Physica C 385 (2003) 162168 www.elsevier.

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Resistive behavior and magnetic phase diagram of MgB2 single crystals

Yu. Eltsev
*
Superconductivity Research Laboratory, ISTEC, 10-13 Shinonome, 1-Chome, Koto-ku, Tokyo 135-0062, Japan

Abstract I report on the resistive behavior below Tc and magnetic phase diagram of MgB2 single crystals. Strong current induced resistive transition broadening has been found at magnetic elds above 1.52 T in H kc-axis eld orientation. I discuss this behavior in relation with possible eects of the vortexliquid state, surface superconductivity, excess conductivity as well as double-energy superconducting-gap structure in MgB2 . 2002 Elsevier Science B.V. All rights reserved.
PACS: 74.25.Fy; 74.70.Ad; 74.60.Ec Keywords: Resistivity; Single crystal; Upper critical eld; Anisotropy

1. Introduction The discovery of superconductivity in MgB2 in January 2001 [1] has provided a new point of scientic interest towards studies of various properties of this intermetallic compound with a relatively high Tc around 39 K. Remarkable research activity in about two years since this discovery resulted in a rapid progress in understanding physics of magnesium diboride, and at present it is widely accepted that MgB2 is a moderately anisotropic type-II two-gap superconductor with a phononmediated pairing interaction. Study of the resistive behavior in the mixed state of MgB2 is of great importance for basic re-

* Present address: Solid State Physics, Royal Institute of Technology, 16440 Stockholm-Kista, Sweden. Tel.: +46-8-7904182; fax: +46-8-752-7850. E-mail address: yuri@pollux.imit.kth.se (Yu. Eltsev).

search as well as applications. In particular, measurement of the electrical transport properties is a powerful technique to obtain valuable information on critical elds and critical currents as well as vortex pinning and dissipation mechanisms. On the other hand, existence of two superconducting gaps in MgB2 with a smaller one attributed to the 3D tubular network and a larger one residing on the 2D hole-sheets was predicted from the rstprinciples calculations [2] and experimentally evidenced by the measurements of the quasi-particle tunneling [3,4], specic heat [57], and penetration depth [8]. To the best of our knowledge there are no theoretical models discussing the electrical transport in the mixed state of a two-gap superconductor, like MgB2 . Thus, it remains unclear how the presence of two superconducting gaps with two dierent anisotropies aects magnetotransport properties of MgB2 single crystals. Another unresolved issue concerns signicant dierence between the estimates of the upper crit-

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 2 3 1 2 - 2

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ical eld anisotropy ratio c Hc2k =Hc2? derived from the measurements of the electrical transport properties of MgB2 single crystals and c value obtained by other techniques. In particular, clear signs of the anisotropic superconducting properties of MgB2 expected from the layered crystal structure of this compound were observed already in the rst measurements of the upper critical eld in aligned crystallites [9], thin lms [10] and ne powder [11] samples. Further studies of Hc2 anisotropy performed on MgB2 single crystal by various techniques including electrical transport [1217], torque magnetometry [18], and magnetization measurements [19,20] conrmed anisotropic nature of the superconducting state of MgB2 . Moreover, some of these measurements [1619] revealed very unusual temperature dependent behavior of the upper critical eld anisotropy. However, as obtained from the analysis of magnetic measurements the Hc2 anisotropy ratio increases up to $5 with decreasing temperature [18,19] in contrast to the results of resistive measurements giving maximal c value of about 3 at T 25 K [16,17]. Here we address to these still open questions. Following a brief description of our experimental set-up, we present results of measurements of the currentvoltage response in magnetic elds applied both perpendicular and parallel to the ab-planes of MgB2 single crystals. We discuss the possible origins of a remarkable broadening of the in-plane resistive superconducting transition and strong non-linearity developing in H kc-axis geometry in the entire transition region in relation with vortex-liquid behavior, surface superconductivity, uctuation conductivity and a doubleenergy superconducting-gap structure. Finally, we present magnetic phase diagram of MgB2 single crystal derived from our transport measurements and compare it with available in the literature data for Hc2 T phase diagram obtained from the magnetization measurements.

