconductor capable of freely adjusting the a, b, and c axis lengths of a single superconductor within a certain range was obtained. But superconductor obtained by mixing the raw material solution none J _c value is decreased, 1: J _c values of the superconductor obtained when the solution was mixed with 1 ratio 1MA / cm ² (77K, 0T ) Decreased to the extent. The lanthanoid acetate, which is the Ln-based raw material used here, has a purity of 97-98%, and there was a possibility that the ratio of a / b axis oriented particles was increased due to impurities and the characteristics were lowered. .
T. Araki and I. Hirabayashi, Supercond. Sci. Technol. 16, R71 (2003). T. Araki, Cryogenics 41, 675 (2002). T. Araki, et al, J. Appl. Phys. 92, 3318 (2002). RH Hammond and R. Bormann, Physica C 162-164, 703 (1989). Patent 3,556,586 T. Araki, et al, Supercond. Sci. Technol. 14, L21 (2001). T. Iguchi et al. Physica C 392-396 900 (2003). T. Iguchi et al, Supercond. Sci. Technol. 15, 1415 (2002).

  An object of the present invention is to adjust the lattice constant of a mixed superconductor film obtained by mixing a plurality of raw material solutions of Ln-based superconductors. When a thick film is formed on a substrate, c-axis oriented particles It is an object of the present invention to provide an oxide superconductor having a high ratio and high characteristics.

In the oxide superconductor according to one embodiment of the present invention, the main component is a general formula LnBa ₂ Cu ₃ O _7-x (where Ln is selected from the group consisting of Gd, Tb, Dy, Ho, Er, Tm, and Y). And the content of each element is 10 to 90 mol%), and is characterized by containing 10 ⁻² to 10 ⁻⁶ fluorine of copper in a molar ratio.

  The method for producing an oxide superconductor according to another aspect of the present invention includes metal Ln (where Ln is two or more selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er, and Tm). The content of each element is 10 to 90 mol%), and each solution of acetate, barium acetate and copper acetate alone or mixed is reacted with fluorocarboxylic acid and purified to gel A coating solution is prepared by dissolving alcohol in a solvent mainly containing metal Ln, barium and copper in a molar ratio of 1: 2: 3, and coating the coating solution on a substrate forms a film. In the method of manufacturing the oxide superconductor by performing calcination and main firing, the gel obtained in the first purification is dissolved in alcohol to obtain a solution containing impurities, and then the solution is purified again To do Characterized in that to obtain a gel having reduced impurities.

  According to the present invention, an oxide superconductor having a composition containing two or more of Gd, Tb, Dy, Ho, Er, Tm and Y in a wide range of ratios and exhibiting good characteristics can be obtained.

Hereinafter, embodiments of the present invention will be described.
In the method according to the embodiment of the present invention, an oxide superconductor is manufactured by the following procedure.
First, with reference to FIG. 1, the process of purifying by reacting mixed metal acetate with fluorocarboxylic acid will be described. In FIG. 1, the mixed metal acetate a1 is used as a general term for metal acetate containing metal Ln, barium acetate, and copper acetate. As the metal Ln, two or more selected from the group consisting of gadolinium, terbium, dysprosium, holmium, erbium, thulium and yttrium are used. In addition, after preparing each acetate separately, it can also mix and a solution can also be obtained, and the mixing time of each solution is not specifically limited. The molar ratio of metal Ln, barium, and copper is approximately 1: 2: 3. However, even if these molar ratios deviate by about 10% from 1: 2: 3, the properties of the resulting superconductor are not critically affected.

  The mixed metal acetate is mixed and reacted with the fluorocarboxylic acid (a2) of a2 for purification. The fluorocarboxylic acid is selected from the group consisting of trifluoroacetic acid (TFA), pentafluoropropionic acid (PFP), and heptafluorobutanoic acid (HFB). However, since barium acetate produces a precipitate by reaction with PFP or HFB, it is necessary to avoid the combination of barium acetate and PFP or HFB. When PFP or HFB is used for the reaction with another acetate, at least barium acetate is purified by reacting with TFA, and then mixed with the reaction product of the other acetate. In the case of preparing a solution with barium acetate and TFA, the purified product obtained in the middle is a translucent white powder, but other than that, there is no big difference from the ordinary method shown in FIG. When barium trifluoroacetate and other metal salts of pentafluoropropionic acid are used at concentrations above a certain level, precipitation does not occur.

  Note that the fluorocarboxylic acid does not change significantly even when a substance in which fluorine is partially substituted with hydrogen is used. However, as the amount of hydrogen increases, the dissociation constant decreases and a large amount of unreacted acetate remains, so it is empirically found that the molar amount of hydrogen is preferably about 10% or less of the total fluorine amount. When TFA is used as the fluorocarboxylic acid, that is, when a fluorocarboxylic acid having 2 carbon atoms is used, since there is no substance that causes precipitation, all acetates can be dissolved and reacted in ion-exchanged water at once. . Even when a small amount of about 10 mol% of difluoroacetic acid or monofluoroacetic acid in which fluorine is partially substituted with hydrogen is contained in the TFA-based fluorocarboxylic acid, no critical deterioration of the superconductor is observed.

  It is known that carboxylic acid and fluorocarboxylic acid are remarkably different in chemical properties, and carboxylic acid is weak acid, whereas fluorocarboxylic acid is very strong acid. This is because when the acid is dissociated and becomes ions, the oxygen that forms a pair tends to be negatively charged. In a carboxylic acid having no fluorine, hydrogen directly bonded to carbon donates an electron to oxygen through carbon, so that oxygen is easily negatively charged at the time of dissociation. On the other hand, in the case of fluorocarboxylic acid, fluorine whose electronegativity is higher than that of oxygen attracts oxygen electrons through carbon, so that oxygen is neutralized and stabilized during dissociation. Therefore, it becomes a strong acid easily maintaining the ionized state of hydrogen ions. For this reason, for example, since acetic acid and trifluoroacetic acid have dissociation constants different by 4 digits, it is considered that almost all substances are replaced at the moment when acetate and trifluoroacetic acid are mixed.

