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Optical study on strongly correlated electron system LiV2O4

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2010 J. Phys.: Conf. Ser. 200 012068 (http://iopscience.iop.org/1742-6596/200/1/012068) View the table of contents for this issue, or go to the journal homepage for more

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International Conference on Magnetism (ICM 2009) Journal of Physics: Conference Series 200 (2010) 012068

IOP Publishing doi:10.1088/1742-6596/200/1/012068

Optical study on Strongly Correlated Electron System LiV2O4

Akinori Irizawa1, Kotaro Shimai1, Takao Nanba1, Seiji Niitaka2,3, Hidenori Takagi2,3,4
1 2 3 4

Graduate School of Science and Technology, Kobe University, Hyogo, Japan RIKEN, Saitama, Japan CREST, Japan Science and Technology Agency, Saitama, Japan Department of Advanced Materials Science, University of Tokyo, Chiba, Japan

E-mail: irizawa@kobe-u.ac.jp
Abstract. We investigate the change in the electronic states of LiV2O4 under high pressures and low temperatures analyzed by an infrared spectromicroscopy. The optical spectra clearly exhibit the change from a metallic state under ambient pressure to an insulating state under high pressures with a newly opened gap of 2 ~ 0.5 eV. The modification in the electronic band structure is featured by the appearance of a characteristic phonon. The absorption coefficient of LiV2O4 in the pressure-induced insulating state is compared to that of AlV2O4 in the temperature-induced one.

1. Introduction
LiV2O4 is known to be the first material among transition metal oxides which exhibits heavy fermion properties below 40 K at ambient pressure [1]. The compound shows metallic conduction between 4 and 300 K where the V-ion has a half-integer valence number of +3.5. The crystal keeps cubic spinel structure down to 9 K. The optical study denotes the spectral change in the wide energy across the characteristic temperature T* ~ 20 K [2]. The large coefficient A = 2.0 cm/K2 of T2 term in the electrical resistivity and the large ~ 350 mJ/molK2 obey the Kadowaki-Woods relation. Only a short-range magnetic correlation is identified down to 20 mK [3-5]. Once under pressure, it undergoes a metal-insulator transition (MIT) at lower temperatures [6, 7]. The crystal symmetry is reduced from cubic to rhombohedral under higher pressures where the structural modification is similar to that of temperature-induced charge-ordering state in AlV2O4 [8-11]. In the insulating state of LiV2O4, vanadium should exhibit the alternated valence numbers such as V3+:V4+ = 1:1 or V3+:V5+ = 3:1. This indivisibility of the valence number facilitates a charge distribution in this compound, so called a charge ordering state. Fig.1 shows the measured electronic resistivity curves () of LiV2O4 with temperature under different pressures [6] (the insertion indicating the V sub-lattice of pyrochlore network). From the curves, LiV2O4 shows a metallic conduction below 4.5 GPa, and above 6 GPa the resistivity at a lower temperature region drastically increases as an insulating behavior. Coming up to 8.5 GPa, the indicates a multiple behavior with the minimum around 200 K and a shoulder structure around 50 K. Such a complex change in is quite different from the manner expected for a conventional metal-insulator transition due to the simple 1st order phase transition. For the purpose of direct observation of the change in electronic states in relation to the above mentioned phenomena under pressures, the optical reflectivity measurement by an infrared (IR)-THz spectromicroscopy using a diamond anvil cell (DAC) is one of the powerful techniques. Diamond has been known to be clear

c 2010 IOP Publishing Ltd

International Conference on Magnetism (ICM 2009) Journal of Physics: Conference Series 200 (2010) 012068

IOP Publishing doi:10.1088/1742-6596/200/1/012068

between far infrared (FIR) and ultraviolet (UV) regions where the transparency is up to 70 % except for the absorption band around 0.25 eV with that of 30 %. Thus, the optical measurement using DAC is theoretically effective up to 5 eV combined with adequate spectrometers [12]. In this paper, we report the results of optical studies on LiV2O4 under high pressures and low temperatures also on AlV2O4 for the comparison.

