METHOD OF MANUFACTURING MAGNESIUM DIBORIDE SUPERCONDUCTING THIN FILM WIRE AND MAGNESIUM DIBORIDE SUPERCONDUCTING THIN FILM WIRE

Abstract

A method of manufacturing an MgB2 thin film wire having an optimum average grain size is done by providing an optimum average grain size range to increase a pinning force and improve Jc with respect to the MgB2 thin film wire. In this method, the MgB2 thin film wire is made of an aggregate of MgB2 grains having a columnar structure which alignment is controlled to be in a direction perpendicular to a surface, a ratio of MgB2 to a total volume of the thin film wire is 90% or more, an average grain size of the grains is 30 nm or more and 200 nm or less by forming the MgB2 thin film having a film thickness of 1000 nm or more and 10000 nm or less in the lateral direction, and the average grain size of the grains is 40 nm or more and 100 nm or less.

Claims

1.-9. (canceled)

10. An MgB.sub.2 thin film wire which is made of an aggregate of MgB.sub.2 grains having a columnar structure of which alignment is controlled to be in a direction perpendicular to a surface of a substrate, wherein a grain boundary interval formed by the MgB.sub.2 grains is eight times or more of a coherence length, wherein a thin film of the MgB.sub.2 thin film wire is 1000 nm or more and 10000 nm or less, and wherein an average grain size of the MgB.sub.2 grains is 30 nm or more and 200 nm or less.

11. The MgB.sub.2 thin film wire according to claim 1, wherein the average grain size of the MgB.sub.2 grains is 40 nm or more and 100 nm or less.

12. A method of manufacturing an MgB.sub.2 thin film wire which is made of an aggregate of MgB.sub.2 grains having a columnar structure of which alignment is controlled to be in a direction perpendicular to a surface of a substrate, comprising: forming a film of Mg and B on the substrate by deposition or sputtering, wherein a grain boundary interval formed by the MgB.sub.2 grains is set to be eight times or more of a coherence length, wherein a thin film of the MgB.sub.2 thin film wire is set to be 1000 nm or more and 10000 nm or less, and wherein an average grain size of the MgB.sub.2 grains is set to be 30 nm or more and 200 nm or less.

13. The method of manufacturing an MgB.sub.2 thin film wire according to claim 3, wherein the average grain size of the MgB.sub.2 grains is set to be 40 nm or more and 100 nm or less.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0026] FIG. 1-a is a schematic diagram illustrating magnetic flux quanta infiltrating into a semiconductor with grain boundaries and a direction of a Lorentz force.

[0027] FIG. 1-1-1 is a schematic diagram illustrating magnetic flux quanta infiltrating into a semiconductor with grain boundaries and a direction of a Lorentz force.

[0028] FIG. 1-1-2 is a schematic diagram illustrating magnetic flux quanta infiltrating into a semiconductor with grain boundaries and a direction of a Lorentz force.

[0029] FIG. 1-2-1 is a schematic diagram illustrating magnetic flux quanta infiltrating into a semiconductor with grain boundaries and a direction of a Lorentz force.

[0030] FIG. 1-2-2 is a schematic diagram illustrating magnetic flux quanta infiltrating into a semiconductor with grain boundaries and a direction of a Lorentz force.

[0031] FIG. 2 is a schematic diagram illustrating a distribution of a pin potential depending on a grain boundary interval in a periodic case.

[0032] FIG. 3 is a diagram illustrating a distribution of pin potential in the vicinity of grain boundaries depending on a grain boundary interval in a periodic case.

[0033] FIG. 4 is a diagram illustrating a distribution of pinning force in the vicinity of grain boundary depending on a grain boundary interval in a periodic case.

[0034] FIG. 5 is a schematic diagram illustrating the existence of an optimum average grain size for improving Jc in the present invention.

[0035] FIG. 6 is a schematic diagram defining a grain size in the present invention.

[0036] FIG. 7 is a diagram illustrating dependency of Jc on average grain size taking into consideration the contention between grain boundary density and element pinning force.

[0037] FIG. 8 is a diagram illustrating dependency of an average crystal grain size on a film thickness of an MgB.sub.2 film in the embodiment of the present invention.