  Further, after reacting a metal acetate containing metal Ln with a fluorocarboxylic acid having 3 or more carbon atoms, such as pentafluoropropionic acid, it may be substituted with a fluorocarboxylic acid group having a lower carbon number, such as a trifluoroacetic acid group. . In the TFA-MOD method, a carbon driving mechanism acts at the time of calcination, and harmful carbon is easily removed. However, since a small amount of carbon may remain, trifluoroacetic acid is more desirable than pentafluoropropionic acid. Substituting with a fluorocarboxylic acid having a smaller carbon number does not cause a problem in solubility, but rather improves the solubility. That is, if all salts are converted to trifluoroacetate and then mixed, precipitation does not occur at any concentration.

  Purification is carried out after reacting acetate and fluorocarboxylate, and Solvent-Into-Gel (SIG) method is used for this purification. In the SIG method, a large amount of methanol is added to the gel to replace impurities (water and acetic acid), and the powder or gel having a low impurity content is obtained by intentionally taking in methanol. In this way, by using the SIG method in which the powder or gel is dissolved again in methanol to obtain a high-purity solution, water particularly harmful to the TFA-MOD method can be reduced to about 1/20.

  Next, referring to FIG. 2, a coating solution in which a plurality of solutions are mixed is prepared, this coating solution is formed on a substrate to form a gel film, calcined and baked, and oxide superconductivity The process of obtaining a body will be described. In FIG. 2, the element corresponding to the metal Ln is different between the solution A and the solution B. Here, the metal M and the metal N are used. Solutions A and B can be mixed in any ratio, and in the resulting coating solution of b, the sum of metals M and N, the molar ratio of barium and copper is approximately 1: 2: 3. This coating solution is formed on a substrate to form a gel film. Thereafter, calcination (primary heat treatment) and main firing (secondary heat treatment) and further pure oxygen annealing are performed to obtain an oxide superconductor. In FIG. 2a, an oxide superconductor can be obtained in the same manner even when three or more types of solutions are used.

  The formed gel film undergoes calcination in an electric furnace to become a calcination film made of a metal oxyfluoride. FIG. 3 shows an example of a temperature profile (and atmosphere) during calcination.

(1) The temperature in the heat treatment furnace is rapidly increased from room temperature to 100 ° C. from time 0 to t _a1 (about 7 minutes from the start of heat treatment). At this time, the inside of the heat treatment furnace is placed in a dry oxygen atmosphere at normal pressure. All subsequent heat treatment steps can be performed under normal pressure.

(2) When time t _a1 is reached, the atmosphere in the heat treatment furnace is changed to a humidified atmospheric oxygen atmosphere. Then, the temperature in the heat treatment furnace is increased from 100 ° C. to 200 ° C. between time t _a1 and t _a2 (about 42 minutes from the start of heat treatment). At this time, the humidified pure oxygen atmosphere is set in a range of, for example, a humidity of 1.2% to 12.1%. The above humidity corresponds to dew points of 10 ° C and 50 ° C. The humidity can be adjusted by passing bubbles of atmospheric gas (oxygen gas) through water at a predetermined temperature. That is, the humidity is determined by the saturated water vapor pressure in the bubbles when passing through water. The saturated water vapor pressure is determined by temperature. In order to set the temperature corresponding to the dew point of humidity to be lower than room temperature, the gas is diverted and only a part of the water is passed through the bubbles of atmospheric gas and then mixed. This humidification mainly consists in partial hydrolysis of copper fluoroacetate, which is most easily sublimated, to make an oligomer and to increase the apparent molecular weight to prevent sublimation. When fluoroacetic acid is trifluoroacetic acid, hydrolysis is performed as described below, hydrogen bonds are formed between F and H atoms at both ends of the copper salt, and the apparent molecular weight is increased by connecting 4 to 5 molecules. Therefore, sublimation is suppressed.
CF ₃ COO-Cu-OCOCF ₃ + H ₂ O → CF ₃ COO-Cu-H + CF ₃ COOH ↑.

(3) The temperature in the furnace is gradually increased from 200 ° C. to 250 ° C. between times t _a2 and t _a3 (about 4 hours 10 minutes to 16 hours 40 minutes). The reason for the moderate increase is to prevent the partially hydrolyzed salt from burning due to an abrupt reaction and leaving a carbon component. The covalent bond portion of the salt is opened by a long-time decomposition reaction, and the bond between the metal atom and oxygen (Y—O, Ba—O, Cu—O) or the metal oxide (Y ₂ O ₃ , BaO, CuO) temporarily And Y and Ba are substituted with fluorine as described in Non-Patent Document 1 to form a non-stoichiometric compound with oxygen fluorine. Since the reaction proceeds gradually in this state and the temperature is maintained, only CuO, which is a single substance, grows and becomes nano-crystals of several tens of nanometers. The Y and Ba components having an indefinite ratio of fluorine and oxygen cannot be grown and become amorphous.

(4) The temperature in the heat treatment furnace is increased from 250 ° C. to 400 ° C. during times t _a3 to t _a4 and t _a4 to t _a5 (about 2 hours during this period). Unnecessary organic substances decomposed between time t _a2 and t _a3 remain in the film due to hydrogen bonds or the like. In this step, unnecessary organic substances are removed by heating.

(5) After time t _{a5, the} furnace is cooled while flowing gas. The calcined film thus obtained becomes a superconductor through a main heat treatment and pure oxygen annealing in an electric furnace.

FIG. 4 shows an example of the temperature profile (and atmosphere) during the main firing.
(6) The temperature in the heat treatment furnace is rapidly increased from room temperature to 100 ° C. from time 0 to t _b1 (about 7 minutes from the start of heat treatment). At this time, the inside of the heat treatment furnace is placed in an atmospheric pressure oxygen mixed argon gas atmosphere. The optimum oxygen concentration at this time is determined by the metal type of the superconductor to be fired and the firing temperature. The optimum firing condition of the conventional Y-based (YBa ₂ Cu ₃ O _7-x ) is that the oxygen partial pressure in the case of firing at 800 ° C. is 1000 ppm, and every time the temperature is lowered by 25 ° C., the oxygen concentration is almost halved. It was considered preferable. In all the solutions of the present invention, it is preferable that the oxygen concentration is almost halved every time the temperature is lowered by 25 ° C., but the oxygen partial pressure in baking at 800 ° C. is different depending on whether or not it contains Gd element. When Gd is not included, it is 1000 ppm as in the conventional Y. When Gd is included, the oxygen partial pressure when Gd is 0% and 100% is set to 1000 ppm and 250 ppm, and an oxygen partial pressure that is logarithmically proportionally distributed according to the mixing ratio is used to obtain an almost optimal superconductor. It is done. It has been found that the superconducting property does not become zero even if it is 1000 ppm where it should be 250 ppm, and a superconductor reduced to about 1/3 can be obtained. All subsequent heat treatment steps can be performed under normal pressure.

