Physica C 470 (2010) 13381341

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Physica C
journal homepage: www.elsevier.com/locate/physc

Fabrication of silver stabilization layer of coated conductor using organic silver complexes
J.B. Lee a, S.J. Park a, S.S. Kim c, S.H. Moon d, H.G. Lee a,b, J.H. Kim e, S.X. Dou e, G.W. Hong a,e,*
a

Graduate School of Knowledge-based Technology & Energy, Korea Polytechnic University, 2121 Jungwang-dong, Siheung-si, Gyeonggi-do 429-793, Republic of Korea Department of Advanced Materials Engineering, Korea Polytechnic University, 2121 Jungwang-dong, Siheung-si, Gyeonggi-do 429-793, Republic of Korea c NANOCMS, 8-5BL, Jiksan-eup, Mosi-ri, Cheonan-si, Chungnam 330-314, Republic of Korea d SuNAM Co., Manan-gu, Anyang 430-817, Republic of Korea e Institute of Superconducting and Electronic Materials, University of Wollongong, Wollongong NSW 2522, Australia
b

a r t i c l e

i n f o

a b s t r a c t
Silver stabilizing layer of coated conductor has been prepared by dip coating method using organic silver complexes containing 10 wt.% silver as a starting material. Coated silver complex layer was dried in situ with hot air and converted to crystalline silver by post heat treatment in owing oxygen atmosphere. A dense continuous silver layer with good surface coverage and proper thickness of 230 nm is obtained by multiple dip coatings and heat treatments. The lm heat treated at 500 C showed good mechanical adhesion and crystallographic property. The interface resistivity between superconducting YBCO layer and silver layer prepared by dip coating was measured as 0.67 1013 X m2. Additional protecting copper layer with the thickness of 20 lm was successfully deposited by electroplating. The critical current measured with the specimen prepared by dip coating and sputtering on same quality YBCO layer showed similar value of $140 A and proved its ability to replace sputtering method for industrial production of coated conductor. 2010 Elsevier B.V. All rights reserved.

Article history: Available online 15 May 2010 Keywords: Organic silver complexes Silver stabilizer layer Coated conductor

1. Introduction Coated conductor fabricated by depositing a thin oxide high temperature superconducting (HTS) lm epitaxially on a buffered metal substrate is expected to be widely used in electric power device replacing copper wire because of its excellent current carrying capacity at a boiling temperature of liquid nitrogen. Intensive studies by many researchers have been made to enhance its properties such as high critical current density, low AC losses, mechanical strength and handling ability. From technical points of view, most technical issues have already been solved and several companies including SuperPower Inc., and American Superconductor began to produce and sell their products with high productivity. However, from economical points of view, the production cost of coated conductor is still too expensive for broad application compared with conventional conductor. Therefore, it is needed to develop new production techniques which can enhance the competitiveness of the coated conductor. Recently, SuperPower Inc. reported that the production cost of a silver stabilizer layers

* Corresponding author. Address: Graduate School of Knowledge-based Technology & Energy, Department of Advanced Materials Engineering, Korea Polytechnic University, 2121 Jungwang-dong, Siheung-si, Gyeonggi-do, Republic of Korea. Tel.: +82 31 8041 0335; fax: +82 31 8041 0349. E-mail address: gwhong@kpu.ac.kr (G.W. Hong). 0921-4534/$ - see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.physc.2010.05.107

took part in 17% of total fabrication cost of coated conductor [1]. Silver layer in coated conductor takes a role to provide a good electrical contact between superconducting layer and current leads and a proper mechanical protection for the further processing of the copper lamination. Copper protection layer takes charge of thermal stabilization and by-passing excess current in case of quench and provide a good ohmic electrical contact with current leads as well as mechanical strength to the coated conductor for device fabrication. Copper lamination is generally made by electroplating or soldering. Therefore, silver stabilizer layer should be capable of protecting YBCO layer from corrosion by an acidic electrolyte during electroplating or from diffusion of solder materials during lamination process. Currently, most commercial coated conductors include silver layer with a thickness of 12 lm. Recently, Lee et al. [2] reported a successful deposition of silver stabilizer layer having good electrical and mechanical characteristics by dip coating method using nano silver paste as a coating medium. The coating solution used for dip coating is prepared by dispersing the nano silver paste within high viscosity dispersion solvent such as alpha-terpineol and uniform dispersion is important for uniform coating thickness. But the use of high viscosity dispersing solvent makes the thickness control of coated lm difcult when coating speed is high. Also the residues left on the inner surface of container decrease the ratio of raw materials usage that resulted

