The present disclosure relates to quality control methods for superconducting tapes, and more specifically to non-destructive and non-contact methods for measuring the surface resistance of a superconducting tape during tape growth.
Recent progress in the manufacturing of second-generation (2G) high temperature superconductor (HTS) deposited on buffered flexible metal substrates open more possibilities for electric power grid and superconducting magnet applications. In the current manufacturing process, HTS tapes such as YBa2Cu3O7−x, on Hastelloy substrate (YBCO/Hastelloy) often have in situ quality control of surface morphology using high-speed cameras that can detect and flag defects and X-ray diffractometers to access and regulate the tape texture. However, these tools do, not provide direct information on the expected critical current performance of the superconductor tape. Since, kilometers long 2G tapes are manufactured by the MOCVD (or other) process, an ideal solution would encompass a non-contact and non-destructive technique capable of providing real time information about both the buffer and superconducting layers at each point of the manufacturing process. Such non-contact evaluation technique that can correlate normal state properties of the HTS tape during the MOCVD process to its superconducting properties has been elusive thus far.
The present disclosure relates to quality control methods for superconducting tapes, and more specifically to non-destructive and non-contact methods for measuring the surface resistance of a superconducting tape during tape growth, which can be correlated with the complex conductivity and superconducting properties of the tape.
The present disclosure demonstrates that DR methods can be modified and tailored specifically for characterization of a normal/superconducting state conductivity of superconducting tapes. One of an array of DR resonators can be used. The method is both a non-destructive and non-contact technique. In general, such resonators can be used to measure, in situ, the surface resistance (in general complex conductivity) vs. temperature of the fabricated tapes and to provide ,quality control during YBCO tape growth. It will allow detection of information about, potential superconducting properties of tapes deposited at room or higher temperature. YBCO tapes for energy application (dc current application) are deposited on metallic substrate, which makes characterization in normal state much different than characterization of YBCO thin films deposited on epitaxially polished dielectric substrate. However, the method of the present disclosure will also work when tapes are deposited on other than metallic alloy substrates, for example, dielectric substrates. The method also will work not only for high critical temperature superconductors (HTS), but also for other kinds, such as, for example, low critical temperature superconductors (LTS). This assumes that the slope of Rs(T) in normal state of the LTS is correlated with superconducting parameters. It can work even for quality control of metals. In normal state, what is called “a superconductor” behaves like and is essentially just a normal metal.
Microwave material characterization techniques can be used in a variety of techniques, ranging from large scale remote sensing to detection of tumors or cardiovascular plaques in the human body. Microwave resonators can be used to measure the complex impedance of sample material. Microwave resonator techniques can be non-destructive, and in specific configurations, contact between the apparatus and the material to be characterized is not required. The present method can also measure surface impedance of a material in a very wide range, of several orders of magnitude.
Microwave material characterization techniques have been used in a large number of applications and are classified as a nondestructive evaluation (NDE) methods. One such method, a microwave dielectric resonator (DR) technique, has been successfully used for characterization of HTS in a superconducting state. For such an application, the DR is designed for maximum measurement sensitivity and large dynamic range of measured parameters and consists of an extremely low loss dielectric disk terminated with two endplates made of the HTS sample. The geometry and type of dielectric of a DR can be selected to according to the requirements of different applications.
In general, a material parameter of the complex conductivity is not directly measured, but instead the complex surface impedance Zs=Rs+iXs is probed. The imaginary term represents the surface inductive reactance and the real part Rs gives the surface losses per unit area. For the multilayered structures investigated herein, such defined impedance is a function of all parameters describing properties of the multilayers, which in the most general cases include superconductor/dielectric buffer/substrate/metal enclosure conductor. The formula:
for wave impedance derived for a bulk good conductor can be adopted for thick (larger than penetration depth) superconductors in local limit, which in turn makes Zs directly related to the complex conductivity σ(ω)=σ1(ω)−iσ2(ω), where the real σ1 and imaginary σ2 described as a function of frequency ω are related to the thermally excited quasiparticles (normal electrons) and the electronic excitation spectrum (superfluid density), respectively.
