Physica C 383 (2003) 417420 www.elsevier.

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High temperature magnetic anomalie in Nax WO3 single crystals at low sodium content
N.N. Garifyanov *, E.L. Vavilova
Kazan Physical-Technical Institute, 420029 Kazan, Russia Received 15 November 2001; accepted 13 February 2002

Abstract Sodium tungsten bronze single crystals with low sodium content x 0:14 were grown by the electrochemical reduction method. The magnetic and transport properties of the obtained Nax WO3 samples were investigated. The results of SQUID magnetic measurements show presence of a magnetic anomalie at 150 K. It indicates the possible existence of the high-temperature superconducting phase in sodium tungsten bronzes. 2002 Elsevier Science B.V. All rights reserved.
PACS: 74.25.Ha; 74.62.Bf Keywords: Non-cuprate superconductors; Tungsten bronzes

1. Introduction The tungsten bronzes are non-stoichiometric compounds with general formula Mx WO3 . The most extensive studies were carried out for the alkali metals, especially for sodium. Interest into tungsten bronzes has enhanced in 1964 when Raub reported superconductivity in the tetragonal sodium tungsten bronze [1]. It should be noted that this was one of the rst superconducting metaloxides. After the discovery of high-Tc superconductivity the interest into this class of materials diminished. However the results of our previous investigations [2,3] show that tungsten bronzes and cuprate systems have several common features.

The recent discovery of new high temperature superconductors, e.g. MgB2 [4], revives the interest into dierent non-cuprate systems. Hence it is time to revise the experimental facts dealing with the earlier known metaloxides. In spite of the long time investigation on sodium tungsten bronzes, the low sodium content region is poorly investigated up to now due to the diculties in the preparation. However, we believe, this is the region that should attract attention because of its interesting properties (see, for example, [5]).

2. Sample preparation It is very dicult to prepare the low sodium content Nax WO3 single crystals. In principle there is the possibility to reach the low doping range by solid-state reaction methods [6], but the obtained

Corresponding author. Fax: +7-8432-765-075. E-mail address: nadir@kfti.knc.ru (N.N. Garifyanov).

0921-4534/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 1 - 4 5 3 4 ( 0 2 ) 0 1 4 5 7 - 0

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single crystals are extremely small. Therefore we used an electrochemical reduction method [7]. The growth parameters for preparation of Nax WO3 crystals with sodium content x 0:14 were found. The sodium content was estimated from growth phase diagram [7]. Two single crystals with slightly dierent growth parameters were prepared. The approximate size of crystals are 1 1 2 mm, which is large enough for magnetic and transport investigations.

3. Results The magnetic properties of the obtained samples were studied by SQUID magnetometry. The temperature dependence of the magnetic susceptibility of the sample N1 is shown on the Fig. 1. A Curie-like behavior is observed at low temperatures. Usually this is typical for small amounts of uncontrolled magnetic impurities. At high tem-

peratures the susceptibility does not change. Apparently there are two contributions to magnetic susceptibility: A diamagnetic (core) and a Pauli one. The most interesting feature in the magnetic susceptibility is the anomaly around 150 K. The data obtained for the sample N2 are similar to the ones of the sample N1 and show the same anomaly in the temperature dependence of magnetic susceptibility. In both cases this anomaly disappears at eld cooling (H 10 Oe). The eld dependency of the magnetization was measured just below and above the anomaly. Fig. 2 shows the dierence between the magnetization at these two temperatures. The eld dependence MT 1 MT 2 has a remarkable minimum at H 50 Oe. The resistivity data were obtained by standard four points measurement and its temperature dependence is shown at Fig. 3. The value of measuring current was 10 lA. The same temperature dependence was observed at 100 lA. This dependence shows a semiconductor-like behavior, which is

Fig. 1. Magnetic susceptibility of the sample N1 versus temperaturezero eld cooling and eld cooling process. H 100 Oe.

Fig. 2. Dierence in magnetization values between 150 and 100 K as function of external magnetic eld.

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Fig. 3. The temperature dependence of the resistivity of the sample N1.

typical for sodium tungsten bronzes with low doping level.