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in decrease of process effectiveness. All above issues affect the productivity of the nano silver paste negatively and also the relatively high cost of the paste itself led us to nd another substitute for nano silver paste. An organic silver complexes is a precursor solution containing silver as a form of positive ionic salts having carboxylic acid or ammonia as ligand [3,4]. Because of its ionic nature it is not a dispersed solution of nano size silver solid particle but a clear solution without any solid precipitate and can be prepared as dilute solution with low viscosity suitable for fast uniform double side coating. The coating thickness can be controlled by adjusting the concentration of the solution or applying multiple coating. The characteristics of the organic silver complexes such as its decomposition temperature, solubility of silver, and sensitivity for light can be controlled by various chemical method studied by others [5,6]. The dip coated precursor lm can be converted to crystalline silver phase by short heat treatment of 5 min in low temperature of 150200 C without undecomposed residual components and showed good electrical conductivity and mechanical adhesiveness [7]. In this study, the silver stabilizing layer was prepared on YBCO coated conductor by dip coating method using organic silver complexes as starting material. Its microstructure, electrical and mechanical properties were characterized by scanning electron microscope (SEM), 4-probe method and adhesiveness test, respectively. The electroplating of copper on prepared silver layer was also conducted to conrm the compatibility of the process for industrial production of coated conductor.

resistance between YBCO and coated silver layer, the coated silver layer was patterned as shown in Fig. 1 as suggested by Kato et al. [8].

3. Results and discussion Fig. 2 shows the eld emission SEM surface microstructures of silver layer prepared with single coating (A) and quadruple coating (B). Both specimens were heat treated at 500 C for 5 min in owing oxygen atmosphere. The silver layer prepared with single coating showed disconnected silver islands with poor surface coverage and YBCO grains were observed through uncovered region while quadruple coated silver layer showed good surface coverage and dense silver grain structure with few pin holes at grain boundary
I1 V1 V2 I2

silver YBCO Buffer/Hastelloy

Fig. 1. Schematic illustration of the conguration for VI measurement of contact resistance of interface between YBCO and silver stabilizer layer [8].

2. Experiments Organic silver complexes (InkTech TEC-010, Korea) purchased from commercial company and HTS coated conductor without silver protective layer were prepared as coating solution and testing substrate. The YBCO coated substrate was immersed in the dip coating bath lled with organic silver complex and pulled upward with a speed of 1.6 mm/s. then the coated lm was dried by blowing hot air heated to 200250 C directly onto the specimen surface for a few second. The color of coated silver layer changed into light gray color during drying process. To satisfy the requirement of good electrical contact and physical protection for underlying YBCO layer, silver stabilizing layer should have dense microstructure and mechanical linking to the YBCO layer. For this purpose, a certain thickness of silver layer is required. To prepare a thicker coating thickness, multiple coating was conducted by repeating dip coating and drying at same condition. Finally, the dried lm was heat treated for 5 min at 200500 C in owing oxygen atmosphere to densify and crystallize coated layer. Adhesive force between silver layer and YBCO layer was tested by ASTM D 3359 adhesiveness test. Microstructure and phase formation of silver were characterized by using eld emission scanning electron microscope (S-4700, HITACHI) and X-ray diffractometer (Mac Science, M18XHF). Copper electroplating was conducted after characterization of silver layer. Silver coated specimen was degreased with NaOH solution before dipping into electroplating bath. Temperature of electroplating bath was controlled at 25 C and 3 A/dm2 was applied to the electrode immersed in a mixture of CuSO4, H2SO4, HCl plating solution. Coating thickness was controlled by a process time. The 20 lm-thick copper layer was obtained by 28 min plating. The critical current was measured by a DC 4-probe method using a nanovoltmeter (Agilent 34420A) and dc power supply (Agilent 6682A) at 77 K in the self-eld. For measuring the interface

Fig. 2. Surface SEM micro graphs of the single coated (A: 2000) and multiple coated (B: 10,000) silver layer for the coated conductor which were sintered at 500 C for 5 min.