In literature, a typical approach for ascertaining the complex impedance of superconductors from measured frequency shift and Q-factor is to use perturbation theory. It has been shown that extended perturbation theory with the addition of impedance transformation, allows for determining the wave impedance of a superconductor with typical thickness of few hundred of nanometers with accuracy similar to the rigorous electromagnetic fields calculation approach. However, it has been shown that significant differences appear between the rigorous and perturbation methods for thin superconducting films (below 50 nm) at temperatures T that are close or above the critical temperature Tc of the superconductor. In the latter temperature range, the film thickness (typically a few hundred nanometers) becomes comparable to or smaller than the penetration (or at the normal state the skin depth). In such a case, electromagnetic fields penetrate through the film and the sample cannot be treated as a bulk case as it is in the superconducting state. As a consequence, the surface impedance of the sample is no longer defined just in terms of the intrinsic (bulk) properties of the superconductor, because it also depends on other parameters, including its thickness, substrate permittivity (for dielectrics), and measurement technique related parasitic losses.
Therefore, for thin film normal state superconductor measurements, a different configuration of DR must be used than for the superconducting state, in order to discern YBCO/Hastelloy material properties. The conductivity of Hastelloy has been found to be comparable with the normal state conductivity of YBCO and in such a case the multilayered HTS tape structure with a metallic substrate and buffer layers poses a complicated electromagnetic problem and should be approached by a rigorous electromagnetic calculations method.
There have been several studies aimed at analyzing the correlation between normal/superconducting state and dc/high frequency properties of superconductor tapes. The correlation between grain sizes and normal and superconducting states was investigated, also information on the percolation, doping, and the presence of the defects obtained from the dc properties measured in the normal state was used to interpret the superconducting state parameters. There are also a few reports on existing correlations between normal state resistivity and critical current Jc as well as about correlation between rf and dc Jc and their dc magnetic field dependences. It has been shown that normal state surface resistance slope on temperature can be correlated with HTS tape superconducting properties.
Superconducting tapes are produced for use in superconducting magnets or in electric motors. Therefore, these tapes must sustain superconductivity even when high dc magnetic fields are applied to them. The main parameter describing the properties of such tapes is maximum critical current density (Jc), which a superconducting tape can hold at given temperature and the dependence of this critical current on dc magnetic field. Tapes have to maintain superconducting properties at very high field when used in superconducting magnets and/or electric motors. Conventional methods of characterizing superconducting properties of tapes is done after the fabrication process is finished. However, if a defect is detected after fabrication, it is no longer possible to change process parameters and correct it. The present process and apparatus provide real time feedback on the fabrication process, because the characterization is done in-situ at room temperature.
The present disclosure comprises a dielectric technique for measuring the complex impedance of HTS tapes. This dielectric resonator technique is a versatile and relatively inexpensive technique.
In one embodiment, dielectric resonators are used to perform in situ surface resistance testing of the fabricated, tapes. The dielectric resonators are designed to operate either in microwave or mm wave range, depending on the material to be measured. The dielectric resonator techniques can be adapted for measurements at the elevated temperatures used during annealing as well as at room and lower temperatures.
In certain embodiments, the resonators are specialized for characterization of normal state HTS tapes and dielectric buffer layers. Hardware and software used in these techniques for NDE process and quality control are described.
In certain embodiments, one or more microwave resonators/sensors placed in the process/annealing chamber of an apparatus for producing HTS tapes allow for real time monitoring of surface resistance as the tapes are produced. Either rutile or sapphire discs can be used in a TE01δ configuration for a several mm2 area of the measured tapes, because the criteria for material to be used as dielectric disk includes relatively high dielectric constant and low loss tangent parameters. High dielectric constant allows for making such disk a small diameter disk, and low loss tangent allows for high sensitivity. In some cases single crystal material such as sapphire and rutile are used, in other cases a special low loss tangent ceramic is selected.
The present apparatus and method measure the surface resistance as a function of temperature (Rs=Rs(T)). In certain embodiments, this is accomplished by measuring at least two temperature points of Rs(T) dependence. The temperature dependence of normal state resistivity correlates with the critical current density Jc value. Jc is related to dc magnetic field dependence. Moreover, there is strong correlation between superconducting parameters and the slope of Rs vs. T in the normal state.
Correlations between Rs vs. T plots and superconducting state parameters have been investigated (Muller 1987, Yoshihara 1995). In the present disclosure, the slopes of normal state microwave Rs vs. T plots are correlated with superconducting state parameters such as critical temperature, critical temperature width, and residual surface resistance. It is also shown that the slope of an Rs vs. T plot can be correlated with parameters describing dc (direct current) critical current Jc capability of tapes. Dc parameters such as critical current Jc and its dependence on magnetic field are usually used for evaluation of the quality of YBCO tapes for various applications. In general, it can be expected that the steeper slope, the better the superconducting film.
