High Temperature Superconductivity - Manupatra

Journal of Intellectual Property Rights Vol 7, July 2002, pp 295-307

High Temperature Superconductivity: Challenges in IPR Regime and Strategies for National Initiatives J Koshy, R Jose, Asha M John, J K Thomas, S Suresh Kumar† and A D Damodaran Regional Research Laboratory (CSIR), Trivandrum 695 019 (Received 8 April 2002)

Superconductivity offers unique opportunities for a developing country like India to be a global leader because of the availability of trained manpower resources and the scientific infrastructure. This paper describes briefly the developments made in the area of high temperature superconductivity (HTS) for the last 15 years and the challenges in IPR regimes. The strategies adopted by countries like US, Japan and Germany in the development and commercialization of HTS are described. Comparison of time line to commercialization of HTS with other technologies like semiconductor, digital network and fibre optics is presented. Importance of national initiatives at governmental and industrial levels, and strategical alliances involving industry, research organizations and academics for superconductor technology development is highlighted.

One of the most exciting developments in science in recent times was the discovery of high temperature superconductivity with the publication of a paper with a cautious title “Possible high temperature superconductivity in La-Ba-Cu-O system” by J G Bednorz and K A Muller in 1986. It has captured the imagination of the public with front-page stories in newspapers and cover stories in international magazines and has attracted unprecedented media coverage. This discovery has been heralded as the much sought after solution to an array of problems requiring high technical inputs. ________ † for correspondence

New applications have been projected for vital areas like communication and transportation, energy and health, and if one looks back on their futuristic projections, one may very well remark that spectacular progress has been made during the last 14 years and the emerging industry is well on its way on fulfilling these expectations. History of Superconductivity Superconductivity is the physical property by which electrical conductors lose all resistance. It was first observed in

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1911 by Dutch Physicist H Kammerlingh Onnes in the course of his experiment on electrical conductivity of metals at low temperatures. He observed that mercury cooled to near absolute zero in liquid helium would abruptly and completely lose all resistance to the flow of electricity at 4.2 K. In this state of zero resistivity it is expected that a current flowing around a superconducting ring will flow indefinitely as long as the temperature is maintained below that for the transition from normal to superconducting state. The temperature at which this transition takes place is called critical temperature. It was soon found that many other elements, intermetallics and alloys become superconducting when cooled near to absolute zero temperature. Over the years, the highest transition temperature had been gradually increased from 4K to 23K in alloys of niobiumaluminium-germanium. These developments led to some important practical applications of superconductivity using superconducting wires comprising of NbTi alloy embedded in a matrix of copper. These low temperature superconductivity (LTS) wires allowed the construction and demonstration of superconducting magnets, superconducting generators and motors using LTS wires worldwide. In late 1970s the first magnetic resonance imaging (MRI) prototype was built and tested using LTS wires, which led to the rapid growth of new MRI industry. In a parallel development on thin films using LTS materials, a new ultrasensitive superconducting quantum interference devices (SQUID) entered in the global

market to detect extremely small magnetic fields both for brain imaging and geophysical research. High Temperature Superconductivity Since the discovery of superconductivity in 1911 in mercury there was worldwide search for new materials which superconduct at a higher temperature. However, till 1986 the highest transition temperature achieved was only 23 K. The real breakthrough in superconductivity occurred in 1986 when Bednorz and Muller of the IBM laboratory at Zurich discovered a ceramic compound consisting of barium, lanthanum, copper and oxygen which was found to be superconducting1 at 35K. The expectation raised by this discovery was so high that they were awarded Nobel Prize in Physics the very next year, which might be the shortest time gap between the discovery and the award of Nobel Prize. In 1987 another milestone was reached when Wu et al. at the University of Houston at Alabama produced a ceramic oxide containing yttrium, barium and copper, which is superconducting2 at 92 K. This discovery was quickly reproduced by many workers throughout the world and it was soon established that the phase that is superconducting is YBa2Cu3O7- sometimes referred to as 123 phase 3,4. The early pace of discovery of HTS materials following the results of Paul Chu and his colleagues was spectacular. In the year 1987 itself, eight new materials were reported that are superconducting above 77 K. This excitement has subsequently shifted to other copper oxide systems containing