[0038] FIG. 9 is a diagram illustrating scanning microscopic images of MgB.sub.2 films having different film thicknesses in the embodiment of the present invention.

[0039] FIG. 10 is a diagram illustrating dependency of Jc of an MgB.sub.2 thin film wire on average grain size measured at 20 K and 5 T in the embodiment of the present invention.

[0040] FIG. 11 is a diagram illustrating phase images obtained by measuring the MgB.sub.2 thin film 140 formed to have a film thickness of 1000 nm at heating temperatures of the substrate of 200 C., 250 C., and 300 C. by using an atomic force microscope (AFM).

[0041] FIG. 12 is a diagram illustrating dependency of the average grain size of the MgB.sub.2 thin film on the film thickness.

[0042] FIG. 13 illustrates Jc of the prepared MgB.sub.2 thin film wires which is measured at 20 K, 5 T plotted to be overlapped on FIG. 7.

DESCRIPTION OF EMBODIMENTS

[0043] FIG. 2 is a schematic view illustrating a distribution of a pin potential (hereinafter, abbreviated to U) depending on a grain boundary interval in a case where periodic grain boundaries exist. If the grain boundary interval becomes too small, it is considered that a spatial variation amount U (hereinafter, abbreviated to U) of the pin potential decreases, and thus, an element pinning force decreases.

[0044] FIG. 3 is a pin potential distribution diagram in the vicinity of the grain boundaries depending on the grain boundary interval in the case of taking into consideration periodic grain boundaries. The grain boundary interval is denoted by a.sub.GB (hereinafter, abbreviated to a.sub.GB). In the case of changing the a.sub.GB from two times to twelve times of the coherence length .sub.ab (hereinafter, abbreviated to .sub.ab), with respect to U in the vicinity of the grain boundaries, U does not change if the a.sub.GB is eight times or more of the .sub.ab, and U decreases if the a.sub.GB is less than eight times of the .sub.ab. Since the spatial differentiation of U gives a pinning force, if the grain boundary interval becomes too small, it is considered that the pinning force decreases, and thus, Jc decreases.

[0045] FIG. 4 illustrates a distribution of a pinning force per grain boundary pin in the vicinity of the grain boundaries with the grain boundary interval as a parameter in the spatial differentiation of FIG. 3. If the a.sub.GB is eight times or more of the .sub.ab, it converges to one curve, and the pinning force per grain boundary pin does not change, and thus, as the grain boundary density increases, the element pinning force per unit volume linearly increases. However, if the a.sub.GB becomes less than eight times of the .sub.ab, the pinning force per grain boundary pin decreases, and thus, a proportional relationship does not exist between the element pinning force and the grain boundary density.

[0046] FIG. 5 is a schematic diagram illustrating an optimum region for improving Jc according to the present invention. The optimum region may be obtained by taking into consideration the effect of contention between grain boundary density and pinning force per grain boundary pin. The horizontal axis indicates the average grain size, and the vertical axis indicates Jc. It is possible to optimize Jc by controlling the average grain size.

[0047] FIG. 6 is a schematic diagram defining a grain size 25 (a.sub.GB) according to the present invention. The MgB.sub.2 thin film wire 200 according to the present invention is made of an aggregate of MgB.sub.2 grains 21 having a columnar structure in the thickness direction of which alignment is controlled to be in a direction perpendicular to the surface and having a ratio of MgB.sub.2 to a total volume of the thin film wire being 90% or more. And the interval between the grain boundaries 22 corresponding to the interface between the superconducting grains determines the Grain size.

[0048] In the present invention, the grain size 25 is defined as the maximum size of the grain in the lateral direction 24 of the thin-film wire, and the average grain size is represented by the average value. In the present invention, the optimum average grain size of MgB.sub.2 is numerically limited by the following method.

[0049] In a case where a current (J) is applied in the magnetic field (B) , the MgB.sub.2 thin film superconducting wire according to the present invention, a Lorentz force represented by the following Mathematical Formula 1 per unit length is applied to the magnetic flux quanta.

f.sub.L=J.sub.0e.sub.z [Matematical Formula 1]

[0050] Herein, 0 is a magnetic flux quantum and is represented by the following Mathematical Formula 2.

