Journal of the Korean Physical Society, Vol. 52, No. 2, February 2008, pp.

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Anisotropic Magnetization and Charge Density Wave in a Na0.78 CoO2 Single Crystal
Jong-Soo Rhyee, J. B. Peng and C. T. Lin
Max-Plank-Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart, Germany D-70569

S. M. Lee
Advanced Materials Lab., Samsung Advanced Institute of Technology, Suwon 440-600 (Received 15 October 2007) Single crystals of Na0.78 CoO2 were grown using the oating zone method. The static magnetic susceptibility M/H(T ) of Na0.78 CoO2 showed signicant anisotropic behavior for dierent crystal orientations of H (ab) and H (c). While (M/H)ab (T ) for a magnetic eld H = 1 T in an ab-plane followed the Curie-Weiss law at high temperatures (T 100 K), (M/H)c (T ) for H c-axis deviated from Curie-Weiss behavior, which may be understood by using phonon localization from strong electron-phonon coupling. The impurity spin-1/2 eect, dressed by spin uctuation, was signicant at low temperatures (T 30 K) for both eld orientations of H (ab) and H (c). The electrical resistivity (T ) of Na0.78 CoO2 showed a clear metallic character down to 16 K, with a weak increase in the resistivity (T ) at low temperatures (T 16 K). The gap-like behavior of (T ) was insensitive to applied magnetic elds up to 7 T, which indicates a non-degenerate charge gap. The electrical conductivity (T ) followed the density wave behavior with a small energy gap (0.64 meV) at low temperatures. We discussed the electrical resistivity (T ) and the anisotropic M/H(T ) behavior of Na0.78 CoO2 in terms of the charge density wave and a strong electron-phonon interaction.
PACS numbers: 75.30.Gw, 75.50.Ee, 71.45.Lr, 75.30.Mb Keywords: Magnetic anisotropy, Crystal growth, Electron-phonon interactions, Valence uctuations

I. INTRODUCTION Much attention has been given to the Nax CoO2 system because of its emergent unconventional physical properties since the discovery of superconductivity at Tc 4.5 K for hydrated compounds of Nax CoO2 yH2 O (x 0.35, y 1.3) and because of the signicantly enhanced thermopower of Na0.85 CoO2 [13]. Nax CoO2 is a layered compound in which the Na charge reservoir layer is interspaced between CoO2 layers. The Na deintercalation and hydration reinforce the two-dimensional character of Nax CoO2 by expanding the charge reservoir layer [4, 5]. The two-dimensional anisotropic properties are still evident for non-hydrated Nax CoO2 series compounds in terms of electronic and magnetic ground states. From the polarized- and unpolarized-neutron inelastic scattering measurements of Na0.75 CoO2 , the ferromagnetic spin uctuation was observed within the CoO2 layers whereas the antiferromagnetic correlation was seen perpendicular to the layers, which corresponds to A-type antiferromag Corresponding E-mail:

Author: js.rhyee@samsung.com; ct.lin@fkf.mpg.de

netic ordering [6,7]. The two-dimensional spin state of the Nax CoO2 system (x 0.75), which neutron diraction studies conrm as following an A-type antiferromagnetic order, is not trivial for the broad range of Na non-stoichiometry x. The magnetic spin of this system is strongly correlated with the competing orders of the charge, orbital, and lattice degrees of freedom. The spectral ellipsometry measurement shows that the spin-charge coupling is strong in the Na0.82 CoO2 compound, which means a charge-induced spin-state transition of the Co3+ ions [8]. In addition, the A-type antiferromagnetic order of Na0.82 CoO2 was characterized by spin wave dispersions in a neutron diraction experiment [9]. The magnetic ground states and the anisotropic properties of Nax CoO2 are very dierent with respect to the Na concentration x because of the spin state of Co in the Nax CoO2 system being strongly inuenced by the Na concentration. The parent compound of CoO2 is regarded as an orbitally nondegenerate spin-1/2 antiferromagnetic Mott insulator with Co4+ [10]. In stoichiometric NaCoO2 , the Co spin state is the low spin state of Co3+ (t6 ) with S = 0. 2g For the intermediate region of Na concentration (x < 1),
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a mixed valent system between Co3+ and Co4+ would be revealed in the Nax CoO2 system. The Na concentration controls both the carrier concentration and the magnetic moment due to Co4+ ions. From the unconventional magnetic ground states of the A-type antiferromagnetic order and the spin density wave behavior in Na0.75 CoO2 and Na0.82 CoO2 , respectively, the unconventional spin state and the anisotropic properties of the magnetic and the electronic transport for Nax CoO2 (0.75 x 0.82) compounds are of particular interest. Presented in this paper are the anisotropic magnetic ground states and the electrical transport properties of a high-quality Na0.78 CoO2 single crystals grown using the oating zone method. The crystals two-dimensional characteristics are identied by using the density wave gap in the electrical resistivity (T ) and the strong anisotropic behavior of the magnetization M/H(T ) with respect to dierent magnetic eld directions of H (c)axis and H (ab)-plane of the Na0.78 CoO2 compounds. The magnetic susceptibilities under a magnetic eld H along the c- and the ab-directions show logarithmically divergent behaviors of (M/H)ab (T ) at low temperatures (T 20 K) and non-Curie-Weiss behaviors of (M/H)c (T ) at high temperatures (T 100 K), respectively. The unconventional electronic and magnetic properties are interpreted in terms of charge density wave and strong electron-phonon coupling under a spin uctuation background, respectively.

Fig. 1. X-ray diraction pattern of the single-crystalline compound Na0.78 CoO2 . The sharp (00l) peaks indicate well aligned high quality single crystal.

II. EXPERIMENTAL DETAILS The single crystals of Na0.78 CoO2 were obtained using the traveling solvent optical oating zone method [11]. Because of the strong volatilization of Na during the feed rod synthesis and the crystal growth, an excess of Na was added with an initial molar ratio of Na : Co = 0.85 : 1.0. A well-mixed powder of Na2 CO3 and Co3 O4 was put in an alumina crucible, calcined and sintered at 750 C and 850 C for a day, respectively. The sintered powder was reground and made into a 6 mm 150 mm cylindrical bar with a hydrostatic pressure of 80 kN for 1 min. The bar was sintered at 850 C for a day with owing oxygen in a tube furnace. The sintered rod was premelted at a high traveling rate of 27 mm/h for a predensication of the rod. The premelted rod and a small piece of the same body (20 mm) were used for the feed and the seed rod, respectively, for the crystal growth. The feed and the seed rods were rotated at 15 rpm in opposite directions for homogeneous melting. The crystal growth traveling rate was 2 mm/h under an oxygen environment (200 cc/min). The grown large single crystal could be easily cleaved due to the layered structure. The chemical concentrations of the nominal compound Na0.85 CoO2 were carefully analyzed using energy dispersive X-ray spectroscopy (EDX) and inductively coupled plasma-atomic

emission spectroscopy (ICP-AES). The nal chemical formula was conrmed as Na0.78 CoO2 . The chemical distribution images generated by EDX conrmed that the chemical inhomogeneity of the Na ions was less than 2 at.%. The X-ray diraction patterns of the pulverized single crystals conrmed that the crystals were single phase with Nax CoO2 (P63/mmc phase). The lattice parameters of Na0.78 CoO2 were c = 10.80 and a = A 2.83 . The crystal orientation was determined using A the X-ray diraction measurements. Figure 1 shows the well-aligned sharp (00l) peaks in the caxis, perpendicular to the crystal plane. The temperature-dependent DC-magnetization M (T, H) and the electrical resistivity (T, H) were measured using a magnetic property measurement system (MPMS) and a physical property measurement system (PPMS, Quantum Design, USA) in the temperature range of 2 K T 300 K under the indicated magnetic elds.