KOSHY et al.: HTS — CHALLENGES IN IPR REGIME

bismuth-strontium-calcium-copper oxide5, with Tc = 110 K 5 and thallium-bariumcalcium-copper oxide6 with Tc = 125 K. In 1993 transition temperature was pushed up to 135 K in mercury-bariumcalcium-copper oxide compound 7,8. This is the highest verified critical temperature at atmospheric pressure so far. It is reported that the Tc could be further increased to 150 K in Hg-Ba-Ca-Cu-O if

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synthesized at high pressure9. Figure 1 summarizes the evolution of superconductivity from its discovery to the recent developments in high temperature oxide superconductors 10. Futurists have made high profile projections of new levels of transportation, communication systems, energy saving power transmission, ultrasensitive medical equipments, etc

Fig. 1—Evolution of superconductive transition temperature subsequent to the discovery of the phenomenon

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through the use of new superconductors while others have suggested that the superconductors may affect virtually every industry and service in the next century. However, the expectation of immediate applications of HTS in transformers, power motors, generators, transmission cables by replacing copper wires could not be realized as fast as expected due to the complexity of the problems associated with the new HTS materials like low current carrying capacity, lack of stability in atmosphere, etc. Comparison with Semi-conductor, Digital Network, Fibre Optics Systems It may be pertinent here to investigate the R&D developments and time line to commercialization in similar tech areas like semi-conductors, fibre optics and digital networks that have historically been followed11. In all these areas, ideas and preliminary trials have preceded market penetration, diffusion and commercial success by as much as 3 to 4 decades as can be seen from Figs 2 and 3. The initial research and development of transistor began in 1943 and it took almost four years for Bardeen, Shockley and Brattain of AT&T Bell Laboratory to demonstrate the transistor for the first time in 1947. Eleven more years were necessary for the development of first IC in 1958 and it took altogether fifty years or more for the semi-conductor to go to the present size of a multibillion-dollar industry. The case of fibre optics/wave guide communication is not very different. The concept of channeling light was first suggested in 1858 by English

physicist John Tyndall and in 1880 the idea of communication by light was introduced by Graham Bell. It was only in 1971 the first prototype of optical fibres was developed by Corning. The convergence of telecommunications and computing technologies and service into a new medium offering integrated services through digital networks though predicted in 1970s is beginning to have major socio-economic impacts only now 12. These historical developments in high tech ‘niche’ areas suggest a tiered infrastructure of learning curves based not only on the breakthrough but also prompted by strategies for endogenous capabilities 13. Recently a new realistically projected time line in superconductor technology is given in Fig.4. International IPR Activity in HTS Patenting activity has now become an important indicator of the technological competitiveness of a country and the patent data represent a widely accepted measure of the technology output of a particular area of science. A complete information about any sealed patent in US, Europe or in Japan can now be down loaded from the Internet either by using the patent number or the name of the inventor. In the case of superconductivity up to 1986 it was regarded as a field of foremost scientific interest with only a few products specially in nuclear and medicinal technology. However, after the discovery of HTS in 1986, we observe an increasing number of commercial companies in US, Europe and Japan with activities in HTS. Naturally the patent applications also have increased


Fig. 2—Semiconductor technology development time line

Fig. 3—Optical fibre technology development time line

Fig. 4—Superconductor technology development time line

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tremendously during 1986-88 period. Fig. 5 shows the bar diagram of a number of patent applications in Europe Patent Office in superconductivity during 1981 to 1992. Before the invention of HTS in 1986, the number of patent applications had not exceeded 50 per year. As can be seen from the data, the patent activities in superconductivity increased sharply in 1986-88 to nearly about an average of 400 patent applications on high Tc materials during the period. Japan accounted for about 45% of the patents, US about 30% and Germany about 10% (Fig. 5). The average number of patent applications in Europe patent office on superconductivity now is about 150 per year.

We have recently conducted a study on number of HTS patents sealed in USA since 1988 in various sub-fields. Our data shows that 1,279 patents have been sealed in US patent office on high temperature superconductivity during 1988-2000, Table 1 gives details of sealed US patents on various sub-fields/applications. Prior to 1986, superconductivity being a highly science driven technology, only large firms or companies with traditional processes on science based developments were involved in this area. But this situation has changed remarkably after the discovery of HTS where a large number of small and medium level entrepreneurs and institutions have

Fig. 5—European patent applications in HTS during 1981-92


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Table 1 —The US patents sealed in HTS till 2000 Sub-fields Processing of superconductor (YBCO, BISCCO single crystal growth techniques etc.) Microelectronic device, SQUID applications, (Antenna, resonator, bolomets, filters, etc)