Fig. 1. Typical zero-eld superconducting transition for MgB2 single crystal measured at current of 1 mA kab-planes. Inset: Normalized temperature dependence of the in-plane resistivity for the same sample.

high pressure and temperature of 46 GPa and 14001700 C respectively [12]. Several plate-like single crystals of size of about 0:5 0:1 0:05 mm3 with dierent quality of lateral surfaces kcaxis (see e.g. Fig. 1 in Ref. [12]) have been chosen for the in-plane transport measurements. Electrical contacts in usual four probes linear geometry were made using gold or silver paste without subsequent heat treatment. Contact resistance was around 1 X for current contacts and slightly higher (about 35 X) for potential ones. The experiments were carried out in a Quantum Design Physical Property Measurement System with a single crystal mounted on a horizontal rotator. To measure current voltage response we used usual low frequency ($17 Hz) ac technique with an excitation current in the range 0.14.0 mA 1 and voltage resolution below 1 nV.

3. Results and discussion High quality of MgB2 single crystals used in our study is illustrated in Fig. 1 where we show typical

2. Experimental Magnesium diboride single crystals have been grown in quasi-ternary MgMgB2 BN system at

In our study of the electrical transport with current directed along the ab-planes we used a few single crystals of approximately the same size $0:5 0:1 0:05 mm3 . Thus, in all our inplane transport measurements the excitation current of 1 mA corresponds to the current density of about 20 A/cm2 .

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zero eld resistive superconducting transition with a transition width DT < 0:3 K and Tc dened as the resistivity onset with criterion of 2% of the full resistivity drop, around 38.8 K. In the inset in Fig. 1 we also present the T -dependence of the inplane resistivity for the same sample showing remarkably high residual resistivity ratio RRR q273 K=q40 K 6:6 compared to RRR values reported by other groups for MgB2 single crystals grown by various techniques [1315]. Fig. 2 shows resistive superconducting transitions at several magnetic elds up to 6 T for H kcaxis (upper panel) and up to 9 T for H kab-planes (lower panel). The anisotropy of the upper critical eld of MgB2 single crystals is clearly seen from dierent transition temperatures in the magnetic elds H kc-axis and H kab-planes of the same magnitude. Furthermore, with the increase of the magnetic eld the structure of the resistive transition itself changes in a very dierent way in two eld orientations. For H kab-planes, increasing magnetic eld results in a shift of the transition to

Fig. 2. Upper panel: Superconducting transitions at various magnetic fieldska-axis up to 6 T as indicated in the gure. Lower panel: Superconducting transitions in the magnetic fieldskab-planes. In both eld orientations excitation current is 0.5 mA and its direction is perpendicular to the magnetic eld.

lower temperatures with slightly eld dependent DT value. On the other hand, for H kc-axis magnetic eld orientation, one can see drastic change of the shape of the resistive superconducting transition at elds of about 1.5 T and substantial transition broadening at higher elds. Very similar behavior of the resistive transition with increasing eld in H kc-axis geometry has been found in other our samples and also reported by dierent groups [21,22], thus, indicating its intrinsic origin. Observed transformation of the structure of superconducting transition at H 11.5 T resembles resistive behavior of clean high-Tc single crystals of YBa2 Cu3 O7d near the critical point in the melting line where sharp resistive step reecting the rst-order uxlattice melting transition was replaced by a continuous second order vortex glass transition at higher elds above the critical point (see e.g. [23]). Signicant broadening of the resistive superconducting transition in high-Tc cuprates above the rst- or second-order vortex melting and below Hc2 was associated with a wide region of the vortexliquid phase showing linear currentvoltage response [23]. However, broadening of the resistive transition in MgB2 single crystals seems cannot be attributed to the vortex-liquid state behavior since in striking contrast to the resistive behavior of high-Tc compounds it is strongly current dependent. The non-linear currentvoltage behavior in MgB2 single crystal is demonstrated in Figs. 3 and 4 where we show resistive transitions measured as a function of temperature and magnetic eld, respectively, with excitation currents within the range of 0.14 mA. It should be noted that similar non-ohmic behavior has been reported for Lorentz-force-free conguration with H kI kc-axis [20]. From Fig. 3 it is immediately clear that non-ohmic voltage response developing with the increase of the magnetic eld in H kc-axis orientation cannot be explained by simple thermal eects since non-linearity is negligible in zero-eld measurements and signicantly reduced in H kabplanes geometry. From Figs. 3 and 4 one can also see that current dependent transition broadening observed at high temperatures (T P 25 K) and low elds (H 6 1:5 T) is very dierent from that found in low-temperature-high-eld part of the magnetic

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Fig. 3. Typical non-linear voltage response in H kc-axis (top panel) and H kab-planes (bottom panel) magnetic eld orientations.