III. RESULTS AND DISCUSSION Figure 2 shows the temperature-dependent magnetic susceptibility (M/H)ab (T ) under a magnetic eld of H = 1 T for the in-plane direction of the Na0.78 CoO2 crystal within a temperature range of 2 K T 300 K. The magnetic susceptibility (M/H)ab increases with decreasing temperature, following the broad peak near T = 30 K. At low temperatures (T 20 K), (M/H)ab signicantly increases with decreasing temperature. The inverse magnetic susceptibility (H/M )ab (T ) is shown in the upper right inset of Figure 2. It follows the CurieWeiss law (T ) = C/(T ) at high temperatures (T 100 K). From the Curie-Weiss tting in this temperature region (100 K T 300 K), the eective magnetic mo-

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Fig. 2. Temperature-dependent static magnetic susceptibility (M/H)ab (T ) of Na0.78 CoO2 under a magnetic eld of H = 1 T parallel to the ab-direction in the temperature range of 2 K T 300 K. The upper right inset shows the inverse magnetic susceptibility (H/M )ab (T ) of Na0.78 CoO2 . The Curie-Weiss behavior tted the data well in the hightemperature region (T 100 K). The lower left inset shows a semi-log plot of the magnetic susceptibility (M/H)ab versus the inverse temperature 1/T in the temperature range of 2 K T 7.5 K. The logarithmic divergent behavior at low temperatures indicates an impurity spin-1/2 eect dressed by the spin uctuation: = 0 + ln(T /T )/T .

ment and the Weiss temperature are estimated as ef f = 0.69 B and p = 3.98 K, respectively. The small negative Weiss temperature p refers to a weak antiferromagnetic interaction in the basal plane. If we assume the low-spin state of Co ion, the eective magnetic moments of Co4+ (3d5 , S = 1/2) and Co3+ (3d6 , S = 0) are 1.732 B and zero B , respectively. Under the assumption of Co low-spin states, the magnetic susceptibility comes from Co4+ ions with a partial fraction of 40 at.%. The partial fraction of the Co4+ ion indicates mixed valent states of Co3+ and Co4+ ions. The Co3+ ion, however, might have undergone a spin state transition from low spin (LS, S = 0) to intermediate spin (IS, S = 1) in the Nax CoO2 system. From the optical conductivity measurements of Na0.82 CoO2 , the charge excitation pseudo-gap was observed [8]. The pseudo-gap can be understood by using the spin state transition from low spin to intermediate spin of Co3+ ions. Bernhard et al., from their muon spin rotation (SR) experiment, argued that a low-spin Co4+ (S = 1/2) is surrounded by six intermediate-spin Co3+ (S = 1) ions in Nax CoO2 [12]. The spin state transition is widely observed in layered cobaltates, as for example, in perovskite cobaltates R1x Ax CoO3 (R: rare earth and A: alkaline-earth elements) [13]. In this system, the Co3+ spin state varies via a spin-state transition from a low