No. 443

Percentage 35%

269

22%

HTS superconductivity film High power application (AC cables, NMR, MRI magnets, electromagnets) Magnetic shield, levitation, etc Superconducting wire, tapes, coated conductor Superconductor metal/insulator composites Total

205 145

16% 11%

99 83 35 1279

8% 7% 3%

entered the field with their own R&D activities. One of the initial problems for large scale application of the new superconductors was definitely on the processing aspects and that accounts for the large number of patents sealed in US on the processing aspects of HTS especially during the period up to 1995. It was also realized that the immediate application of the new high TC materials are in microelectronics, which resulted in large number of patents in thin film and device applications. The high power applications of the new materials are just emerging and patents along these lines are mainly after 1992. Potential HTS Revolution in Industry Since the discovery of HTS, prospects of commercial application of the technology has increased tremendously. We observe an increasing number of commercial companies with activities in superconductivity. One of the unique things about superconductivity is that it

presents possibilities for both electrical and electronic applications. The current carrying capacities of superconducting wires and tapes have been increased exponentially during the last few years making their use in high power applications a real possibility 13. New families of HTS YBCO current leads, which can carry a steady current of over 13,000 amperes at liquid nitrogen temperature, have been developed by Eurus Technologies 14. Rigorous tests recently conducted have demonstrated that by replacing the conventional current leads of copper used in the superconducting magnetic systems in the CERN’s Large Hadron Collider (LHC) programme in Switzerland intended to investigate the fundamental forces of matter and energy, the consumption of helium can be reduced by 80%. The tests marked the culmination of an international industry-university development project aimed at developing electrical power leads for commercial use in power applications utilizing HTS

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current leads. The encapsulated HTS current leads are not only cost effective but also the best in the class. Magnetic separators are another important main stream markets in which high temperature superconductor will displace the existing technology because of its superior cost per performance. Earlier in 1997, Du Pont reported the first results of a successful magnetic separation of mineral contaminants from kaolin clay using HTS magnets. The development of HTS magnets would rapidly penetrate the industry. Such high field magnets could also produce long range benefits in chemical manufacturing process. Potential opportunities have been identified in several other areas including pretreatment of water to prevent scale formation, treatment of aqueous waste water, benificiation of mineral and ore feedstocks and purification of industrial products by removal of low level magnetic contaminants. A large number of practical applications using high temperature BiSCCO superconductors have also been identified and demonstrated by successfully developing superconducting BiSCCO tapes with high critical current density at liquid nitrogen temperature. Through the development of innovative continuous manufacturing processes and reduction in the amount of silver, the cost of BiSCCO tape has been reduced to a level where it can be sold as a commodity product. HTS thin films can make a significant advancement in microelectronics in devices like low phase oscillators, ultra high-Q resonators, high power filters,

inductors, high speed switches, high power relay lines, broad band spiral antennas and networks, multi-chip modules, NMR and MRI pick up coils, digital and Josephson junction based electronic components. By 1995 the high temperature superconducting quantum interference devices sensors have already entered the market. The unparalleled growth of wireless communication industry has created a multi-million $ market for HTS based high performance resonators and filters using superconducting YBCO thin films. Recently, Japan has made tremendous progress in the development of HTS based electronics for mobile communication industry using YBCO thin films. Two of the US DOE National Laboratories, Oak Ridge and Loss Alamos have recently developed YBCO tapes on commercially available textured Nickel alloys by the usual thin film technology 15. These new generation of coated HTS wires, gave critical current density of over 7x105 A/cm2 at one Tesla, making several HTS applications such as motors, generators, current limiters, magnetic storage devices, commercially feasible due to the ability to operate at liquid nitrogen temperature. Similarly, HTS power transmission using these tapes could be more attractive due to the ability to carry high current in a small volume with minimal resistive losses. Strategies in US and Japan Developmental strategies in HTS in Japan and US involve departmental initiatives, industrial collaborations and 16 advocacy groups . The fifth