4. Discussion As known, tungsten trioxide is diamagnetic. When we introduce Na into the WO3 matrix, each sodium ions contributes one electron to the conduction band. It leads to the appearing of the Pauli contribution to the magnetic susceptibility. Both of those contributions are temperature independent. However it is known that sodium tungsten bronze related compounds have several structural phase transitions at high temperatures [8], which can be the reason of changing the density of electron states at the Fermi level and, hence, the Pauli susceptibility. It can cause the observed anomaly in the susceptibility at 150 K. However our estimates indicate that the value of the conduction electron susceptibility is not enough to explain the

magnitude of the observed eect. Moreover, from this point of view it is impossible to understand the disappearance of the anomaly in the eld cooling experiments as well as the eld dependence of the magnetization. As an attempt to explain the observed anomaly we should note that these curves look like the magnetic curves observed in superconductors when only a small part of the sample undergoes a superconducting transition. If the superconducting regions are distributed in the normal matrix and have week links between each other, there is a distinction between magnetization curves in eld cooling and zero eld cooling measurements. A possible opportunity to explain the obtained results is the supposition that there are regions in Nax WO3 crystal that became superconducting with decreasing temperature. For a type II superconductor it is possible to determine the lower critical eld value Hc1 from the eld dependence of the magnetization. As assuming, our sample consists of superconducting and normal state regions, the eld dependence of the magnetization below Tc contains the contributions of both type regions. The contribution to the magnetization from the normal part of the sample, in contrast to the superconducting one, should not signicantly change when temperature goes through Tc . That is why we can obtain data, which contain the eld dependence of the superconducting region magnetization by subtracting the curve obtained below 150 K from the curve obtained above 150 K. The curve shape (Fig. 2) is actually typical for a type II superconductors. From this data we can estimate the lower critical eld value as 50 Oe. From magnetic measurements data it is possible to conclude that the average size and total volume of superconducting regions are very small. That is why it is no wonder that there is no sharp resistivity decrease below 150 K. Moreover as Fig. 1 shows the supposed superconducting transition is spread over a wide temperature region. A broad superconducting transition of a very small part of the sample will not lead to a jump in resistivity curve (which comes from semiconductor behavior of the main crystal volume). This model allows to understand the obtained results, however the critical temperature value is really surprising. Critical temperatures obtained from early

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investigated tungsten bronzes were not higher than 3 K [5]. Never the less in a recent paper [9] it was reported the observation of Tc 90 K in tungsten trioxide single crystal with a surface doped with a small quantity (0.05) of sodium. Field and temperature dependencies of magnetization presented in this article are similar to our curves. Their lower critical eld value is comparable to Hc1 for our samples. The authors [10] supposed that superconductivity exists in the thin surface layer contained practically all of sodium been introduced into the single crystal. In our case the samples are sodium tungsten bronze single crystals. The similarity of the obtained results indicates that the above mentioned thin layer is the sodium tungsten bronze developed into tungsten trioxide single crystal surface. As the surface layer structure is essentially dierent from WO3 crystal lattice, so apparently there is a mismatch interlayer with heavy structure tension. That structure tension can essentially modify the tungsten trioxide properties (see, for example, [11]). In contrast to the above mentioned papers [9,10] in our sample bronzes are not only the crystal surface but also the bulk crystals. Electrochemical reduction crystal growth phase diagram [7] has a number of peculiarities in the low sodium content region. Therefore even small growth conditions deviations can result the local inhomogeneity of the crystal. Apparently the very low sodium content regions exist in the sample, although the total volume of these regions is obviously small. Never the less the heavy structure tension perhaps arises on the borders of these regions due to lattice constant dierence. If observed magnetic and transport features are mainly deter-

mined by superconductivity, as it was supposed in papers [9,10], the origin of the superconductivity in our samples should be the same. So, the low sodium content as well as crystal structure tension are favorable to observed high superconducting transition temperature. The large scattering of Tc value indicates that the optimal for superconductivity sodium content is not found up to now.

Acknowledgement The work of one of us (EV) is supported by RFBR grant 01-02-17533.

References
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