2. Experiments
The prepared samples are; the single crystals of LiV2O4 for the optical reflectivity and the powder of the polycrystal AlV2O4 for the optical transmittance. The measurements of optical reflectivity were carried out at BL43IR in the SPring-8 with synchrotron radiation light source, also at our laboratory with conventional thermal light sources. The hydrostatic pressures up to 13 GPa were determined by the ruby-fluorescence technique for ruby tips settled near the samples in the DAC [13]. The reliable reflectivity through DAC was obtained by the multistep compensation procedure using an evaporated Au reference on the sample [14]. The optical conductivity was obtained from the Kramers-Kronig transformation for the measured reflectivity. The optical transmittance measurement of AlV2O4 was executed for the spread fine powder of the sample with a uniform thickness on an adequate substance, i.e. polypropylene for the FIR region. The result was transformed to the absorption index , which is compared to that of LiV2O4 in the following discussion.

3. Results and Discussion

Fig. 2 demonstrates the changes of the spectra of reflectivity and optical conductivity of LiV2O4 through the pressure-induced MIT at 40 K. The metallic behavior at ambient pressure clearly changes to the insulating one at 13 GPa. At ambient pressure the reflectivity towards 1.0 at 0 eV which corresponds to the Drude reflection of conduction electrons in a metallic state. Under high pressure of 13 GPa the intensity of reflectivity below 1.5 eV is reduced with the uprising of a characteristic peak at around 0.05eV. This peak structure is a kind of phonon absorption usually observed in typical ionic compounds, so called Reststrahlen band. Additionally, newly intraband peak grows up around 1 eV in the optical conductivity accompanied by the MIT. The change in the spectral shape is up to 2 eV which means the strong band modification through the MIT. To determine the detail of the characteristic peak structure at 0.05 eV, several optical constants are posted in Fig. 3(a): where 1 and 2 are the real and imaginary parts of dielectric function, (0) and () are the extrapolations of 1 toward = 0 and = , TO and LO are the transverse and longitudinal optic frequencies. The estimated TO and LO are 400 and 600 cm-1. Although the uncertainty is involved because of the limitation of experimental photon energy by a diffraction-limit (lower) and the optical absorption of diamond through DAC (higher), (0) and () are estimated at about 6.8 and 3.5. The Lyddane-Sachs-Teller (LST) relation described as TO2 / LO2 = () / (0) is roughly approved by these obtained parameters, but some deviations still exist. As for the reason, a slight decomposition of this peak structure is supposed from the comparison between LiV2O4 and AlV2O4. Fig. 3(b) shows the absorption coefficient of LiV2O4 at 13 GPa and that of AlV2O4 at ambient pressure. In the spectrum of AlV2O4, there are two sets of adjacent two or more peaks at around 0.06 and 0.09 eV. The factor group analysis yields 4 infrared active phonon modes of F1u in the spinel structure. In the case of AlV2O4 about 4 peaks are indentified for the two sets of F1u mode oscillators. The split of them are caused by the structural distortion from a cubic lattice to a lower symmetric one through the temperature-induced charge ordering (CO) [8, 10]. The other two oscillators of F1u are undetectable in the photon energy between 25 meV and 1 eV similar to the other spinel compounds because of the low intensity. Going into detail, the peak structure in of LiV2O4 is also composed by two or more components with the comparable line width to that of AlV2O4. This fact supports the existence of structural distortion in LiV2O4 in the high-pressure insulating phase. Instead of the presence of two sets of phonon peaks in the spectrum of AlV2O4, only one set can be recognized in that of LiV2O4. We have no compelling reason for this fact so far, but the other invisible oscillator around 0.09 eV of LiV2O4 should be associated with the oxygen ion vibrations in LiO4 tetrahedra instead of VO6 octahedra according to the difference between LiV2O4 and AlV2O4 [15].

4. Acknowledgements
This work is partly supported by Grant-in-Aid for Scientific Research (No. 19560665) from MEXT, Japan. The measurements were partly performed using the infrared microscope at BL43IR in SPring-8 with technical assistance of the beamline staffs Dr. T. Moriwaki and Dr. Y. Ikemoto.