(7) The temperature in the heat treatment furnace is changed from 750 ° C. to 825 from t _b1 to t _b2 (from 33 minutes to 37 minutes, heated to about 20 ° C. per minute until the maximum temperature is reached) and t _b2 to t _b3 (about 5 minutes). Increase to the maximum heat treatment temperature of ℃. At time t _b1 , the dry gas is humidified in the same manner as in the calcination. The humidification amount at this time can be selected in a wide range from 1.2% (dew point 10 ° C.) to 30.7% (dew point 70 ° C.). Increasing the amount of humidification increases the reaction rate. The amount of increase is estimated to be 0.5 power (detailed description in Non-Patent Document 1). The reason for decreasing the rate of temperature increase from t _b2 to t _b3 is to reduce the excess of the electric furnace temperature at t _b3 . The pseudo liquid phase formation described in Non-Patent Document 3 starts inside the film with the calcined film and water vapor at a temperature of about 650 ° C., and the network is formed inside the film.

(8) Pseudo liquid phase network between time t _b3 and t _b4 (45 minutes to 3 hours and 40 minutes, this time depends on the maximum temperature and the final film thickness and becomes the longest when the temperature is low and the film thickness is thick) To LnBa ₂ Cu ₃ O ₆ (Ln is two or more selected from Gd, Tb, Dy, Ho, Er, Tm, and Y) are sequentially formed on the substrate, and HF gas and the like are simultaneously released. The simplified chemical reaction at this time is described as follows.

(Ln-OF: amorphous) + H ₂ O → Ln ₂ O ₃ + HF ↑
(Ba-OF: Amorphous) + H ₂ O → BaO + HF ↑
(1/2) Ln ₂ O ₃ + 2BaO + 3CuO → LnBa ₂ Cu ₃ O ₆
(9) The gas is switched to the dry gas from time t _b4 . The oxide LnBa ₂ Cu ₃ O ₆ formed up to t _b4 is stable to water vapor at a high temperature around 800 ° C., but is decomposed by water vapor at around 600 ° C., so it is switched to a dry gas.

(10) Subsequent to time t _b4 to t _b5 (about 10 minutes), the temperature in the heat treatment furnace is continuously lowered from time t _b5 to t _b6 (about 2 hours to 3 hours 30 minutes). During this time, there is no change in the oxide formed.

(11) At time t _b6 , the gas is switched from oxygen-mixed argon gas to dry pure oxygen gas. By this pure oxygen annealing, LnBa ₂ Cu ₃ O ₆ becomes LnBa ₂ Cu ₃ O _7-x (x = 0.07), and a superconductor is obtained. This pure oxygen switching temperature differs depending on the metal Ln. In the case of conventional Y, the temperature was 525 ° C. However, it is better to start annealing at a slightly lower 425 to 525 ° C. when Gd is included as Ln.

  In addition, with reference to FIGS. 5A and 5B, the growth mechanism of crystal grains of the superconductor during the main firing will be described. FIG. 5A shows the initial stage of growth, and FIG. 5B shows the middle stage of growth. As shown in FIG. 5A, in the initial stage of growth, nuclei 4 of superconducting particles are uniformly formed in the superconductor precursor 3 constituting the film 2 after calcination formed on the substrate 1. As shown in FIG. 1B, in the middle stage of growth, the crystal 5 grows in the horizontal direction in the figure starting from the nucleus 4, and a grain boundary 6 is formed where it hits the adjacent crystal 5.

  In a superconductor grown by such a mechanism, grain boundaries are regularly arranged every 5 to 50 nm where microcrystals collide with each other. The period of this grain boundary seems to change at 5 to 50 nm depending on the annealing conditions during the main firing. This periodic grain boundary formation in the microscopic region is effective for trapping magnetic flux, and is considered to enhance both the characteristics and reproducibility of the superconductor manufactured by the method of the present invention. In fact, it has been reported that a current of about 200 A is obtained with high reproducibility between both ends of a 10 m class wire.

  In addition to the direct influence of residual carbon as described above, factors that degrade the superconducting characteristics include a decrease in the c-axis oriented grain ratio due to heat treatment conditions and impurities in the solution. In the Ln-based superconductor, similarly to the Y-based, c-axis oriented grains are formed on the substrate surface, so that a superconducting current flows in a direction horizontal to the surface. However, since the a-axis and b-axis lengths are substantially equal and are about 1/3 of the c-axis length, a / b-axis oriented grains, which are side-by-side textures of c-axis oriented grains, are likely to be formed depending on conditions. When this structure is formed, current flows only in a direction perpendicular to the substrate surface, so that the superconducting current in the parallel direction is interrupted and the characteristics are degraded. Further, it is considered that the c-axis oriented grains have a growth rate in the direction parallel to the substrate surface that is nearly 100 times the rate in the stacking direction. That is, in the case of an a / b axis oriented grain, it grows fast in the direction perpendicular to the substrate surface and becomes a factor of deteriorating superconducting properties.

The nucleation probability of the c-axis oriented grains and the a / b-axis oriented grains is considered to be determined by the consistency with the lattice constant of the substrate surface, and the c-axis oriented grains are selected by selecting the heat treatment conditions (oxygen partial pressure and firing temperature). It is possible to maximize the formation probability. However, it has also been confirmed on the other hand that the presence of impurities results in the formation of a / b-axis oriented grains even under conditions where c-axis oriented grains are likely to be formed, resulting in poor characteristics. The characteristics of the thick Y-based superconducting film obtained by using a solution synthesized without using the SIG method are particularly deteriorated. The structure of the a / b-axis oriented grains grows to the vicinity of the surface by nucleation. However, in the thick film, the a / b-axis oriented grain generation rate per unit area increases, and the characteristics are likely to deteriorate. On the other hand, when a Y-based superconducting film is obtained by the TFA-MOD method using a high-purity solution by the SIG method, the influence of the a / b axis oriented grains is small, and as described above, the J _c value is high with good reproducibility. Is obtained.