.sub.0=2.06710.sup.15 [Wb][Mathematical Formula 2]

[0051] Under the magnetic field B, the average magnetic flux distance <a0> (hereinafter, abbreviated to <a0>) is represented by the following Mathematical Formula 3.

[00001]$\begin{array}{cc}{a}_0\left(B\right)=\sqrt{\frac{2.Math.{}_0}{\sqrt{3}.Math.B.Math.}}& \left[\mathrm{Mathematical}.Math..Math.\mathrm{Formula}.Math..Math.3\right]\end{array}$

[0052] Therefore, there are magnetic flux quanta of nv=B/0 [number/m.sup.2] on average per unit area.

[0053] By taking into consideration the competition between the grain boundary density and the pinning force per grain boundary pin, the energy per magnetic flux quantum is represented by the following Mathematical Formula 4,

[00002]$\begin{array}{cc}{E}_i=\underset{p}{.Math.}.Math.E_{p.Math..Math.i.Math..Math.n}\left(r_{\mathrm{ip}},\right)+\frac{1}{2}.Math.\underset{ji}{.Math.}.Math.E_{\mathrm{vv}}\left(r_{\mathrm{ij}},\right)+E_{\mathrm{FL}}\left(r_i\right)& \left[\mathrm{Mathematical}.Math..Math.\mathrm{Formula}.Math..Math.4\right]\end{array}$

[0054] The first term n the right-hand side represents the contribution of pinning, and the second term represents the modified Bessel function by the repulsive type magnetic flux quanta interstitial phase E function. The third term represents the contribution of the Lorentz force. r[A1].sub.ip is a distance between the grain boundary and the magnetic flux quantum, U.sub.0 is a pin potential per grain boundary pin, .sub.ab and .sub.ab are a coherence length and a magnetic field penetration length of the MgB.sub.2 grains of which alignment is controlled to be in the direction perpendicular to the surface. in addition, e.sub.z is a unit vector in the z direction. The contribution from the right-hand side is represented by the following Mathematical Formulas 5 to 7.

E.sub.pin=U.sub.0 exp((r.sub.ip/{square root over (2)}.sub.ab).sup.2) [Mathematical Formula 5]

E.sub.vv=(.sub.0/4.sub.ab).sup.2 K.sub.0(r.sub.ij/.sub.ab) [Mathematical Formula 6]

E.sub.FL=(J.sub.0e.sub.z).Math.r [Mathematical Formula 7]

[0055] By using the applied current J in a certain area, the average grain size <a.sub.GB>, and the average magnetic flux distance <a0> corresponding to a magnetic field as parameters, an average drift distance <v.sub.drift> of the magnetic flux quanta at 20 K in the steady state was numerically calculated on the basis of Mathematical Formula 4 by using the Monte-Carlo method.

[0056] Based on this, Jc was evaluated from the value of J realized by <v.sub.drift> exceeding a certain value. FIG. 7 illustrates the dependency of Jc on average grain size at 20 K with the magnetic field as a parameter, calculated by taking into consideration the contention between grain boundary density and pinning force per grain boundary pin.

[0057] The average grain size at which Jc has the maximum value does not depend on the magnetic field. Jc has the maximum at about 50 nm, and Jc significantly decreases at less than 30 nm. On the other hand, in the region with a low average grain boundary density, Jc decreases with an increase in average grain size. Jc decreases to about of the peak value at 100 nm, and Jc decreases to about or less of the peak value at 200 nm.

[0058] From the results of the above-described numerical calculation, it can be understood that the MgB.sub.2 thin film wire which can obtain high Jc is made of an aggregate of MgB.sub.2 grains of which alignment is controlled in the direction perpendicular to the surface, a ratio of MgB.sub.2 to a total volume of the thin film wire is 90% or more, and the lower limit of the average grain size of the grains is at least 30 nm or more, preferably, 40 nm or more in the lateral direction. On the other hand, Jc can be improved by setting the upper limit of the average grain size of the MgB.sub.2 thin film to be at least 200 nm or less, preferably, 100 nm or less. Therefore, examples of the method of manufacturing the MgB.sub.2 thin film of which the average grain size is controlled within the above-described range will be described below.

