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Li NMR studies in magnetically frustrated LiV2O4: Evidence for a spin-liquid ground state?
N. Bttgen, H. Kaps, W. Trinkl, A. Loidl, M. Klemm, and S. Horn

Abstract: 7 Li NMR measurements were performed in the metallic spinel LiV2 O4 . The temperature dependence of the spin-lattice relaxation rate is documented in the temperature range 100 mK < T < 280 K. A comparison with the spin-glass behavior of Li1x Znx V2 O4 for small concentrations of x is given. For low temperatures T < 1 K we observe a maximum for the spin-lattice relaxation rate in LiV2 O4 . The frequency dependence of this maximum is indicative for a slowing down of spin uctuations. The NMR results can be explained by a spin-liquid behavior and the opening of a spin gap of the order 1 K. PACS Nos.: 75.20Hr, 75.50Lk, 76.60Es, 76.60-k Rsum : Des mesures RMN sur 7 Li ont t faites dans le spinelle mtallique LiV2 O4 . La dpendance en temprature du taux de relaxation du rseau de spin est chantillonne dans le domaine 100 mK < T < 280 K. Nous comparons avec le comportement verre de spin du Li1x Znx V2 O4 pour de petites concentrations x. basse temprature, T < 1 K, nous observons un maximum du taux de relaxation de verre de spin dans LiV2 O4 . La dpendance en frquence de ce maximum indique un ralentissement des uctuations de spin. On peut expliquer les rsultats RMN par un comportement de liquide de spin et louverture dun intervalle (gap) de spin de lordre de 1 K. [Traduit par la Rdaction]

1. Introduction
Among the transition metal oxides with spinel structure there are only two compounds that reveal the fcc (face-centered cube) normal-spinel structure and exhibit metallic conductivity to low temperatures: LiTi2 O4 [1] and LiV2 O4 [2]. In these compounds the transition-metal ions occupy the sites of a regular tetrahedron and hence they are geometrically frustrated against the evolution of simple antiferromagnetic structures. The former, LiTi2 O4 is a superconductor [1] with a transition temperature as high as 12.5 K, the latter LiV2 O4 has been reported to be a heavy-fermion transition-metal oxide [36] with a high Sommerfeld coefcient of the heat capacity ( = 420 mJ/mol K2 ) and a high and almost

Received June 12, 2000. Accepted August 8, 2001. Published on the NRC Research Press Web site on December 4, 2001. N. Bttgen,1 H. Kaps, W. Trinkl, and A. Loidl. Experimentalphysik V, Elektronische Korrelationen und Magnetismus, Institut fr Physik, Universitt Augsburg, D86135 Augsburg, Germany. M. Klemm and S. Horn. Experimentalphysik II, Institut fr Physik, Universitt Augsburg, D86135 Augsburg, Germany.
1

Corresponding author.
DOI: 10.1139/cjp-79-11/12-1487 2001 NRC Canada

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Fig. 1. Temperature dependence of the magnetization divided by the applied eld of 1 kOe in Li1x Znx V2 O4 and Li(V1x Tix )2 O4 between 1.9 K < T < 30 K. Arrows indicate the spin-glass temperatures Tf . The inset displays the zero-eld-cooled (ZFC) and eld-cooled (FC) measurements for the Zn-doped sample x = 0.2 [10].

temperature-independent magnetic susceptibility at low temperatures [3, 6]. An interpretation, within the framework of heavy fermions due to Kondo compensation of localized moments, has been corroborated by band structure calculations [7]. It is interesting to note that both compounds that reveal the cubic spinel structure exhibit no long-range magnetic order down to the lowest temperatures, which possibly results from the geometrical frustration, and, as outlined above, is an inherent property of the spinel structure where the transition-metal ions form corner-sharing tetrahedra. In this contribution we report low-temperature NMR experiments extending to 30 mK. The temperature dependence of the spinlattice relaxation rates convincingly demonstrates that in LiV2 O4 the spin dynamics slows down exponentially but exhibits no static magnetic order. We conclude that LiV2 O4 is similar to other frustrated spinuctuation systems like -Mn [8] or Sc doped YMn2 [9], but in addition reveals the opening of a spin gap at low temperatures. We speculate about an unconventional magnetic ground state. It is unclear how this behavior can be reconciled with Kondo compensation effects.