spin (LS, t6 , S = 0) to an intermediate spin (IS, t5 e1 , 2g 2g g S = 1) or a high spin (HS, t4 e2 , S = 2) with respect 2g g to temperature. The coexistence of the spin-state transition from the low (S = 0) to the intermediate spin states (S = 1) of the Co3+ ions and the mixed valence between the Co3+ and Co4+ ions can easily invoke a spin uctuation behavior. Actually, CoO2 intrinsically develops spin uctuation at low temperatures, as conrmed by the 59 Co NMR study [14]. In the Nax CoO2 system, the spin uctuation in the CoO2 layer is widely observed for a broad range of Na non-stoichiometries via the neutron scattering and NMR measurements [6,7,15]. The broad shoulder of (M/H)ab near T 30 K and the sharp increase in its magnetic susceptibility at low temperatures (T 20 K) may have originated from the spin uctuation of the Co ions between Co3+ (LS and IS) and Co4+ in the Na0.78 CoO2 compound. At low temperatures (T 20 K), the (M/H)ab (T ) logarithmically diverges. The lower left inset of Figure 2 shows a semilog plot of the magnetic susceptibility (M/H)ab versus the inverse temperature 1/T in the temperature range of 2 K T 7.5 K. This shows a logarithmic behavior of the reciprocal temperature as ln(1/T ). The strong Curie divergence at low temperatures is commonly observed in the two-channel Kondo model [16]. Clarke et al. argued that the sublattice symmetric impurity spin coupled with an antiferromangetic background is equivalent to the two-channel Kondo eect [17]. In the case of the spin-1/2 impurity, the spins form a collective motion of spinons through spin pairing, which results in a degenerate ground state. If the impurity spin-1/2 is dressed by a spin uctuation under a background antiferromagnetic state, the susceptibility diverges logarithmically: = 0 + ln(T /T )/T , where T is the characteristic temperature (T T ) dened by T J exp(Const.J/g) for weak coupling g J (g: coupling strength, J: transfer integral). The tting parameters 0 = 2.5 104 emu/moleOe and T = 10,451.02 K = 0.9 eV are derived from = 0 + ln(T /T )T . The magnetic susceptibility (M/H)c (T ) under a magnetic eld H = 1 T along the c-direction is quite dierent from (M/H)ab (T ), as shown in Figure 3. It does not follow the Curie-Weiss law at high temperatures. The (M/H)c (T ) decreases with decreasing temperature down to 40 K, with a subsequent signicant increase in susceptibility for 10 K T 30 K. The antiferromagnetic ordering is observed near TN = 8 K, which is reasonable due to the antiferromagnetic interaction, as conrmed by the Weiss temperature p = 3.98 K from the CurieWeiss tting in the ab-direction. In an intermediatetemperature region, 60 K T 180 K, a logarithmic temperature behavior of the susceptibility is observed via the expression = 0 + q ln(r + T ), where 0 , q and r are free parameters of 0 = 0.21 103 emu/moleOe, q = 0.12 103 emu/KmoleOe, and r = 2.41 K. The logarithmic temperature-dependent behavior of the susceptibility is from the localized phonon based on the

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Fig. 3. Temperature-dependent static magnetic susceptibility (M/H)c (T ) of Na0.78 CoO2 under a magnetic eld of H = 1 T parallel to the c-direction in the temperature range of 2 K T 300 K. The inset shows an expanded plot in the temperature range of 60 K T 180 K. The tted line is based on the localized phonon model, which is described by = p + q ln(r + T ), due to a strong electron-phonon coupling.

Fig. 4. Temperature-dependent electrical resistivity (T ) of Na0.78 CoO2 from 2 K to 300 K in which an electric current is driven along the ab-plane. The upper left inset shows an expanded plot of the electrical resistivity (T, H) under various magnetic elds, as indicated, at low temperatures (2 K T 20 K). The lower right inset shows the conductivity versus the inverse temperature 1/T at low temperatures (2 K T 10 K). The exponential thermal excitation behavior tted the data well in this temperature region.

strong electron-phonon coupling [18,19]. Strong electronphonon coupling is observed in compounds of the higher Na concentrations. The optical conductivity measurement for Na0.85 CoO2 shows a phonon mode, strongly coupled with lattice vibration, for a broad range of temperatures [8]. The anomalous phonon mode may have come from a pinned collective phase mode of the charge density wave and from the polaronic band [20]. Because of the strong electron-phonon interaction, polaronic hopping is revealed in the marked blue shift of the optical conductivity in Na0.85 CoO2 . The signicant increase in (M/H)c (T ) with decreasing temperature (10 K T 30 K) can be understood via an impurity spin uctuation behavior, as in the case of (M/H)ab (T ) at low temperatures. The charge density wave or polaronic hopping transport can be found in the electrical transport properties of Na0.78 CoO2 . The electrical resistivity (T ) of Na0.78 CoO2 is presented in Figure 4. It shows a typical metallic character from room temperature down to 16 K. At low temperatures (T 15 K), (T ) slightly increases with decreasing temperature. In this temperature range, there is no indication of a phase transition. The energygap property of (T ) can be expressed by an exponential temperature behavior of the electrical conductivity (T ) = 1/. The lower right inset of Figure 4 shows the electrical conductivity versus the inverse temperature 1/T . It follows the exponential behavior of (T ) given by the equation (T ) = 0 +A exp(/kB T ), where the residual conductivity 0 , the prefactor A and the energy gap are 0 = 23.75 (m-cm)1 , A = 26.31 (m-cm)1