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Fig. 3. XRD patterns of pure YBCO (a), single coated (b) and multiple coated silver layer (c) by organic silver complexes after sintering for 5 min at 500 C.

Fig. 5. Cross section SEM micro graphs of silver layer with multiple coating 10 times on LAO single crystal.

junctions. Island type poor surface coverage of silver layer in single coated specimen is the results of self-assembled agglomeration of thin silver layer shrink by the surface tension on YBCO surface because the layer thickness provided by the single coating was not enough to reveal the sufcient tensile strength which can overcome the tensile stress exerted by surface tension. And there is a certain thickness limit required to overcome the surface tension and provide overall coverage surface coverage which was fullled by quadruple coating for organic silver complex. Fig. 3 shows XRD patterns of the silver lms prepared on YBCO lm by single coating and multiple coating and heat treated at 500 C for 5 min in owing oxygen atmosphere. It is seen that only XRD peaks from YBCO phase and silver were observed without any peaks from other second phases. Therefore, it can be said that organic silver complex was decomposed completely, converted into silver metal rapidly by low temperature annealing. Mechanical integrity of coated silver lm is very crucial for applying this technique for industrial application of coated conductor to practical device such as electric power cable or magnet coil. Peel-off test by 3 M scotch tape (ASTM D 3359) was conducted to check the adhesive force of coated silver layer on YBCO layer. Fig. 4 shows the results of Peel-off test for the coated samples heat treated at various temperatures from 200 C to 500 C for 5 min. The peel-off test revealed that all samples showed good adhesiveness of over 95% of retained silver layer even for the sample heat treated at 200 C for 5 min and 100% integrity when sample was sintered at 500 C for 5 min. The results showed great improvement in mechanical integrity of silver layer compare with our previous result using nano silver complex where 100% of silver layer integrity was accomplished by the long sintering of 5 h at 700 C and only 65% for the sample sintered at 500 C [2]. The fast sinter-

ing of silver layer prepared by organic complex might be due to the smaller size of silver atomic cluster compare with the silver particle contained in the nano size silver paste. The cluster of silver ions agglomerated in organic complex decomposed to the nano size atomic cluster by heat treatment during drying of organic complex and may be directly proceeded to the crystallization resulted in rapid sintering. In order to measure the coated thickness of silver, a relatively thick lm was prepared by dip coating 10 times on LaAlO3 (LAO) single crystal. Drying process at 200250 C using heat gun was conducted for a few second after each coating. First coating layer on LAO may have different thickness compared to that on YBCO layer owing to difference of surface condition. But the effect is only act on the rst layer because second coating is done on silver layer coated previously. Fig. 5 is a cross sectional SEM microstructure of the silver layer prepared on LAO single crystal by 10 dip coatings. The total thickness of silver layer prepared by 10 dip coatings was measured as 580 nm and it can be said that about 60 nm of silver layer was formed by one process of dip coating and drying. From this result, the thickness of silver layer prepared with quadruple coating was estimated as about 240 nm. The direct observation of silver layer thickness prepared on YBCO/IBAD metal template was very difcult and indirect estimation referring LAO substrate was used. The thickness of the rst layer on LAO single crystal and YBCO may be different a little but the difference can be negligible from the second layer and was assumed to be same in both cases. The low interfacial resistivity between silver layer and YBCO superconducting layer is one of the most critical requirements for good electrical current transport. To measure the interfacial resistivity silver layer was patterned as shown in Fig. 1. The overall

Fig. 4. Results of 3 M tape test for the sample sintered at various temperature of 200500 C.