Also in the present invention, the influence of a / b axis oriented grains can be reduced by using a high purity solution by the SIG method. In the present invention, in order to prevent deterioration of characteristics, all the Ln-based raw material solutions are made into high purity solutions by the SIG method. It was found that the _Jc value was reduced to about half in the Ln-based simple substance when the purity was not high. When two kinds of solutions containing these impurities are mixed at a ratio of 1: 1, the _Jc value is particularly remarkably reduced, and the value is reduced to about 1/3 of that before mixing. Mechanism J _c value is greatly reduced when the solution was mixed is not known at present, but there are inherent impurities Ln system respectively, large J _c value in synergy impurity type is increased by mixing It is thought to decline.

More specifically, the oxide superconductor according to the embodiment of the present invention can be defined as follows. That is, it is formed as a film on the substrate, and the main component is LnBa ₂ Cu ₃ O _7-x (where Ln is selected from the group consisting of gadolinium, terbium, dysprosium, holmium, erbium, thulium and yttrium 2 And the content of each element is 10 to 90 mol%), and contains 10 ⁻² to 10 ⁻⁶ fluorine of copper in a molar ratio. In this specification, the term “film” refers to a film having a thickness of 0.05 μm to 10 μm. Assuming that the peak intensity of the c-axis oriented grains is I _c and the peak intensity of the a / b-axis oriented grains is I _ab , _rab = I _ab / (I _c + I _ab ). In the oxide superconductor according to the embodiment of the present invention, _rab is 15% or less for all metals Ln. Further, by TEM observation in a cross section perpendicular to the substrate surface, the ratio of the biaxially oriented layer at the interface between the substrate and the LnBa ₂ Cu ₃ O _7-x is 95% or more, and the biaxially oriented ratio of the surface layer is 80%. It is as follows. Further, by TEM observation on a plane parallel to the substrate moved by 50 nm in the vertical direction from the substrate, a grain boundary having a bond angle of about 0.2 to 1 degree is regularly arranged every 5 to 50 nm.

By the method according to the embodiment of the present invention, a solution in which the amount of impurities is reduced by the SIG method in the MOD method using a fluorocarboxylic acid is prepared, and the essential a, b, and c axis lengths are changed by mixing the raw material solutions. An oxide superconducting thin film reflected in the _c value can be produced. For this reason, it is possible to preferentially form c-axis oriented particles on a metal substrate with an intermediate layer whose lattice constant can be changed relatively freely as well as when producing a thick superconductor on a single crystal. Therefore, it is possible to obtain a superconductor having a higher J _c value than the conventional one. Further, an oxide superconductor whose characteristics are not deteriorated even when Gd, Tb, Dy, Ho, Er, Tm, and Y are mixed at an arbitrary ratio is obtained.

(Example 1)
About 3.7 hydrate powder of (CH ₃ OCO) ₃ Y, (CH ₃ OCO) ₂ Ba anhydride, and about 1.0 hydrate blue powder of (CH ₃ OCO) ₂ Cu An acetate solution was prepared by dissolving in ion-exchanged water so that the ratio was Y: Ba: Cu = 1: 2: 3, and the total reaction equimolar amount of trifluoroacetic acid (CF ₃ COOH, TFA) and eggplant-shaped flask Mixed and stirred in. Using a rotary evaporator, this mixed solution was placed under reduced pressure for about 10 hours for reaction and purification to obtain a dark blue gel SL1Yspg (system preliminary gel).

  The gel SL1Yspg was completely dissolved by adding methanol corresponding to about 100 times its weight to obtain a blue solution. Using a rotary evaporator, this blue solution was placed under reduced pressure for about 12 hours and purified again to obtain a dark blue gel SL1Ysg (hereinafter, this method is referred to as SIG (Solvent-Into-Gel) method). This gel SL1Ysg was dissolved again in methanol and diluted with a measuring flask to obtain a coating solution SL1Ys of 1.50 mol / L in terms of metal ion.

  Weight measurement was performed before and after concentration adjustment using a volumetric flask to measure the density of the solution, and the amount of the mixed substance was calculated by weight control during solution mixing described later.

Metal ion conversion in the same manner as above except that (CH ₃ OCO) ₃ Gd powder of about 4.4 hydrate was used instead of (CH ₃ OCO) ₃ Y about 3.7 hydrate. A 1.50 mol / L coating solution SL1Gds was obtained.

(CH ₃ OCO) instead of about 3.7 hydrate of _{3 Y, (CH 3 OCO)} 3 except for using a powder of about 5.1 hydrate of Ho is in the same manner as described above, terms of metal ions A 1.50 mol / L coating solution SL1Hos was obtained.

Metal ion conversion in the same manner as above except that (CH ₃ OCO) ₃ Tm about 4.3 hydrate powder was used instead of (CH ₃ OCO) ₃ Y about 3.7 hydrate. A coating solution SL1Tms of 1.50 mol / L was obtained.

  Coating solution SL1Ys and coating solution SL1Gds are mixed at a ratio of 9: 1, 8: 2, 7: 3, 6: 4, 5: 5, 4: 6, 3: 7, 2: 8, or 1: 9. Thus, mixed coating solutions SL1x91YGd, SL1x82YGd, SL1x73YGd, SL1x64YGd, SL1x55YGd, SL1x46YGd, SL1x37YGd, SL1x28YGd, SL1x19YGd were obtained.

  The coating solution SL1Ys and the coating solution SL1Hos were mixed as described above to obtain mixed coating solutions SL1x91YHo, SL1x82YHo, SL1x73YHo, SL1x64YHo, SL1x55YHo, SL1x46YHo, SL1x37YHo, SL1x28YHo, SL1x19YHo.