and = 7.46 K = 0.64 meV, respectively. The energy gap is very small and is insensitive to the applied magnetic eld, as shown in the upper left inset of Figure 4. Up to an applied magnetic eld H = 7 T, the (T ) does not change. This indicates that the energy gap is not a spin gap but a charge gap. If the energy levels near the band gap edge are degenerated, the energy gap decreases under a magnetic eld due to Zeeman splitting. Lowering the local symmetry breaks the degeneracy. The localized positive charge of the Co4+ ion and the neighboring oxygen can easily lower the local symmetry of the Co3+ ion. The eld-insensitive behavior of (T ) refers to a non-degenerated charge gap caused by local symmetry breaking. The non-degenerated charge gap can be understood from the charge density wave gap by considering the universal two-dimensional transport properties of the Nax CoO2 system. As mentioned previously, the strong phonon mode of Na0.85 CoO2 from the optical conductivity can be characterized by either polaronic transport or a collective phase mode of the charge density wave. The charge density wave develops a single-particle energy gap near the Fermi level. In the charge density wave state, the electrical conductivity follows an exponential temperature behavior at low temperatures, as shown in the lower right inset of Figure 4. However, no charge density wave phase transition is observed in the temperature range of 2 K T 300 K. If the three-dimensional long-range order and the second-order phase transition

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of the charge density wave is considered, the weak coupling BCS (Bardeen-Cooper-Schrieer) theory predicts the relationship between the charge density wave gap and the transition temperature T3D as 2/kB T3D = 3.25 [21]. From this assumption, the T3D should be near 4.2 K. As we mentioned previously, however, the intrinsic nature of the Nax CoO2 system is two dimensional. Therefore, the charge density wave transition may be observed at temperatures lower than 2 K. Another thing is that the second-order phase transition with a small energy gap cannot be detected via the electrical resistivity. In this case, a hidden second-order phase transition can be found in a specic heat measurement at temperatures lower than 2 K.

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IV. CONCLUSION In summary, a high-quality single-crystalline compound of Na0.78 CoO2 was successfully synthesized using the traveling solvent oating zone method. The magnetization measurement showed a highly anisotropic behavior with dierent eld orientations of H (ab) and H (c). The (M/H)ab (T ) with H = 1 T along the (ab)direction followed the Curie-Weiss law at high temperatures (T 100 K). The broad shoulder near 30 K and the subsequent signicant increase of (M/H)ab (T ) with decreasing temperature (T 20 K) may imply a spin uctuation and an impurity 1/2-spin eect dressed by a spin uctuation, respectively. The non-Curie-Weiss behavior for (M/H)c (T ) along the magnetic eld in the (c)-direction may be understood by using the localized phonon mode from the strong electron-phonon coupling. A two-dimensional nature was observed via electrical resistivity measurements and the anisotropic behavior of the magnetic susceptibility. In the electrical resistivity (T ) at low temperatures (T 16 K), a small gap-like increase of (T ) was revealed. The eld-insensitive behavior of (T, H) for various magnetic elds up to 7 T may come from a non-degenerate small charge density wave gap = 0.64 meV, which is evidence for the twodimensional nature of the Na0.78 CoO2 compound.

ACKNOWLEDGMENTS The authors acknowledge G. Gtz and Christof Busch o for their technical assistance.