2. Experimental details
2.1. Sample preparation Polycrystalline samples of Li1x Znx V2 O4 and Li(V1x Tix )2 O4 were prepared by sintering a mixture of powders of LiVO3 and VO with slight excess of LiVO3 to compensate for Li evaporation. Platinum crucibles were used for reaction of the powders at 750 C for 10 days. From EPR and magnetic susceptibility measurements, we estimated a number of 0.1% V defects for our LiV2 O4 sample. In X-ray diffraction experiments, we found the fcc spinel structure for all concentrations (x = 0, 0.05, 0.1, 0.2, and 0.3). Figure 1 shows the magnetization measured in an applied eld of 1 kOe. These magnetization measurements were performed with a commercial SQUIDmagnetometer from QUANTUM DESIGN [10]. While the pure compound LiV2 O4 exhibits a continuous increase towards low temperatures the magnetization levels-off below a given temperature for x > 0. The temperature of this anomaly increases with increasing Zn-concentration from 2 K (for x = 0.05) to 13.8 K (for
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Fig. 2. 7 Li eld-sweep spectra of LiV2 O4 ; the continuous lines are ts to a Lorentzian line. The spectrometer frequency was approximately 17 MHz. The inset shows the temperature dependence of the spin-echo intensity multiplied by temperature (I T ).

x = 0.3) and is indicative of static spin freezing similar to observations in canonical spin-glass systems. The arrows indicate the spin-glass freezing temperatures Tf . The freezing temperatures in the Zn-doped compounds of Tf = 9 K for x = 0.2 and 13.8 K for x = 0.3 are enhanced compared with the results of Ueda et al. [11] where Tf = 5 K (x = 0.2) and 9 K (x = 0.3) have been deduced from zero-eld-cooled measurements. Such pronounced spin-glass behavior could not be observed for Li(V1x Tix )2 O4 . However, a signicant change of slope in these compounds occurs for x = 0.2 and x = 0.3 close to 4 K (lower frame in Fig. 1). 2.2. 7 Li NMR experiment The NMR measurements were performed with a phase-coherent pulse spectrometer probing the 7 Li nuclei (spin I = 3/2, gyromagnetic ratio = 16.546 MHz/T). The spectra were obtained using eld sweeps at constant frequencies /2 = 7.59,17.3, and 72.7 MHz. Cryogenic temperatures were provided by a 3 He/4 He dilution refrigerator with the NMR resonant circuit inside the mixing chamber. Conventional spin-echo sequences /2 D were used to collect the spectra. The spin-lattice relaxation rate 1/T1 was determined from the inversion recovery of the spin-echo intensity with an inversion pulse length of 40 s. At low temperatures, a stretched exponential relaxation behavior of the nuclear magnetization M(t) exp[(t/T1 ) ] was observed as has been reported previously [12]. 7 Li spectra for very low temperatures are displayed in Fig. 2. Since the Li nucleus is located on cubic lattice sites accompanied by a tetrahedral coordination, no electric eld gradient splits the line in the powdered sample. The spectra are almost symmetric and can reasonably be described using a Lorentzian line shape down to the lowest temperature (continuous lines in Fig. 2). In the pure compound, the intensity increases with a Curie law towards decreasing temperature and the line width broadens slightly. The inset in Fig. 2 shows the product of intensity and temperature (I T ). At the lowest temperatures only a small fraction of nuclear spins contribute to the signal as is clearly shown by the drastic decrease of the NMR intensity for temperatures T < 1 K.

3. Results and discussion

The temperature dependence of the spin-lattice relaxation rate 1/T1 of Zn- and Ti-doped compounds is shown in Fig. 3. Compared with Zn- and Ti-doped compounds the pure compound LiV2 O4 exhibits the smallest relaxation rates within the entire temperature range. In Li1x Znx V2 O4 for x = 0.05, 0.1,
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Fig. 3. 7 Li spin-lattice relaxation rate 1/T1 vs. temperature T . For the Zn-doped samples (upper frame) the sharp anomalies are indicative for spin-glass behavior in Li1x Znx V2 O4 [10, 11].