  The coating solution SL1Ys and the coating solution SL1Tms were mixed in the same manner as described above to obtain mixed coating solutions SL1x91YTm, SL1x82YTm, SL1x73YTm, SL1x64YTm, SL1x55YTm, SL1x46YTm, SL1x37YTm, SL1x28YTm, SL1x19YTm.

Each single coating solution and mixed coating solution was spin coated onto a (100) LaAlO ₃ single crystal orientation substrate. The spin coating conditions were an acceleration time of 0.2 seconds, a rotational speed of 2,000 rpm, and a holding time of 150 seconds. Next, calcination was performed by the method shown in FIG. At this time, the heat treatment from t _{a2 to} t _a3 was performed from 200 ° C. to 250 ° C. over 11 h 43 m in a 4.2% humidified pure oxygen atmosphere. Subsequently, calcination was performed under the conditions shown in FIG. At this time, heat treatment in a 4.2% humidified 1000 ppm oxygen mixed argon atmosphere of t _{b3 to} t _b4 was performed at 800 ° C., and heat treatment in a dry pure oxygen atmosphere after t _b6 was performed at 525 ° C. or less. Thus, a superconductor was obtained from each coating solution. The obtained superconductor samples were named so that Fm was added to the end of the coating solution. For example, the superconductor obtained from the coating solution SL1Ys is SL1YsFm, and the superconductor obtained from the coating solution SL1x55YTm is SL1x55YTmFm.

  Regarding the calcined film after calcining the coating solution SL1YsFm and the superconducting film SL1YsFm obtained by the main firing, the element distribution from the film surface to the substrate direction was measured by SIMS. These results are shown in FIG. 6 and FIG.

  As shown in FIG. 6, in the calcined film, F is distributed throughout the film. In terms of molar ratio, F is about 1/10 of Cu, which is a considerably large amount.

On the other hand, as shown in FIG. 7, in the superconducting film obtained by firing, F is distributed in a large amount on the film surface (near zero on the X axis), but decreases as it gets closer to the substrate. Thus, the phenomenon of fluorine remaining in the film is deeply related to the fact that the removal of hydrogen fluoride is the reaction rate-limiting in the chemical equilibrium reaction during the main firing. The superconducting film manufactured by the TFA-MOD method has a unique fluorine amount distribution shown in FIG. 7 and contains residual fluorine of about 10 ⁻² to 10 ⁻⁶ of Cu in molar ratio.

  The Ln-based mixed superconductor obtained from the mixed coating solution also has substantially the same residual fluorine amount distribution because the basic chemical reaction does not change only by replacing part of Y with Ln.

All samples were measured for critical current density (J _c ) and critical temperature (T _c ) by the induction method. All measurements were performed under conditions of 77K and 0T. In order to examine the distribution of the experimental data, unmixed YBCO superconducting films were manufactured for each of the three mixed systems, and J _c and T _c were measured, respectively. The thickness relates J _c measured by the inductive method, the sample was divided into small pieces of approximately 3mm square to calculate the average film thickness of a material amount of ICP (inductively excited plasma emission spectroscopy). The film thickness was 150 to 220 nm.

  Table 1 summarizes the characteristics of the Y-Gd mixed superconducting film, Table 2 summarizes the characteristics of the Y-Ho mixed superconducting film, and Table 3 summarizes the characteristics of the Y-Tm mixed superconducting film.

FIG. 8 shows the relationship between the content of Gd, Ho or Tm in the metal Ln and T _c . First, as can be seen from the result of the unmixed YBCO superconducting film 3 sample, it is considered that the T _c value includes an error of ± 0.2 to 0.3K. T _c of YBCO / GdBCO mixed superconducting films, even in consideration of an error, it is understood that the intermediate value between the YBCO superconducting film and GdBCO superconductor film. Strictly speaking, the other two types of mixed superconducting films cannot be said to be intermediate values of the two single superconducting films, but can be said to show _Tc values that are not significantly deviated. Of the three mixed superconducting films, the most low T _c of YBCO / TmBCO mixed superconducting films, which reflects that the Tc of TmBCO superconductor film unmixed is considered the lowest.

The result of FIG. 8 suggests that the T _c value of the superconductor may be determined by the atomic radius of the metal entering the Y site, and that the metal elements entering the Y site are uniformly mixed in the mixed superconductor. It also shows. This is because it is conceivable that a network connecting only the Gd-based superconductors is completed in the Y-based superconductor in which 50% of the Gd component is mixed, and if the network exists, the T _c value is about 92. If it is shut off, it is likely to take about 90.3K of the Y system, but it is actually an intermediate value. From this, the atoms are uniformly dispersed, and it is highly possible that the T _c value is determined by the average atomic radius.

Gd in the metal Ln in Fig. 9 shows the relationship between Ho or Tm content and J _c. Except for a part of the YBCO / GdBCO system, the other superconducting films show a J _c value of about 6.5 MA / cm ² (77K, 0T). It turns out that the superconductor of a high characteristic is obtained by setting it as a highly purified solution. In the YBCO / GdBCO system having low characteristics, it is considered that the conditions of firing at 800 ° C. and oxygen partial pressure of 1000 ppm are not suitable. The optimum firing condition for the GdBCO superconducting film is 800 ° C. and an oxygen partial pressure of about 250 ppm. In the YBCO / GdBCO mixed superconducting film, high characteristics can be obtained by logarithmically distributing the oxygen partial pressure from 1000 ppm to 250 ppm depending on the amount of the Gd component.

Table 4 shows J _c and T _c of the superconducting films obtained by performing firing at an optimum oxygen partial pressure at 800 ° C. for SL1 × 37YGdFm, SL1 × 19YGdFm, and SL1GdsFm. As is apparent from Table 4, when the optimum firing condition is adopted, a J _c value of about 6.5 MA / cm ² (77K, 0T) is obtained.

Improvement of J _c values are confirmed by the ratio of a / b-axis-oriented grains can be reduced in the XRD pole figure. In the film formation on the LaAlO ₃ substrate, the intensity ratio cannot be known because the a / b-axis oriented particles overlap with the substrate peak. However, by using the (103) plane of the polar figure, the a / b-axis oriented The diffraction intensity caused by the particles and c-axis oriented particles can be measured. Here, when a diffraction intensity was I, the ratio of the intensity of a / b-axis-oriented grains of the total intensity of a / b-axis-oriented grains and c-axis-oriented _{grains, r ab = I ab / (} I c + I _ab ).