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Fig. 8. IV curves at 77 K in zero magnetic eld for the sample that silver stabilizer layer was prepared by dc sputtering method and dip coating method, respectively. Oxygenation and densication heat treatment was carried out at 500 C for 5 min. Fig. 6. IV curves at 77 K in zero magnetic eld for the coated sample with sintering at 500 C for 5 min by organic silver complexes from 0 A to 100 A.

ing excellent compatibility of dip coating method using organic silver complex for making silver protection layer over YBCO layer in coated conductor. 4. Conclusions Silver stabilizer layer of coated conductor has been successfully prepared by dip coating method using organic silver complexes. A continuous pure silver layer with dense microstructure, good surface coverage and proper thickness of 230 nm is obtained by multiple dip coating and heat treatment. The lm heat treated at relatively low temperatures of 500 C showed good mechanical adhesion and crystallography. The interface resistivity between superconducting YBCO layer and silver layer prepared by dip coating was measured as 0.67 1013 X m2, which was similar value compared to that of sputtering method. Also, the dip coated silver layer was compatible to the next process for copper electroplating with the thickness of 20 lm. The critical currents of the specimen prepared by dip coating with organic silver complexes and sputtering on same quality YBCO layer were measured as similar value showing excellent compatibility of dip coating method for coated conductor. Acknowledgements This research was supported by a grant from Center for Applied Superconductivity Technology of the 21st Century Frontier R&D Program funded by the Ministry of Education, Science and Technology, Republic of Korea and 2009 Australian Research Council International Fellowship program LX0989591. References
[1] X. Xiong, in: Appl. Super. Conf., August 1822, 2008, Chicago, IL 4MX06. [2] J.B. Lee, S.U. Lee b, S.S. Kim, B.J. Kim, H.J. Kim, Y.S. Yoo, J.G. Kim, G.W. Hong, H.G. Lee, Physica C 469 (2009) 952. [3] C. Oldham, Prog. Inorg. Chem. 10 (1968) 233. [4] E.P. Katchalski, C.B. Klibanski, A. Berger, J. Am. Chem. Soc. 73 (1951) 1829. [5] D.A. Edwards, M. Longley, J. Inorg. Nucl. Chem. 40 (1978) 1599. [6] G. Kaupp, U. Pogodda, A. Atfah, H. Meier, A. Vierengel, Angew. Chem. 31 (1992) 770. [7] J.C. Lin, C.Y. Wang, Mater. Chem. Phys. 45 (1996) 136. [8] J.Y. Kato, N. Sakai, S. Tajima, S. Miyata, M. Konishi, Y. Yamada, N. Chikumoto, K. Nakao, T. Izumi, Y. Shiohara, Physica C 445448 (2006) 686.

Fig. 7. Digital camera images of multiple coated sample by organic silver complexes on YBCO (A) and copper deposited sample (B) on the prepared silver layer.

resistance measured between V1 and V2 is the sum of bulk silver resistance and interface resistance. The interface resistance was calculated by subtracting the resistance of silver layer from the measured resistance calculated from the slope of IV curve shown in Fig. 6. The interface resistance of silver layer prepared by quadruple dip coating was calculated as 0.67 1013 X m2, which was comparable to the value of 0.5 1013 X m2 measured in ordinary silver layer prepared by sputtering method [8]. Another important check point for silver protection layer is the compatibility of silver layer prepared by dip coating with next step process, a copper electroplating process. Fig. 7 shows digital camera images of silver dip coated specimen and copper electroplated specimen, respectively. Electroplating was conducted with process current of DC 0.35 A for 28 min. on sample coated with silver by quadruple dip coating and sintered at 500 C. The electroplated copper showed a bright metallic color and smooth surface roughness without any sign of failure, and measured thickness was about 20 lm. To check the electrical performance of protection layer composed of dip coated silver and electroplated copper, critical current of the specimen was measured by DC 4-probe method at 77 K without external magnetic eld. A specimen with sputtered silver and electroplated copper was also prepared as reference sample and the results are shown in Fig. 8 The IV curve of two samples showed similar results with the critical current of $140A, exhibit-