The following drawings form part of the present specification and are included to further demonstrate certain aspects of the subject matter. The subject matter may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.
It will be readily apparent to one skilled in the art that various substitutions and modifications may be made in the subject matter disclosed herein without departing from the scope and spirit of the invention.
The present disclosure provides real-time methods of monitoring the quality of HTS tapes during production, including the measurement of the complex impedance of HTS tapes using dielectric resonator techniques. These techniques can be non-destructive and non-contact, and are relatively inexpensive.
The present methods and apparatus can be used with any high critical temperature superconductor and any substrate. Examples of applicable superconductors include YBCO, thallium, and bismuth based superconductors. Examples of applicable substrates include Hastelloy, or any other substrate onto which superconducting film can be deposited such as silver, copper, similar to Hastelloy alloys, sapphire, zirconia, magnesium oxide, strontium titanate and other dielectrics.
In an embodiment, dielectric resonators are used to perform in situ surface resistance testing of a fabricated HTS tape. The dielectric resonators are designed to operate either in microwave or mm wave range, depending on the material to be measured. The dielectric resonator techniques can be adapted for measurements at the elevated temperatures used during annealing as well as at room and lower temperatures.
In certain embodiments, the resonators are specialized for characterization of normal state HTS tapes and dielectric buffer layers. Hardware and software used in these techniques for NDE process and quality control are provided.
The present disclosure provides methods and apparatus for monitoring quality control of differing compositions of superconducting tapes. In one embodiment, the substrate comprises dielectric material, which can be penetrated by electromagnetic waves. In another embodiment, the substrate comprises metallic material, for example the alloy Hastelloy, from which microwaves are reflected. Measurements using conventional methods are complicated by metallic substrates. The present method can be used for either type of tape.
In certain embodiments, one or more microwave resonators/sensors are placed in the process/annealing chamber of an apparatus for producing HTS tapes to allow for real time monitoring of surface resistance as the tapes are produced. Either rutile or sapphire discs are used in an electromagnetic mode (for example TE01δ) configuration. Such resonators/sensors analyze an area of the measured tapes from a few square mm to several centimeters.
In principle, a preferred dielectric resonator needs a low microwave loss dielectric disk. For a given frequency, the size of this disk will depend on the dielectric constant value. For example, a sapphire (epsilon ˜10) disk resonating at 10 GHz is 9 mm in diameter and 5 mm in height. For the same frequency, a rutile disk will be much smaller (3 mm in diameter and 2 mm in height). BZT is ceramic, inexpensive and easy to make. It is not as good as sapphire, or rutile single crystals (in terms of microwave loss), but it is good enough for some applications. Rutile may be difficult to use, because its dielectric constant is very sensitive to temperature changes. In general a low microwave loss dielectric material with weak dependence on temperature in the range of temperature interest (above 100 K and to 450 K) should be used.
This disclosure refers to and describes single post dielectric resonators (SPDR) and rod dielectric resonators (RDR). These allow measurements having the disk at some distance from the tape (in the SPDR configuration), or the disk can touch the tape (in the RDR configuration). The RDR configuration is still a non-contact method, because no “contact” is deposited. For example, no gold or silver round contacts to which something can be soldered are deposited. Such touching does not do any damage to the tape. A dielectric resonator in general consists of a dielectric disk, a copper enclosure and a coupling structure, for example coaxial cables with a loop or dipole on the end or a microstip placed close to the disk. However, for dielectric disks having a large dielectric constant, an enclosure is not needed because microwave fields are confined in the disk because of this large dielectric constant. This allows for some flexibility. For example,
The present apparatus and method measure the surface resistance as a function of temperature (Rs=Rs(T)). In certain embodiments, this is accomplished by measuring at least two or three temperature points of Rs(T) dependence. The temperature dependence of normal state resistivity correlates with the critical current density Jc value. Jc is related to dc magnetic field dependence. Moreover, there is strong correlation between superconducting parameters and the slope of Rs vs. T in the normal state.