In the conventional method, r _ab was less are not characteristic to below 0.15. For example, in SL1x55YGdFm membranes prepared by conventional methods (3 samples), r _ab are each 0.165,0.250,0.181, J _c value (77K, 0T) is 1 MA / cm ² as low value Met.

On the other hand, in the SL1x55YGdFm membrane produced by the method of the present invention, the r _ab 0.034, J _c value (77K, 0T) is 6.83MA / cm ^2, significant improvement was observed.

(Example 2)
A powder of about 3.7 hydrate of (CH ₃ OCO) ₃ Y and a blue powder of about 1.0 hydrate of (CH ₃ OCO) ₂ Cu have a molar ratio of Y: Cu = 1: 3. An acetate solution was prepared by dissolving in ion-exchanged water and mixed and stirred in an eggplant type flask with a total reaction equimolar amount of pentafluoropropionic acid (CF ₃ CF ₂ COOH, PFP). Using a rotary evaporator, this mixed solution was placed under reduced pressure for about 10 hours for reaction and purification to obtain a dark blue gel SL2YCupg-PFP. This gel SL2YCupg-PFP was purified by the SIG method to obtain gel SL2YCug-PFP, which was then dissolved in methanol to obtain a solution SL2YCu-PFP of 1.50 mol / L in terms of metal ions.

1.50 mol in terms of metal ion in the same manner as above except that heptafluorobutanoic acid (CF ₃ CF ₂ CF ₂ COOH, HFB) was used instead of pentafluoropropionic acid (CF ₃ CF ₂ COOH, PFP). / L solution SL2YCu-HFB was obtained.

(CH ₃ OCO) ₂ Ba anhydride was mixed and stirred in a reaction flask with an equimolar amount of CF ₃ COOH. Using a rotary evaporator, the mixed solution was placed under reduced pressure for about 10 hours for reaction and purification to obtain a white powder SL2Bapg. After this powder SL2Bapg was purified by the SIG method to obtain SL2Bag, it was dissolved in methanol to obtain a solution SL2Ba of 1.50 mol / L in terms of metal ions. In this case, when barium acetate is reacted with pentafluoropropionic acid or heptafluorobutanoic acid, a precipitate is formed, and therefore these fluorocarboxylic acids are not used.

  The solution SL2YCu-PFP and the solution SL2Ba were mixed at a molar ratio of Y: Ba: Cu = 1: 2: 3 to obtain a coating solution SL2YsPFP. The solution SL2YCu-HFB and the solution SL2Ba were mixed in the same manner as described above to obtain a coating solution SL2YsHFP. Moreover, coating solution SL2Ys was obtained using only TFA as fluorocarboxylic acid.

  Coating solutions SL2HosPFP, SL2HosHFB, and SL2Hos with a molar ratio of Y: Ba: Cu = 1: 2: 3 were obtained in the same manner as above except that holmium acetate was used instead of yttrium acetate.

  N-type mixed coating solutions were prepared by mixing Y-based coating solutions SL2Ys, SL2YsPFP, and SL2YsHFB with Ho-based coating solutions SL2Hos, SL2HosPFP, and SL2HosHFB at a ratio of 5: 5, respectively. The mixed coating solution prepared using SL2Ys is named SL2YHoT (TFA) T (TFA), SL2YHoTP (PFP), and SL2YHoTH (HFB). The mixed coating solution prepared using SL2YsPFP is named SL2YHoPT, SL2YHoPP, SL2YHoPH. The mixed coating solution prepared using SL2YsHFB is named SL2YHoHT, SL2YHoHP, SL2YHoHH.

In the same manner as in Example 1, each of the mixed coating solutions was spin-coated on a (100) LaAlO ₃ single crystal alignment substrate and calcined and baked to obtain a mixed superconducting film. The obtained nine types of mixed superconducting films are SL2YHoTTFm, SL2YHoTPFm, SL2YHoTHFm, SL2YHoPTFm, SL2YHoPPFm, SL2YHoPHFm, SL2YHoHTFm, SL2YHoHPFm, and SL2YHoHFm.

For these mixed superconducting films, J _c and T _c were measured in the same manner as in Example 1. Table 5 shows the results. As shown in Table 5, even in a mixed superconducting film manufactured using PFP or HFB as the fluorocarboxylic acid, the characteristics are not greatly deteriorated. However, the longer the carbon chain of the fluorocarboxylic acid used, the lower the characteristics of the mixed superconducting film. Note that _rab was 0.15 or less for all the mixed superconducting films in Table 5.

(Example 3)
A powder of about 3.7 hydrates of (CH ₃ OCO) ₃ Y is dissolved in ion-exchanged water, mixed with an equimolar amount of trifluoroacetic acid (CF ₃ COOH, TFA) in an eggplant type flask, and a rotary evaporator. Was used for about 10 hours under reduced pressure for reaction and purification to obtain white powder SL3Ypg. This powder SL3Ypg was purified by the SIG method to obtain SL3Yg, which was then dissolved in methanol to obtain a solution SL3Y of 1.50 mol / L in terms of metal ions.

A white powder was obtained in the same manner as above except that a powder of about 4.4 hydrate of (CH ₃ OCO) ₃ Gd was used instead of a powder of about 3.7 hydrate of (CH ₃ OCO) ₃ Y. After obtaining SL3Gdpg, it was purified by the SIG method to SL3Yg, which was dissolved in methanol to obtain a solution SL3Gd of 1.50 mol / L in terms of metal ions.

In place of the powder of about 3.7 hydrate of (CH ₃ OCO) ₃ Y, powder of about 5.1 hydrate of (CH ₃ OCO) ₃ Ho was used in the same manner as above. After obtaining the color powder SL3Hopg, it was purified by the SIG method to obtain SL3Hog, which was dissolved in methanol to obtain a solution SL3Ho of 1.50 mol / L in terms of metal ions.