International Superconductivity Industrial Summit held in Japan in May 1996 forecasted that the total global market for the superconductor based products would be nearly 240 billion US dollars by the year 2020, which is about one million crores of Indian rupees. In view of this colossal market opportunity and the associated impacts on jobs in the creation of this new industry, governments have poured millions of dollars in the development of superconductor technology. Estimated annual support for superconductivity in the governmental and academic sectors in Japan and US is about $277 million and $223 million respectively17. The figure for Europe is $126 million. In US, Council on Superconductivity for American Competitiveness (CSAC) was formed under the leadership of the then President’s Science Advisor in 1989. CSAC became a higher advocacy group in Washington concerned with the technology and public policy aspects of superconductivity. CSAC is a privately funded, non-profit organization charged with developing programmes aimed at moving superconductor technologies into the applied engineering and commercialization stages. The US Office of the technology assessment formulated plans to pursue parallel development of basic research and manufacturing processes. The feedback between these two can speed up the rate of commercialization. In US most of the federal funds are routed through DoE’s (Department of Energy) research partnership with industry participants, which has increased considerably in the past five years.

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Superconductivity Partnership Initiative (SPI) of DoE is aimed at early introduction of energy saving electric systems based on HTS industry. SPI teams are vertically integrated containing a user, manufacturer and superconductivity component supplier to facilitate scale of research findings. Thus, DoE programmes support basic research at government laboratories and development efforts through industry teams. The primary mechanism for this is in the form of collaborative research and development agreements (CRADAS)18. Present Status of High TC Superconductivity in India When high temperature superconductivity was discovered in 1986, because of the existing infrastructure and equipment available in some of the national laboratories, the scientists in India could immediately initiate studies on the new system. A united effort of material scientists, low temperature physicists, theoretician and thin film experts was evident even at the beginning stage of high temperature superconductor research in India. A national coordinated programme consisting of CSIR laboratories, TIFR, IISc, universities and IITs has soon been evolved by setting up a programme management board on superconductivity by the Government of India’s resolution dated 12 June 1987. National Superconductivity Programme of NSTB Secretariat, DST, had identified specific tasks in basic research and applied research. Some of these include superconducting substrates, point

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defect equilibria and electrical behavior, chemical aspects, structure property corelations, crystal growth etc as part of basic research. Preparation of the thin films and single crystals of high Tc superconductors, scale-up in preparation, and characterization of HTS compounds, electromagnet SQUIDS and SQUID devices. Electromagnet development, high Tc tapes, 5 MVA generator, single crystal epitaxial thin film, etc.CSIR labs like NPL, RRL-Trivandrum, CEERI, Pilani, IITs, IISc, TIFR, BARC, IGCAR, SSPL, Delhi, CAT, Indore, and central universities were involved. The coordinated programme was on the basic aspects of HTS and on the development of HTS based SQUID. In fact, the Indian technical initiatives have been no less impressive to start with. The research laboratories in the country have been reportedly performing at par with the international laboratories in this respect. The NPL group has started the work on the fabrication of SQUIDs, based on naturally present grain boundaries in polycrystalline YBCO superconductors, which behave as Josephson junctions. However, the first generation of SQUIDs fabricated by NPL based on these natural grain boundary junctions19 appeared to be not very reliable and hence in recent years considerable efforts have been made in the fabrication of artificial Josephson junctions using high Tc epitaxial films20. The TIFR group concentrated on the fabrication of thin film superconductors by pulsed laser ablation and in the study of the effect of Au and Ag addition in improving the microstructural and

transport properties of the films21,22. The original discovery of superconductivity in borocarbide system23 by TIFR has been very helpful in the understanding of the co-existence of the magnetism and superconductivity. The first observation of non-resonant microwave and rf absorption in high temperature superconductivity24,25 was reported by IISc in 1987. The Centre for Advanced Technology, Indore, has done pioneering work on the effect of magnetic field on superconducting behaviour of low Tc and high Tc materials both in bulk and thin film form 26,27. Extensive work on the cation substitution studies was conducted by BARC group with a view to gain useful information in crystal chemistry aspects and to establish general phenomenological trends that will provide better insights of factors that give rise to superconductivity in cuprate systems28. Scientists at Regional Research Laboratory (RRL), Trivandrum, have developed new oxide ceramic compounds that can be used as substrates for high Tc superconductors 29-31 and have obtained US patents for the process and product for all these materials32-37. YBCO films grown by pulsed laser ablation on the epitaxial layers of the new substrate materials gave a current density as high as 6x106 A/cm2 at 77K, which is one of the highest current density values reported for a superconducting film 38. The RRL group has also reported for the first time a detailed study on the superconductor-insulator percolation behaviour for both YBCO and Bi(2223) superconductor systems 39,40 using the