One embodiment provides a method of evaluating superconducting state parameters such as critical temperature, critical temperature width, and residual surface resistance, with the slopes of normal state microwave Rs vs. T plots of a tape. It is also shown in the instant disclosure that the slope of an Rs vs. T plot can be correlated with parameters describing dc capability of tapes. Dc parameters such as critical current density Jc and its dependence on magnetic field are useful for evaluating the quality of YBCO tapes for various applications. In general, if the slope deviates from an ideal slope, the quality of the superconductor has changed. Moreover, it can be expected that the steeper the slope, the better the superconducting film. A “better” superconducting film may have, for example, a high density critical current and relatively small anisotropy when the critical current is measured versus magnetic field.
Examples of possible dielectric resonator configurations, which can be used to characterize HTS tapes, are shown in
where:
An additional schematic of a measurement apparatus is provided in
YBCO tapes were deposited by metal organic chemical vapor deposition (MOCVD) on an IBAD-MgO template, which has a multilayer structure of LaMnO3/homoepitaxial-MgO/IBAD MgO/Y2O3/Al2O3/hastelloy tape. The precursor solutions for Y, Ba and Cu were mixed together in an appropriate mole ratio and then delivered to a vaporizer by a liquid pump. The resulting precursor vapors were then mixed with oxygen and carried by argon gas to a showerhead using oxygen flow rates. This was followed by spraying of the mixture to produce about 0.9 μm thick YBCO tapes on a heated substrate.
Three tapes of Zr-added (GdY)BCO (Zr0.06Gd0.6Y0.6Ba2Cu3O7) were selected. Tc was about 89.3 K for all three (GdY)BCO tapes and Ic values in zero magnetic field were 165 A, 270 A and 339 A for tapes with thickness of 0.84 μm, 1.02 μm and 1.06 μm, respectively. The amount of Zr dopants (BaZrO3) and abundant nanometer-sized precipitates of RE203 generate the density of defects to enhance the flux pinning in a strong magnetic field and self-field. In such a case, determination of the electrical parameters of superconductors is not as simple as it is for temperatures well below Tc.
The deposition process is completed when 1 mm thick protective silver layer is deposited on top of YBCO film. In modeling of such structure, multilayered configuration is assumed, as depicted in
Two different configurations of dielectric resonators designed to accommodate 12 mm wide YBCO/Hastelloy tapes were used. The first configuration, a single post dielectric resonator (SPDR) operating at 13 GHz in TE01δ mode was designed for maximum measurement sensitivity of lossy and/or thin materials. The construction of the SPDR was similar to the resonator used for measurements of the sheet resistance of graphene. The SPDR with a low loss, high-permittivity barium zirconium titanate (BZT) ceramic (εr=27.93 at 300 K) disk is to measure the conductivity of very thin semi-transparent or/and lossy tapes in the normal state i.e. T>Tc. The BZT dielectric of radius 2.5 mm and height 2 mm is placed inside the copper cavity of radius 9 mm at a height of 3 mm. The sample is placed at a distance of 2.5 mm from the BZT dielectric. The second configuration consists of a rod dielectric resonator (RDR) operating at 9 GHz in TE011 mode with (TiO2) dielectric disk (εr=86 at 300K; 108 at 77K), which was used for measurements of the complex conductivities σ1 and σ2 of the YBCO/Hastelloy tapes in the superconducting state. The samples are placed on either side of the rutile dielectric disk of radius equal to 2.35 mm and height 2.5 mm, and placed in a copper enclosure of radius 7 mm. There is no air gap between rutile disk and YBCO films.
The SPDR and RDR configurations are presented in
The measurements of Q-factor and frequency as a function of temperature were performed with the resonators mounted in a closed cycle liquid nitrogen cryostat. One-port Kajfez method of Q-factor measurements, which included calibration of the network analyzer and cryostat cables losses, was used to measure and calculate the Q-factor. The coupling loop, which inductively excites the appropriate mode in the DR was connected to the HP86390 network analyzer. The GaAs temperature diode, thermally connected to the resonator via indium layer, used a Lake Shore temperature controller to control and measure temperature of YBCO tapes. The measurement data of Q-factor, frequency and temperature were collected at a user-defined time interval, which in the present case was every 10 seconds through a GPIB interfaced computer program.