International Conference on Magnetism (ICM 2009) Journal of Physics: Conference Series 200 (2010) 012068

IOP Publishing doi:10.1088/1742-6596/200/1/012068

References [1] Urano C, Nohara M, Kondo S, Sakai F, Takagi H, Shiraki T and Okubo T 2000 Phys. Rev. Lett. 85(5) 1052 [2] Jnsson P E, Takenaka K, Niitaka S, Sasagawa T, Sugai S and Takagi H 2007 Phys. Rev. Lett. 99 167402 [3] Kondo S, Johnston D C, Swenson C A, Borsa F, Mahajan A V, Miller L L, Gu T, Goldman A I, Maple M B, Gajewski D A, Freeman E J, Dilley N R, Dickey R P, Merrin J, Kojima K, Luke G M, Uemura Y J, Chmaissem O and Jorgensen J D 1997 Phys. Rev. Lett. 78(19) 3729 [4] Mahajan A V, Sala R, Lee E, Borsa F, Kondo S and Johnston D C 1998 Phys. Rev. B 57 8890 [5] Merrin J, Fudamoto Y, Kojima K M, Larkin M, Luke G M, Nachumi B, Uemura Y J, Kondo S and Johnston D C 1998 J. Magn. Magn. Mater. 177 799 [6] Urano C 2000 PhD thesis, University of Tokyo [7] Niitaka S and Takagi H unpublished [8] Matsuno K, Katsufuji T, Mori S, Moritomo Y, Machida A, Nishibori E, Takata M, Sakata M, Yamamoto N and Takagi H 2001 J. Phys. Soc. Jpn. 70 1456 [9] Takeda K, Hidaka H, Kotegawa H, Kobayashi T C, Shimizu K, Harima H, Fujiwara K, Miyoshi K, Takeuchi J, Ohishi Y, Adachi T, Takata M, Nishibori E, Sakata M, Watanuki T and Shimomura O 2005 Physica B 359 1312 [10] Horibe Y, Shingu M, Kurushima K, Ishibashi H, Ikeda N, Kato K, Motome Y, Furukawa N, Mori S and Katsufuji T 2006 Phys. Rev. Lett. 96 086406 [11] Pinsard-Gaudart L, Dragoe N, Lagarde P, Flank A M, Itie J P, Congeduti A, Roy P, Niitaka S and Takagi H 2007 Phys. Rev. B 76 45119 [12] We have constructed a spectromicroscope system having both Fourier transfer (FT) type and grating type spectrometers. The microscope system is sealed in a chamber having diamond windows where the light path can be evacuated for getting better transmittance in the FIRUV region also for changing the temperature of the sample. [13] Mao H K 1986 J. Geophys. Res. B 91 4673 [14] Chen L, Matsunami M, Nanba T, Matsumoto T, Nagata S, Ikemoto Y, Moriwaki T, Hiroko T and Kimura H 2005 J. Phys. Soc. Jpn 74 1099 [15] Popovi Z V, Marzi G De, Konstantinovi M J, Cantarero A, Dohevi-Mitrovi Z, Isobe M and Ueda Y 2003 Phys. Rev. B 68 224302

International Conference on Magnetism (ICM 2009) Journal of Physics: Conference Series 200 (2010) 012068

IOP Publishing doi:10.1088/1742-6596/200/1/012068

Fig. 2 Pressure change of reflectivity and optical conductivity of LiV2O4 at 40 K.

indicate the V-V network in the pyrochlore lattice

(a)

Fig. 1 Temperature change of electronic Fig. 1 Temperature change of electronic resistivity curve under different pressures [6]. resistivity curve under different pressures Red spheres and rods in the insertion indicate [5]. V-V network in andpyrochlore the insertion the Red spheres the rods in lattice.

(b)

Fig. 3 Fig. 3 (a) Optical constants of , phonon peak (a) Optical constants of 1, 2 of absorption comparison of absorption and (b) coefficient between LiV2O4 at 13 LiV2O4 at 13 GPa and (b) comparison of GPa and AlV2O4 at ambient pressure.

coefficient between LiV2O4 and AlV2O4.