First Embodiment

[0059] A method of manufacturing an MgB.sub.2 thin film superconducting wire that realizes an optimum average grain size range obtained from the result of the numerical calculation and superconducting characteristics of the MgB.sub.2 thin film superconductor obtained by the method will be described.

[0060] FIG. 8 illustrates a method for manufacturing an MgB.sub.2 thin film wire formed by co-depositing Mg and B on a tape-shaped substrate in a vacuum.

[0061] In this embodiment, electron beam evaporation is used together with deposition of Mg and B. Two linear evaporation sources 100 filled with Mg metal material and B metal material are irradiated with respective deflected and accelerated electron beams from a linear electron gun 110, Mg and B are co-deposited on a plurality of tape-shaped substrates 130 to be drawn out and wound up by a reel 120. A metal substrate is used as the substrate 130 on which the MgB.sub.2 thin film is formed. If a metal substrate is used, the deposited Mg and B react with the surface of the metal substrate to form an intermediate layer 145 having strong adhesion to both the substrate and the MgB.sub.2 thin film, and thus, even in the case of a thick MgB.sub.2 thin film described later, a film can be formed without peeling.

[0062] Unlike other copper oxide superconductors and the like, the metal material does not require alignment treatment, so that there is no particular restriction. For example, various materials such as a Cu alloy, an AI alloy, an iron alloy such as stainless steel, an Ni-based alloy such as hastelloy, and a high melting point metal such as Nb, Ta, or Ti can be used, and these materials can be used appropriately according to cost and application. For example, low-cost Cu alloys and AI alloys are used for power transmission lines to which only self-magnetic field is exerted, and stainless steel and Ni-based alloys such as hastelloy are used for coils to which strong electromagnetic stress is exerted. With respect to the substrate 13, the substrate 130 is heated in a range of 200 to 300 C. by a heater (not shown) which is installed in the reel 12 or a sheath heater or an infrared heater (not shown) which is provided in the chamber to heat the substrate 130 from the back side or the side, and Mg and B reaching the substrate 130 react and bind to each other to form the MgB.sub.2 thin film. The lower limit of the temperature range is determined from the fact that the reaction between Mg and B is not sufficiently promoted at 200 C. or lower, and the upper limit of 300 C. or higher is determined from the fact that Mg having high volatility no longer adheres to the substrate 130 and, thus, Mg and B do react with each other.

[0063] In this case, although both Mg and B are deposited by using electron beam evaporation, Mg of which a high vapor pressure can be obtained even at a low temperature can be deposited by heating ceramics or metallic citrus (Knudsen cell, effusion cell, or the like) with a heater, so that it is also possible to use electron beam evaporation only for B having a lower vapor pressure and a high melting point. In addition, as a film formation method in the same vacuum, it is also possible to form the film of both Mg and B by a sputtering method. In addition, after the MgB.sub.2 thin film 140 is formed on the substrate 130, a low resistance metal film of Cu or AI is further formed as a stabilizing layer 170, and lamination is performed in a separate vacuum chamber (not shown) connected to a main film forming apparatus.

[0064] FIG. 9(a) is a diagram illustrating a cross-sectional scanning electron microscopic image of a typical MgB.sub.2 thin film 140 formed on a substrate 130 by using vacuum evaporation, and FIG. 2(b) is a diagram schematically illustrating a crystal structure of the MgB.sub.2 thin film. The MgB.sub.2 thin film 14 is formed with fine columnar crystal grains 150 vertically grown on a substrate 13 through an intermediate layer 145 and grain boundaries 160 thereof. FIG. 10 illustrates a shape image and a phase image obtained by measuring the surface of the MgB.sub.2 thin film 140 by using an atomic force microscope (AFM). It can be seen that the MgB.sub.2 thin film 140 has fine columnar crystal grains 150 in close contact with each other and has many grain boundaries 160 therebetween. In the MgB2 thin film 140, since the grain boundaries 160 of the columnar crystal grains 15 pin the magnetic flux, a high critical current density Jc can be obtained.