newly synthesized ceramic oxides as insulators. Strategies for India Contributions to HTS research in India by CSIR, IISc, TIFR, BARC, etc. were of very high international standards, opening the possibility of advanced application in systems and device configurations. We can avail of the advantages of competitive performance at laboratory scale being extended to the technology level also, only if sufficient facilities and opportunities exist within the country. Since some infrastructure has already been built for critical resource inputs, we can enhance the same to the orders required for technology applications through advocacy forums for legislation and coordinated programmes. Taking into account the enormous possibilities of HTS in the 21st century it is essential that we develop a national centre for superconductivity research coordinating the HTS research and development all over the country. Such a centre can function with the participation from corporate houses, public sector industrial agencies and academic institutions. This centre should be entrusted with responsibility for development of materials synthesis, processing capabilities and commercialization stage collaboration with industry. This centre should bring together teams from university and industry and government laboratories to work on high-risk research projects with potential for high pay offs. It is not enough to be at the forefront in making scientific breakthrough or being at par in research with other countries.

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Now in India it is important that the industrial initiatives in high technology areas are forged through legislature. We do not have to wait for technology developments abroad to get them transferred here at huge costs. We should focus on creating market conditions and enhance technological capabilities through appropriate framework conditions. India was almost ignorant about the implication of IPR till the beginning of the present globalization process. But by the time we became aware, developed nations have already patented technology needed for the development for another 25 years, leaving us without any chance even to take off. This may be one of the greatest challenges of IPR and globalization as far as India is concerned. At least in the area of high Tc materials which is relatively a new development we could have performed better if there was a planned strategy. We as a nation fumble at critical stages in science and technology developments. Superconductivity is one of the most recent examples. We can cite other examples of semi-conductor technology development or area of crystal growth in the sixties, where India could have performed exceedingly well. Special provisions have to be made in funding futuristic research in superconductivity. Conclusions Superconductivity offers unique opportunities for a developing country like India to be a global leader because of the availability of trained manpower resources and the scientific infrastructure. It is time for us to establish through legislative efforts a national centre for

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high temperature superconductivity as done in countries like US, Japan and UK. This centre should focus on the industrial applications of new superconducting materials which have immediate potential markets in electronics, digital systems, personal telecommunication networks, sensors, etc and long term applications in magnetic separators, HTS current leads, high power transmission lines, magnetic energy storage system, etc. The explosive growth in the wireless communication industry in India can potentially create a multi million $ market for HTS based ultra-high performance filters and lownoise receivers. These are relevant applications burgeoning in India and capable of making an impact and interest among industries. What we require now is initiatives at governmental and industrial levels, and strategical alliances involving industry, research organizations and academics. References 1 Bednorz J G and Mullerk A, Z. Physics B, 1986, 64, 189. 2 Wu M K, Ashburn J R, Torng C J, Hor. P H, Meng R L, Gao Z J, Wang Y Q and Chu C W, Physical Review Letters, 58, 1987, 908. 3 Maeda H, Tanaka Y, Fukutomy M and Asano T, Japan Journal of Applied Physics, 27, 1998, L209, L548. 4 Sheng Z Z and Herman A M, Nature, 332, 1988, 55. 5 Sheng Z Z, Applied Physics Letters, 52, 988, 52, 1893. 6 Rao C N R, Ganguly P, Ray Choudari A K, Mohan Ram R A and Sreedharan K, Nature, 326, 1987, 856. 7 Cava R J, van B Dover R B Batlogg B and Rietmen A, Physical Review Letters, 58, 1987, 1676. 8 Schilling A, Contoni M, Gao J V, Ott H R, Nature, 363, 1993, 58.

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35 Koshy J,Thomas J K, Kurian J, Yadava Y P and Damodaran A D, US Pat 6040275, 21 March 2000 36 Koshy J, Thomas J K, Kurian J, Yadava Y P and Damodaran A D, European Pat EP 0679615 B1, 21 July 1999 37 Koshy J, Kurian J, Sajith P K, Kumar K S, Jose R, John A M and Damodaran A D, US Pat 6140275, 31 October 2000. 38 Pai S P J Jersudasan, Apte P R, Pinto R, Kurian J, Sajith P K, James J,and Koshy J, Physica C, 290, 1997, 105 39 Koshy J, Paulose K V, Jayaraj M K and Damodara A D, Physics Review B, 47, 1993, 15304 40 Koshy J, Kumar K S Kurian J, Yadava Y P and Damodaran A D, Physics Review B, 51, 1995, 9095.