netic eld directed along the c-axis [22,24]. According to Saint-James and de Gennes [25] surface superconductivity can nucleate at a superconductor-insulator interface parallel to the applied magnetic eld at the eld Hc3 exceeding the upper critical eld, Hc2 , by a factor of 1.695. However, our data for MgB2 single crystals do not follow Saint-James and de Gennes result. In fact, as one can see from Fig. 4 the ratio of two magnetic elds corresponding to the onset of non-ohmic behavior and vanishing resistivity obtained with the excitation current of 0.1 mA gradually decreases from $1.8 at 30 K down to $1.4 at 10 K. To make additional test of possible eect of surface superconductivity on resistive behavior of MgB2 single crystals we also performed measurements of the angular dependence of resistivity at several temperatures and elds corresponding to the dierent parts of resistive superconducting transition. Results of these measurements are shown in Fig. 5. Since the value of Hc3 is very sensitive to the magnetic eld orientation and rapidly decreases with the increase of the angle between the magnetic eld direction and a sample surface [26], a non-monotonic behavior of the angular dependence of

Fig. 4. Voltage response vs magnetic eld at various currents and temperatures as indicated in the gure.

phase diagram (T 6 20 K and H P 2 T). In particular, at higher temperatures resistivity starts to increase from zero at almost current independent temperature while at T 6 20 K and H P 2 T the current induced resistive transition broadening gradually increases with decreasing temperature (Fig. 3) or increasing eld (Fig. 4). Recently, similar observation of strongly nonlinear currentvoltage response in MgB2 single crystals was interpreted as a manifestation of the onset of surface superconductivity at the lateral surfaces of the plate-like crystals parallel to mag-

Fig. 5. Angular dependence of the in-plane resistance at various temperatures near the superconducting transition at H 4 T (upper panel) and at H 1 T (lower panel). h 90 corresponds to the magnetic eld kc-axis.

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resistivity with a dip corresponding to the exact eld alignment along the lateral sample surfaces (H kc-axis) may be expected. However, presented in Fig. 5 data do not show any dip structure for angles close to 90, thus, indicating no eect of surface superconductivity on the resistive behavior of MgB2 single crystal in H kc-axis geometry. Concluding this part of discussion we also note that as mentioned above, in our study we used a few MgB2 single crystal with dierent quality of lateral surfaces kc-axis. All of them displayed quantitatively reproducible non-linear behavior giving additional argument against a possibility of any relation between resistive transition broadening and surface superconductivity. We now discuss another possible origin of superconducting transition broadening in MgB2 single crystals related to the uctuation conductivity. From the numerous studies of the resistive behavior in high-Tc cuprates as well as conventional low-Tc superconductors it is well known that the excess conductivity appearing due to superconducting pairs created by thermal uctuations may also result in deviations from the normal state resistivity value above Hc2 and, thus, broadening of resistive superconducting transition (see, for example [27]). The width of critical region may be estimated as jTc T j < Tc Gi with the Ginzburg number, Gi Tc =Hc2 nc n2 ab =2, where Hc is thermodynamic critical eld and nab and nc the inplane and the out-of-plane coherence length, respectively [27]. In high-Tc superconductors with Tc of about 100 K and extremely small coherence length, nab $ 1:5 nm and nc $ 0:2 nm [27], the uctuation conductivity region extends up to 10 K above Tc . On the other hand, for MgB2 single crystals with 2.5 times lower Tc and about one order of magnitude larger corresponding coherence lengths the width of zero eld critical region is estimated to be below 0.01 K. In suciently high magnetic elds kc-axis, when the cyclotron radius of Cooper pair becomes shorter compared to the coherence length, the width of critical region increases, and for H 3 T it was evaluated of about 0.6 K [20]. However, broadening of the resistive transition DT $ 10 K obtained from our experiments at H P 3 T (see Figs. 2 and 3) exceeds estimated width of the uctuation region in more

