Physica C 470 (2010) S237S238

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

Biopolymer mediated solgel synthesis of LuBa2Cu3O7d

James Dedman a, Stuart C. Wimbush b, Simon R. Hall a,*
a b

Centre for Organized Matter Chemistry, School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS, UK Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK

a r t i c l e

i n f o

a b s t r a c t
The use of biopolymer templates to control crystallization of superconducting phases is a recent phenomenon which is generating a lot of interest both from the superconductor community and more widely in materials chemistry circles. The high temperature superconducting material LuBa2Cu3O7d has been synthesized successfully using the biopolymer dextran, leading to a greatly improved synthesis time of 48 h in comparison to the previous solid state synthesis timescale of over 500 h. 2009 Elsevier B.V. All rights reserved.

Article history: Accepted 20 October 2009 Available online 5 November 2009 Keywords: Cuprate superconductors Biopolymers Templating Synthesis

1. Introduction The quaternary cuprate LuBa2Cu3O7d (Lu123) has previously been synthesized in single crystal form with a superconducting transition temperature Tc of 92.5 K [1], and as a thin lm via pulsed laser deposition [2] and metalorganic chemical vapour deposition [3], with Tc ranging from 86 K to 88 K and critical current densities Jc reportedly up to 5 MA cm2 at 77 K. Attempts to synthesize single-phase Lu123 ceramics have been unsuccessful until recently, however, when there was success using a solid state method [4] that resulted in Lu123 having a Tc of 92 K after an extended period of calcination and annealing taking more than 500 h to achieve phase purity. Here we demonstrate a novel and facile method of synthesising Lu123 via a solgel biopolymer approach. By constraining the nucleation and growth of the superconducting phase within a carbonizing biopolymer, the reaction proceeds to completion in less than 48 h. In the solid state method, precursor materials were ground for over 150 h in order to ensure homogeneity of the reagents. The solgel biopolymer approach is an increasingly common solution to the problem of heterogeneity in the early stages of synthesis, reducing particle size more effectively than mechanical grinding, and allowing for synthetic homogeneity at the atomic level. By pre-organizing precursor metal cations within a biopolymer gel, nucleation of precursor crystalline phases is restricted to the nano-scale. On calcination, the decomposition products of the biopolymer prevent sintering of these nanoparticles before the nal crystallographic transformation to the superconducting product [57]. The cooperative effect of the polymer microstructure
* Corresponding author. E-mail address: simon.hall@bristol.ac.uk (S.R. Hall). 0921-4534/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.physc.2009.10.022

and decomposition products allow an exceptional level of control over nucleation and growth of the superconductor; in addition to the production of nanoparticles, this method has also been used to grow anisotropic, single crystal superconducting nanowires [8,9]. In this work, we used the biopolymer dextran as a matrix for the superconductor synthesis. Dextran is a complex, branched polysaccharide composed of a large number of glucose subunits so that the molecular weight can vary between one thousand and several hundred thousand daltons. The backbone of the dextran molecule consists of a-1,6-glycosidic linkages, with branches forming primarily from a-1,3-links. As dextran is a reducing sugar, the reductive aldehyde groups can be exploited for in situ reduction of metal ions and nucleation of monodisperse metallic clusters. The synthesis of Lu123 was attempted in the presence of dextran. Notably a control was initially carried out with the biopolymer replaced by the organic solvent ethylene glycol. Ethylene glycol acts as an agent to induce hydrogen bonding, controlling the viscosity of the gel and the decomposition temperature of the dried solution during calcination, as well as providing a biopolymer analogue in that it will ensure effective homogeneity of the reaction mixture/ion distribution [10,11].