Instead of (CH ₃ OCO) ₃ Y about 3.7 hydrate powder, (CH ₃ OCO) ₃ Tm about 4.3 hydrate powder was used in the same manner as described above. After obtaining particles SL3Tmpg, it was purified by the SIG method to SL3Tmg, which was dissolved in methanol to obtain a solution SL3Tm of 1.50 mol / L in terms of metal ions.

A blue powder of about 1.0 hydrate of (CH ₃ OCO) ₂ Ba anhydride and (CH ₃ OCO) ₂ Cu is dissolved in ion-exchanged water so that the molar ratio is Ba: Cu = 2: 3. The total reaction equimolar amount of trifluoroacetic acid (CF ₃ COOH, TFA) was mixed and stirred in an eggplant type flask. Using a rotary evaporator, this mixed solution was placed under reduced pressure for about 10 hours for reaction and purification to obtain a dark blue gel SL3BaCupg. The gel SL3BaCupg was purified by the SIG method to obtain a dark blue gel SL3BaCug, which was then dissolved in methanol to obtain a 1.50 mol / L solution SL3BaCu in terms of metal ions.

  The solution SL3Y and the solution SL3BaCu were mixed at a molar ratio of Y: Ba: Cu = 1: 2: 3 to obtain a coating solution SL3Ys. The solution SL3Gd and the solution SL3BaCu were mixed in the same manner as described above to obtain a coating solution SL3Gds. Solution SL3Ho and solution SL3BaCu were mixed in the same manner as described above to obtain a coating solution SL3Hos. The solution SL3Tm and the solution SL3BaCu were mixed in the same manner as described above to obtain a coating solution SL3Tms.

  The coating solution SL3Ys and the coating solution SL3Gds were mixed at a ratio of 9: 1, 7: 3, 3: 7, or 1: 9 to obtain mixed coating solutions SL3x91YGd, SL3x73YGd, SL3x37YGd, SL3x19YGd.

  The coating solution SL3Ys and the coating solution SL3Hos were mixed in the same manner as described above to obtain mixed coating solutions SL3x91YHo, SL3x73YHo, SL3x37YHo, SL3x19YHo.

  The coating solution SL3Ys and the coating solution SL3Tms were mixed in the same manner as described above to obtain mixed coating solutions SL3 × 91YTm, SL3 × 73YTmo, SL3 × 37YTm, and SL3 × 19YTm.

  The coating solution SL3Gds and the coating solution SL3Hos were mixed in the same manner as described above to obtain mixed coating solutions SL3 × 91GdHo, SL3 × 37GdHo, SL3 × 37GdHo, SL3 × 19GdHo.

  The coating solution SL3Gds and the coating solution SL3Tms were mixed in the same manner as described above to obtain mixed coating solutions SL3x91GdTm, SL3x73GdTm, SL3x37GdTm, SL3x19GdTm.

  The coating solution SL3Hos and the coating solution SL3Tms were mixed in the same manner as described above to obtain mixed coating solutions SL3 × 91HoTm, SL3 × 73HoTm, SL3 × 37HoTm, SL3 × 19HoTm.

In the same manner as in Example 1, each of the mixed coating solutions was spin-coated on a (100) LaAlO ₃ single crystal alignment substrate and calcined and baked to obtain a mixed superconducting film. When producing a mixed superconducting film containing Gd, as described in Example 1, the optimum oxygen partial pressure during firing is calculated according to the amount of the Gd component, and the oxygen partial pressure condition is adopted. did. For these mixed superconducting films, J _c and T _c were measured in the same manner as in Example 1.

  Table 6 summarizes the characteristics of the Y-Gd mixed superconducting film, Table 7 summarizes the characteristics of the Y-Ho mixed superconducting film, and Table 8 summarizes the characteristics of the Y-Tm mixed superconducting film. Although the characteristic values shown in Tables 6 to 8 seem to be somewhat lower than those in Tables 1 to 3, there is a possibility of experimental error. It was confirmed that generally good characteristics were obtained.

  Table 9 summarizes the characteristics of the Gd—Ho mixed superconducting film, Table 10 summarizes the characteristics of the Gd—Tm mixed superconducting film, and Table 11 summarizes the characteristics of the Ho—Tm mixed superconducting film. Since the characteristics of the unmixed GdBCO superconducting film, the HoBCO superconducting film, and the TmBCO superconducting film are similar, the mixed superconducting film has similar characteristics. However, in the method of the present invention, unlike the conventional method, it was confirmed that the characteristics were not greatly deteriorated even in the mixed superconducting film.

Example 4
A powder of about 3.7 hydrate of (CH ₃ OCO) ₃ Y and a blue powder of about 1.0 hydrate of (CH ₃ OCO) ₂ Cu have a molar ratio of Y: Cu = 1: 3. An acetate solution was prepared by dissolving in ion-exchanged water and mixed and stirred in an eggplant type flask with a total reaction equimolar amount of pentafluoropropionic acid (CF ₃ CF ₂ COOH, PFP). Using a rotary evaporator, the mixed solution was placed under reduced pressure for about 10 hours for reaction and purification to obtain a dark blue gel SL4YCupg-PFP. After this gel SL4YCupg-PFP was purified by SIG method to obtain gel SL4YCug-PFP, this was dissolved in methanol to obtain 1.50 mol / L solution SL4YCu-PFP in terms of metal ions. A reaction equimolar amount of trifluoroacetic acid (CF ₃ COOH, TFA) was added to this solution and purified by the SIG method to obtain a solution SL4YCu.

(CH ₃ OCO) ₂ Ba anhydride was mixed and stirred in a reaction flask with an equimolar amount of CF ₃ COOH. Using the rotary evaporator, this mixed solution was placed under reduced pressure for about 10 hours for reaction and purification to obtain white powder SL4Bapg. This powder SL2Bapg was purified by the SIG method to obtain SL4Bag, which was then dissolved in methanol to obtain a solution SL4Ba of 1.50 mol / L in terms of metal ions. At this time, when barium acetate is reacted with pentafluoropropionic acid, a precipitate is formed. Therefore, these fluorocarboxylic acids are not used.

  The solution SL4YCu and the solution SL4Ba were mixed at a molar ratio of Y: Ba: Cu = 1: 2: 3 to obtain a coating solution SL4Ys.