Extraction of complex conductivity from measured Q-factor and frequency shift with temperature dependencies requires calculations of the electromagnetic fields in the resonant structure. Numerical simulation of the field calculations were performed using high frequency structural simulator (HFSS), a finite element method (FEM) based tool considering the same dimensions of the DR as in the experimental setup. The material parameters of copper cavity, dielectric and air cavity were defined by their respective permittivity, conductivity and loss tangent. Material properties of Hastelloy along with an impedance boundary condition defining the sheet resistance of the superconducting tape were used to describe the sample under simulation. To ensure the accuracy of the simulation solution, the structure was finely meshed along the dielectric disk and sample regions. Two different analysis methods, driven and eigen modes, were used to calculate numerically the dependence of frequency and Q-factor, respectively, on sheet resistance σ1h (S/m). The eigen mode analysis which is a mode matching technique was used to determine the natural modes of the resonator and the Q-factor at each of the calculated resonant frequencies. Using the DR's experimentally measured resonant frequency as the starting point, the minimum frequency for the eigen mode analysis was determined. The appropriate Q-factor was determined by observing the electric and magnetic field distribution for each resonant mode to identify the TE01n mode.
Parametric analysis over a wide range of sheet resistance values was performed to obtain Q-factor as a function of sheet resistance as shown in
The coupling loop in the driven mode analysis was drawn to mimic a coaxial cable loop made to excite the TE01n mode. A waveport was used to simulate an external wave of power 1 W of magnitude incident on the outer end of the coupling loop. In the driven mode analysis, the interpolating sweep where the solution is interpolated based on the number of frequency points solved was used to determine the one-port S-parameters. The fast sweep utilizing an adaptive Lanczos-Pade sweep (ALPS) algorithm extrapolating the center frequency solution was used to obtain the fields distribution and to check the accuracy of the determined resonant frequency.
For the calculation of the conductivity of YBCO/Hastelloy tape in normal state, the experimental data points of Q-factor i.e. Q(T) is mapped to the HFSS simulated Q-factor as a function of σh. The mapping process is described in the flow chart shown in
Using the two different resonator configurations (i.e. SPDR and rutile rod resonator) the conductivity, later converted into surface resistance Rs, of Hastelloy and Hastelloy/buffer/YBCO were measured at normal and superconducting states.
A YBCO of a few hundred nanometers' thick and deposited on Hastelloy tape is semitransparent to microwaves at X-band frequency in the normal state. Both materials Hastelloy and YBCO have very similar skin depth in this range of temperature. In such a case effective surface resistance Rs is approximately equal to 1/σ*h, where h is the YBCO film thickness and σ* is the effective conductivity. As a result the measured resistance is of an order of Ω not mΩ. The resonator “sees” the difference between Hastelloy and YBCO/Hastelloy Rs. This means that semi-transparent 1 μm thick normal state YBCO layer introduces an additional loss sufficiently large to be sensed by the resonator. Because there is almost no temperature dependence of Rs of Hastelloy and a much stronger temperature dependence for YBCO, this helps to extract Rs of YBCO from the measured YBCO/Hastelloy response. It can be seen that YBCO in normal state, dielectric buffer layers do not change significantly the effective surface resistance of investigated multilayer.
The present disclosure provides a dielectric resonator technique and apparatus for measuring the conductivity of a Hastelloy tape, Hastelloy/buffer/YBCO with and without Ag over-layer over wide enough temperature range to cover both superconducting and normal metal properties of YBCO.
Microwave techniques take advantage of the fact that in contrary to dc currents, rf currents cannot meander, thus the electromagnetic response is integrated over the whole volume where rf currents are induced in the metal/superconductor.
Calculations were performed for YBCO tape thickness of 1 μm and conductivity of the Hastelloy tape was assumed to be equal to 1 μm, conductivity s of Hastelloy was assumed to be equal to 6×105 S/m. Also no temperature dependence was assumed based on measurements.
The possibility of normal state Rs measurements of superconductors was analyzed. Also the possibility of characterization of dielectric buffer layers (deposited directly on Hastelloy substrate below YBCO film) was analyzed. With YBCO tapes deposition on higher conductivity substrate such as copper substrates instead of Hastelloy, it would be possible to characterize the normal state Rs.
This application claims priority to U.S. Provisional Patent Application Ser. No. 61/845,020, filed Jul. 11, 2013, entitled “Method for Production Quality Control of Flexible Superconducting Tapes,” the entire content of which is hereby incorporated by reference.
Number | Date | Country | |
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61845020 | Jul 2013 | US |