2. Experimental Lutetium nitrate (0.902 g), barium nitrate (1.307 g) and copper nitrate (1.744 g) were completely dissolved in distilled water (50 ml) to give a stoichiometric ratio of 1:2:3. For the control samples, ethylene glycol (5 ml) was added to this transparent blue precursor solution and left to dry overnight in an oil bath at 70 C. For the biopolymer-mediated syntheses, dextran (4.00 g) and precur-

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J. Dedman et al. / Physica C 470 (2010) S237S238

Fig. 1. SEM images showing (a) crystalline material synthesized in the presence of ethylene glycol and (b) reticulated structure of Lu123 as synthesized in the presence of dextran. Scale bar in (a) is 2 lm and in (b) is 5 lm.

sor solution (2 ml) were mixed together in a crucible and left to harden at room temperature for 1 day. Once completely dry the samples were heated at a rate of 10 C min1 to 920 C before calcining in air for 1 h. The hard, black solid thus obtained was then ground into a powder. Samples for the scanning electron microscope (SEM; JEOL JSM 5600, 15 kV) were prepared by mounting on aluminium stubs and sputter coating with platinum prior to observation. Powder X-ray diffraction (XRD) was carried out using a Bruker D8 Advance powder diffractometer (Cu Ka radiation, 1.54056 ; 2h values 15 55, step interval 0.02). SQUID magnetometry was performed using a Quantum Design Magnetic Property Measurement System equipped with a 5 T superconducting magnet. The measured data were not corrected for demagnetisation effects. Field cooled (FC) and zero eld cooled (ZFC) dc susceptibility was measured as a function of temperature under an applied eld of 1 mT. The intragrain Jc of the samples was determined by applying a critical state model to full magnetisation loops measured at xed temperatures, taking the particle size from the SEM observations and assuming a density for Lu123 of 7.263 g/cm3 [4]. 3. Results and discussion SEM images of the control sample (ethylene glycol and precursor) revealed a material comprised of well-dened crystals (Fig. 1a). Energy-dispersive X-ray (EDX) analysis showed peaks due to lutetium, barium and copper. This is in marked contrast to syntheses involving biopolymers, which show a more bio-like non-classical structure. Fig. 1b shows an SEM image of Lu123 synthesized in the presence of dextran. In this case, the product is a reticulated, porous network, in which are contained well-dened crystallites of around 1 lm in diameter. Many of these crystallites are intergrown, following the pattern of the bio-matrix as it calcines. EDX again detected peaks due to lutetium, barium and copper. Conrmation of the phase produced was by XRD. In the case of ethylene glycol mediation, the results show peaks only from BaCuO2 (JCPDS #38-1402), Lu2O3 (JCPDS #12-0728) and CuO (JCPDS #48-1548), indicating that the synthesis using ethylene glycol was unsuccessful. This is in contrast to the dextran-mediated synthesis, where in addition to these phases, peaks were present at d = 3.88 (003); 2.74 (103); 2.71 (013); 2.22 (113); 1.90 (020); 1.58 (116) and 1.56 (123), indicative of the Lu123 phase [4]. SQUID magnetometry showed that whilst the ethylene glycolmediated synthesis product was non-superconducting down to 10 K, dextran-mediated Lu123 is superconducting with a Tc of 89 K (Fig. 2a). This is similar to the critical temperature of Lu123 observed in other syntheses. The Jc of Lu123 synthesized in the

Fig. 2. SQUID magnetometry data showing (a) critical temperature (Tc) and (b) critical current density (Jc) of Lu123 material synthesized in the presence of dextran. The control sample synthesized without dextran showed a paramagnetic response and was non-superconducting.

presence of dextran was estimated as 1.2 MA cm2 at 10 K and zero applied eld (Fig. 2b). This is comparable to the value observed for many of the thin lm samples [3], and while unfortunately no data is available for bulk Lu123 material for comparison [1,4], it is somewhat better than that obtained on commercially available superconducting YBa2Cu3O7d (Y123) powder (Aldrich 99.9%) [5], and retains the potential for further improvement using techniques that have been employed successfully with Y123 [12,13]. 4. Conclusion We have demonstrated that LuBa2Cu3O7d can be synthesized successfully via a solgel biopolymer approach which greatly improves on the time taken by current solid state techniques. Synthesis took a mere 48 h in comparison to the previous duration of more than 500 h. The resulting material demonstrates good superconducting properties. Biotemplating approaches offer a means to tackle the synthesis of difcult ceramic materials. Acknowledgments The authors thank the Royal Society and UK EPSRC for nancial support. S.C.W. is supported by The Leverhulme Trust with subsidiary funding from The Isaac Newton Trust. References
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