[0065] The average grain size of the MgB.sub.2 thin film 140 can be controlled by the heating temperature and the film thickness of the substrate 130 at the time of film formation. FIG. 11 illustrates phase images obtained by measuring the MgB.sub.2 thin film 140 formed to have a film thickness of 1000 nm at heating temperatures of the substrate of 200 C., 250 C., and 300 C. by using an atomic force microscope (AFM).

[0066] The respective average grain sizes are about 40 nm, about 60 nm, and about 80 nm.

[0067] FIG. 12 illustrates dependency of the average grain size of the MgB.sub.2 thin film on the film thickness. Although the average grain size has a width depending on the heating temperature, the average grain size depends mainly on the film thickness, and this, the average grain size becomes larger as the film thickness becomes thicker.

[0068] FIG. 13 illustrates Jc of the prepared MgB.sub.2 thin film wires which is measured at 20 K, 5 T plotted to be overlapped on FIG. 7. The thin film wire with an average crystal grain size of 30 nm has Jc=0.810.sup.5 A/cm.sup.2, the thin film wire with an average crystal grain size of 50 nm has Jc=2.010 .sup.5 A/cm.sup.2, the thin film wire with an average crystal grain size of 110 nm has Jc=1.010.sup.5 A/cm.sup.2, and the thin film wire with an average crystal grain size of 150 nm has Jc=0.510.sup.5 A/c m.sup.2. Although the absolute value is slightly lower than the simulation result of FIG. 7, the film thickness dependency exhibits good accordance, and the validity of the simulation can be verified.

[0069] A film thickness range appropriate for the MaB.sub.2 thin film wire is obtained from FIG. 12. Namely, in a case where the film thickness of the MgB.sub.2 thin film wire is as small as 1000 nm or less, it is difficult to set the average crystal grain size to be 30 nm or more even if the substrate temperature is adjusted. On the other hand, in order to maintain the average crystal grain size of the MgB.sub.2 thin film wire to be 200 nm or less, the upper limit condition of the film thickness is 10000 nm.

[0070] In addition, a film having a film thickness of 1000 nm or more can be formed only in the case of using a metal substrate such as duralumin, copper, or aluminum. In the case of using semiconductors such as Si or sapphire which are common in superconducting electronic devices as a substrate or using an insulating substrate, due to insufficient adhesiveness of the film according to non-formation of the intermediate layer 145 or thermal stress, the film having a film thickness of 1000 nm or more easily peeled off and it is difficult to manufacture the film.

[0071] The MgB.sub.2 thin film wire for optimizing Jc in the present invention is made of an aggregate of MgB.sub.2 grains of which alignment is controlled in the direction perpendicular to the surface, a ratio of MgB.sub.2 to a total volume of the thin film wire is 90% or more, the maximum size of the grains is 30 nm or more and 200 nm or less as an average grain size in the lateral direction, and the film thickness is 1000 nm or more and 10000 nm or less. Furthermore, it is more preferable that the maximum size of the grain is 40 nm or more and 100 nm or less, and the film thickness is 1000 nm or more and 10000 nm or less.

REFERENCE SIGNS LIST

[0072] 10 applied magnetic field [0073] 11 applied current [0074] 12 magnetic flux quantum [0075] 13 Lorentz force [0076] 14 superconductor [0077] 15 grain boundary [0078] 141 superconducting wire in the related art [0079] 1410 superconducting grain constituting superconducting wire in the related art [0080] 151 grain boundaries of superconducting wire in the related art [0081] 142 superconducting thin film wire [0082] 1420 superconducting grain having\columnar structure in thickness direction [0083] 152 grain boundaries of superconducting thin film wire 200 MgB.sub.2 superconducting thin film wire [0084] 21 MgB.sub.2 superconducting grains [0085] 22 MgB.sub.2 superconducting grain boundaries [0086] 23 longitudinal direction of wire [0087] 24 lateral direction of wire [0088] 25 MgB.sub.2 superconducting grain size a.sub.GB [0089] 100 linear evaporation source [0090] 110 linear electron gun [0091] 120 reel [0092] 130 substrate [0093] 140 MgB.sub.2 thin film [0094] 145 intermediate layer [0095] 150 columnar crystal grain [0096] 160 grain boundary [0097] 170 stabilizing layer