and 0.2 (upper frame) the sharp anomalies in 1/T1 (T ) most probably indicate the spin-glass freezing. Similar observations are made for Ti-doping (lower frame), but no sharp anomalies could be observed in these compounds. On decreasing the temperatures, in pure LiV2 O4 1/T1 slightly increases, passes through a maximum close to 30 K, and decreases towards the lowest temperatures. The maximum close to 30 K for the pure compound nicely resembles the results reported in the literature [3,13,14]. We point out that such a maximum in 1/T1 (T ) can easily be explained by a CurieWeiss law of the susceptibility with a negative CurieWeiss temperature in combination with a magnetic relaxation rate , which only weakly depends on temperature [15]. This certainly is the case in LiV2 O4 and could result from both, Kondo compensation or frustrated magnetic interactions. Kondo et al. [3] interpreted this temperature as the characteristic temperature T of the Kondo effect in LiV2 O4 where strong hybridization effects between the localized moments and the band states set in and result in an increasing compensation of the localized moments towards low temperatures. Below T /10 moment compensation probably would be fully completed as is the case in traditional heavy-fermion systems. Astonishingly, at low measuring frequencies a clear cusp-shaped maximum appears in 1/T1 (T ) at approximately T = 0.6 K in LiV2 O4 (see Fig. 4). In Fig. 4 the spin-lattice relaxation rate 7 (1/T1 ) for LiV2 O4 is compared to the spin-lattice relaxation for prototypical heavy-fermion systems. We recall that, depending on the exact Ce stoichiometry, CeCu2 Si2 reveals superconductivity (S-phase: + symbols in Fig. 4) or magnetic order (A-phase: ) [16]. The A-phase also is established in CeCu2 (Si1y Gey )2 for low Ge concentrations y < 0.3 [17]. The similarity of the low-temperature anomalies of Ce-based heavy-fermion systems and LiV2 O4 suggests that for LiV2 O4 also slow magnetic uctuations rather than static spin freezing dominates the ground-state properties. To study the anomalous low-temperature relaxation in more detail, we performed a series of experiments at different measuring frequencies and associated magnetic elds (Fig. 5). Below 2 K the temperature dependence of 1/T1 reveals a signicant frequency dependence and the nuclear relaxation is strongly enhanced at low frequencies. This behavior clearly reveals a characteristic similar to the Li nuclear relaxation observed in Li-doped CuO and NiO by Rigamonti and co-workers [19], which has
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Fig. 4. 7 Li spin-lattice relaxation rate in LiV2 O4 at 17.3 MHz for temperatures 100 mK < T < 160 K compared to 63 Cu spin-lattice relaxation rate in the prototypical heavy-fermion compounds CeCu2 (Si1y Gey )2 ; y = 0.1 ( NMR and NQR, TA 1 K (K. Ishida. Private communication.)), y = 0 (+ NMR, Tc = 0.6 K [18]), Ce0.99 Cu2.02 Si2 ( NQR, TA = 0.6 K [16]). The continuous line represents the Korringa relation (T1 T )1 = 0.19 (sK)1 for the conduction electrons in LaCu2.2 Si2 ( ) reconciling the high-temperature Korringa relation in CeCu2 (Si0.9 Ge0.1 )2 , respectively.

been compared to the spin dynamics in cuprate superconductors. On the basis of this interpretation the cusplike anomalies in Fig. 5a signal the slowing down of spin uctuation on a time scale given by the NMR Larmor frequency 0 . At the cusp maximum the measuring frequency corresponds directly to the magnetic relaxation rate and at temperatures T < 0.6 K the slow relaxation regime ( 0 ) is reached. This observation of slow-spin dynamics down to the lowest temperature is in agreement with the SR results where the sample with the lowest impurity concentration revealed a slowing down of spin uctuation with no signature for static freezing [3, 20]. This indeed could be due to the opening of a spin gap or, to magnetic interactions, e.g., magnetic dipolar interactions. In Fig. 5b, we show the low-temperature spin-lattice relaxation rate for 7.59 MHz/4.6 kOe in an Arrhenius representation to indicate the exponential increase of 1/T1 (T ) at low temperatures. From this plot, we deduce a spin gap (or an interaction energy) S = 0.6 K in an applied eld of 4.6 kOe. For frequencies and (or) elds higher than 17.3 MHz/10 kOe the energy gap is suppressed. This behavior nicely resembles the eld-induced closing of the energy gap in SrCu2 (BO3 )2 , which compound reveals a transition from a dimer ground state to a gapless magnetic state [21]. In summary, our observations are in accord with
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Fig. 5. (a) 7 Li spin-lattice relaxation rate 1/T1 vs. temperature T in LiV2 O4 . The symbols indicate different frequencies and (or) external elds, respectively: ( ) 7.59 MHz/4.6 kOe, () 17.3 MHz/10 kOe, and (+) 72.7 MHz/44 kOe. (b) Arrhenius representation of the spin-lattice relaxation rate 1/T1 at 7.59 MHz/4.6 kOe. The continuous line indicates an activated behavior with a spin gap (or an interaction energy) S = 0.6 K.

the predictions for geometrical magnetic frustration, which suppresses long-range magnetic order and favors the formation of a spin liquid or an unconventional non-Nel magnetic ground state [2224].

4. Conclusion
We believe that LiV2 O4 is dominated by frustration effects rather than by moment compensation. Can we exclude a spin-glass transition? Exotic spin-glass behavior in systems without disorder has been proposed by Villain [25] who pointed out that canonical spin-glass behavior is unlikely to occur for spinels like LiV2 O4 . In addition, taking a Kondo-lattice temperature of 30 K, it is hard to understand how random freezing of moments can appear well below 1 K with fully compensated moments. Also, from a purely experimental point of view, the (dynamic) transition below 1 K behaves signicantly differently when compared to the spin-glass transitions observed in disordered Li1x Znx V2 O4 with Zn concentrations x > 0.05 [10]. Instead, we believe we have observed a frequency- and temperaturedependent spin-lattice relaxation indicating a spin-liquid behavior (or another complex non-Nel state) in geometrically frustrated LiV2 O4 .
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Acknowledgements
This work has been supported in part by the Sonderforschungsbereich 484 (Augsburg) of the Deutsche Forschungsgemeinschaft and the BMBF under the contract number EKM 13N6917/0.

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