  A coating solution SL4Hos having a molar ratio of Ho: Ba: Cu = 1: 2: 3 was obtained in the same manner as above except that holmium acetate was used instead of yttrium acetate.

  The coating solution SL42Ys and the coating solution SL4Hos were mixed at a ratio of 9: 1, 7: 3, 3: 7, or 1: 9 to obtain mixed coating solutions SL4x91YHo, SL4x73YHo, SL42x37YHo, SL4x19YHo.

Film formation is performed on a (100) LaAlO ₃ single crystal alignment substrate using the film formation, calcination, and main baking conditions described in Example 1, and an acceleration time of 0.2 seconds, a rotation speed of 2, Film formation was performed under the conditions of 000 rpm and holding time of 150 seconds to obtain SL4x91YHoFm, SL4x73YHoFm, SL4x37YHoFm, and SL4x19YHoFm.

In the same manner as in Example 1, each of the mixed coating solutions was spin-coated on a (100) LaAlO ₃ single crystal alignment substrate and calcined and baked to obtain a mixed superconducting film. For these mixed superconducting films, J _c , T _c and _rab were measured in the same manner as in Example 1. Table 12 summarizes these results.

The flowchart for the coating solution preparation in embodiment of this invention. The flowchart for superconductor manufacture in embodiment of this invention. The figure which shows the temperature profile at the time of calcination in embodiment of this invention. The figure which shows the temperature profile at the time of the main baking in embodiment of this invention. The figure which shows the crystal growth mechanism in embodiment of this invention. The figure which shows the SIMS analysis result of the calcined film obtained by calcining in Example 1. FIG. The figure which shows the SIMS analysis result of the oxide superconducting film obtained by baking in Example 1. Shows the oxide superconductor film, Gd in the metal Ln, the relation between Ho or Tm content and T _c in the first embodiment. Shows the oxide superconductor film, Gd in the metal Ln, the relation between Ho or Tm content and J _c of Example 1.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Film, 3 ... Precursor of superconductor, 4 ... Core of superconducting particle, 5 ... Crystal, 6 ... Grain boundary.

Claims (10)

The main component is a general formula LnBa ₂ Cu ₃ O _7-x (where Ln is two or more selected from the group consisting of Gd, Tb, Dy, Ho, Er, Tm and Y, and each element contains The oxide superconductor is characterized in that it contains 10 ⁻² to 10 ⁻⁶ fluorine of copper in a molar ratio.   The oxide superconductor according to claim 1, wherein the oxide superconductor is formed as a film having a thickness of 0.05 to 10 μm on the substrate.   The ratio of the intensity of a / b-axis oriented particles to the total intensity of a / b-axis oriented particles and c-axis oriented particles observed by X-ray diffraction is 15% or less. The oxide superconductor described in 1. According to TEM observation in a cross section perpendicular to the substrate surface, the ratio of the biaxial orientation layer at the interface between the substrate and the LnBa ₂ Cu ₃ O _7-x is 95% or more, and the biaxial orientation ratio of the surface layer is 80% or less. The oxide superconductor according to claim 1, wherein the oxide superconductor is provided.   The TEM observation on a plane parallel to the substrate moved by 50 nm in the vertical direction from the substrate has a structure in which grain boundaries with a bond angle of about 0.2 to 1 degree are regularly arranged every 5 to 50 nm. 3. The oxide superconductor according to 1 or 2. One solution selected from the group consisting of acetate, barium acetate and copper acetate of Ln (Ln is one selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er and Tm) and fluorocarboxylic acid A gel is produced by reaction and purification, and the gel obtained in the first purification is dissolved in alcohol to obtain a solution containing impurities, and then the solution is purified again to obtain a gel with reduced impurities. Further, a first solution preparation step of preparing the first solution by dissolving the gel in a solvent mainly containing alcohol,
Ln other than Ln selected in the first solution preparation step (where Ln is one selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er and Tm), acetate, barium acetate A solution selected from the group consisting of copper acetate and copper acetate is reacted and purified with fluorocarboxylic acid to form a gel, and the gel obtained in the first purification is dissolved in alcohol to obtain an impurity-containing solution. Obtaining a gel with reduced impurities by repurifying the solution, and further dissolving the gel in a solvent mainly comprising alcohol to prepare a second solution;
The first solution and the second solution are mixed so that the content of each of the two types of Ln is 10 to 90 mol%, and the molar ratio of Ln, barium and copper is 1: 2: 3. And a step of coating the solution on a substrate to form a film, calcining and firing.   The method for producing an oxide superconductor according to claim 6, wherein the fluorocarboxylic acid is selected from the group consisting of trifluoroacetic acid, pentafluoropropionic acid and heptafluorobutanoic acid.   The method for producing an oxide superconductor according to claim 6, wherein the solvent contains methanol as a main component.   The method for producing an oxide superconductor according to any one of claims 6 to 8, wherein the fluorocarboxylic acid used in the reaction is substituted with a fluorocarboxylic acid having a small number of carbons after the reaction. One solution selected from the group consisting of acetate, barium acetate and copper acetate of Ln (Ln is one selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er and Tm) and fluorocarboxylic acid A gel is produced by reaction and purification, and the gel obtained in the first purification is dissolved in alcohol to obtain a solution containing impurities, and then the solution is purified again to obtain a gel with reduced impurities. Further, a first solution preparation step of preparing the first solution by dissolving the gel in a solvent mainly containing alcohol,
Ln other than Ln selected in the first solution preparation step (where Ln is one selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er and Tm), acetate, barium acetate A solution selected from the group consisting of copper acetate and copper acetate is reacted and purified with fluorocarboxylic acid to form a gel, and the gel obtained in the first purification is dissolved in alcohol to obtain an impurity-containing solution. Obtaining a gel with reduced impurities by repurifying the solution, and further dissolving the gel in a solvent mainly comprising alcohol to prepare a second solution;
The first solution and the second solution are mixed to form a solution containing the Ln, barium and copper in a molar ratio of 1: 2: 3, and then the solution is coated on a substrate to form a film. And a method for producing an oxide superconductor, comprising the steps of calcining and calcination.

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