than one order of magnitude. Thus, we have to conclude that the eect of the excess conductivity cannot describe broadening of the resistive superconducting transition in MgB2 single crystals in H kc-axis magnetic eld orientation. Since resistive behavior of MgB2 single crystals does not nd explanation within vortex-liquid as well as surface superconductivity and excess conductivity scenarios it is tempting to suggest that unusual magneto-transport properties may be related to the double-energy superconducting-gap structure of this compound. However, in the absence of any theoretical model considering transport properties in the mixed state of a two-gap superconductor we can only speculate on this behavior. In line with recent theoretical model for penetration depth in MgB2 [28] we suggest that in H kc-axis magnetic eld orientation the low-temperature-high-eld transport properties are determined by the isotropic smaller gap residing on p-bands whereas behavior at higher temperatures reects contribution from both the anisotropic rband with the larger gap and isotropic smaller gap. The inection point in the temperature dependence of penetration depth at about 20 K corresponding to a smooth crossover between two regimes [28] correlates with the drastic change of the structure of resistive transition clearly seen in our data (see Figs. 2 and 3). In a two-gap superconductor both gaps open at the same zero eld Tc . With increasing eld kc-axis in the high-temperature-low-eld region (T > 25 K, H 6 1:5 T) the resistive superconducting transition displays two-step-like behavior corresponding to the subsequent opening of both gaps. At higher elds (H > 2 T) perpendicular to Mg and B sheets the anisotropic larger gap closes more rapidly and resistive transition shows one-step behavior related to the isotropic smaller gap. In this oversimplied model we associate the resistivity onset with Hc2 for the smaller gap while the end-point of the transition corresponds to the upper limit of Hc2 for the larger gap. In H kabplanes magnetic eld orientation the eect of the magnetic eld on the resistive superconducting transition of MgB2 single crystals does not look unusual. We suggest that in this eld orientation the transport properties of MgB2 single crystals are determined by anisotropic larger gap since in

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parallel eld it has much higher Hc2 compared to the H kc-axis geometry. It should be also noted the origin of strongly non-linear behavior found in H kc-axis eld orientation at low temperatures (see Figs. 3 and 4) remains unclear in our picture. This short discussion obviously demonstrates the need for more work on the resistive behavior below Tc of MgB2 including detailed theoretical study of magneto-transport properties in the mixed state of a two-gap superconductor as well as further experiments on MgB2 single crystals. Finally, we briey discuss the magnetic phase diagram of MgB2 single crystals obtained from our experiments and compare it with the recent results of magnetization measurements performed on MgB2 single crystal [19] as well mosaic sample consisting of about 100 aligned MgB2 single crystals [20]. All these data are shown in Fig. 6. One can see that the onset of diamagnetic response observed from magnetization measurements performed on MgB2 single crystal [19] roughly coincides with the end-point of the resistive transition while the onset temperature of magnetization obtained from the measurements on mosaic sample with about 100 times higher diamagnetic signal

approaches the temperature of resistivity onset [20]. This result clearly indicates that strong difference between the onset temperatures obtained from T -dependences of resistivity and magnetization for one MgB2 single crystal may be due to insucient experimental resolution in the measurements of diamagnetic response from a very small single crystal sample. In particular, estimated in Ref. [20] diamagnetic signal for one MgB2 single crystal at temperatures close to resistivity onset is about 108 emu and, thus, does not exceed the resolution limit of a typical SQUID magnetometer. The data presented in Fig. 6 also give a possible way to understand the dierence between values of the upper critical eld anisotropy ratio obtained from the resistive behavior and magnetization measurements on MgB2 single crystal. In fact, magnetization measurements on the mosaic MgB2 sample with a higher diamagnetic response [20] and our resistive measurements give approximately the same value of Hc2 anisotropy ratio (e.g. c % 3 at T 25 K), while from the magnetic measurements on MgB2 single crystal with lower diamagnetic response c value slightly exceeding 4 at T 25 K was found [19]. Probably, the same assumption of underestimated Hc2 value in H kcaxis eld orientation and, thus, overestimated Hc2 anisotropy ratio may be applied to other bulk measurements, like heat capacitance [22,24], torque magnetometry [18], and thermal conductivity [29] also performed on very small MgB2 single crystals.

4. Conclusions In conclusion, we presented results of the electrical transport measurements below Tc of MgB2 single crystals in magnetic eld kc-axis as well as H kab-planes using excitation currents in the broad range of 0.14 mA. We have shown that observed current induced broadening of resistive superconducting transitions in H kc-axis magnetic eld orientation cannot be explained by the vortex-liquid behavior as well as the eects of surface superconductivity and excess conductivity. We suggest that unusual magneto-transport properties in the

Fig. 6. Magnetic phase diagram of MgB2 single crystal. Horizontal lines represent broadening of the resistive transition with increasing eld and vertical bars show transition onset and endpoint. Triangles demonstrate onset of diamagnetic response obtained in Ref. [19] from the magnetization measurements on MgB2 single crystal. Circles represent onset of diamagnetic response obtained in Ref. [20] from the measurements of M T dependences of mosaic sample consisting of about 100 aligned MgB2 single crystals.

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