Interacting Dipoles in Type-I Clathrates: Why Glass-like though Crystal?

Almost identical thermal properties of type-I clathrate compounds to those of glasses follow naturally from the consideration that off-centered guest ions possess electric dipole moments. Local fields from neighbor dipoles create many potential minima in the configuration space. A theoretical analysis based on two-level tunneling states demonstrates that interacting dipoles are a key to quantitatively explain the glass-like behaviors of low-temperature thermal properties of type-I clathrate compounds with off-centered guest ions.From this analysis, we predict the existence of a glass transition

Glasslike vs. crystalline thermal conductivity in carrier-tuned Ba8Ga16X30 clathrates (X = Ge, Sn)

The present controversy over the origin of glasslike thermal conductivity observed in certain crystalline materials is addressed by studies on single-crystal x-ray diffraction, thermal conductivity k(T) and specific heat Cp(T) of carrier-tuned Ba8Ga16X30 (X = Ge, Sn) clathrates. These crystals show radically different low-temperature k(T) behaviors depending on whether their charge carriers are electrons or holes, displaying the usual crystalline peak in the former case and an anomalous glasslike plateau in the latter. In contrast, Cp(T) above 4 K and the general structural properties are essentially insensitive to carrier tuning. We analyze these combined results within the framework of a Tunneling/Resonant/Rayleigh scatterings model, and conclude that the evolution from crystalline to glasslike k(T) is accompanied by an increase both in the effective density of tunnelling states and in the resonant scattering level, while neither one of these contributions can solely account for the observed changes in the full temperature range. This suggests that the most relevant factor which determines crystalline or glasslike behavior is the coupling strength between the guest vibrational modes and the frameworks with different charge carriers.Comment: 8 pages, 4 figures, 4 tables, submitted to Phys. Rev.

Cage-size control of guest vibration and thermal conductivity in Sr8Ga16Si30-xGex

We present a systematic study of thermal conductivity, specific heat, electrical resistivity, thermopower and x-ray diffraction measurements performed on single-crystalline samples of the pseudoquaternary type-I clathrate system Sr8Ga16Si30-xGex, in the full range of 0 < x < 30. All the samples show metallic behavior with n-type majority carriers. However, the thermal conductivity and specific heat strongly depend on x. Upon increasing x from 0 to 30, the lattice parameter increases by 3%, from 10.446 to 10.726 A, and the localized vibrational energies of the Sr guest ions in the tetrakaidekahedron (dodecahedron) cages decrease from 59 (120) K to 35 (90) K. Furthermore, the lattice thermal conductivity at low temperatures is largely suppressed. In fact, a crystalline peak found at 15 K for x = 0 gradually decreases and disappears for x > 20, evolving into the anomalous glass-like behavior observed for x = 30. It is found that the increase of the free space for the Sr guest motion directly correlates with a continuous transition from on-center harmonic vibration to off-center anharmonic vibration, with consequent increase in the coupling strength between the guest's low-energy modes and the cage's acoustic phonon modes.Comment: 7 pages, 7 figures, submitted to PR

Significance of Off-Center Rattling for Emerging Low-lying THz Modes in type-I Clathrates

We show that the distinct differences of low-lying THz-frequency dynamics between type-I clathrates with on-center and off-center guest ions naturally follow from a theoretical model taking into account essential features of the dynamics of rattling guest ions. Our model analysis demonstrates the drastic change from the conventional dynamics shown by on-center systems to the peculiar dynamics of off-center systems in a unified manner. We claim that glass-like plateau thermal conductivities observed for off-center systems stem from the flattening of acoustic phonon dispersion in the regime |k|<|G|/4. The mechanism is applicable to other systems such as glasses or relaxers

Optical conductivity of rattling phonons in type-I clathrate Ba8_8Ga16_{16}Ge30_{30}

A series of infrared-active optical phonons have been detected in type-I clathrate Ba$_8$Ga$_{16}$Ge$_{30}$ by terahertz time-domain spectroscopy. The conductivity spectra with the lowest-lying peaks at 1.15 and 1.80 THz are identified with so-called rattling phonons, i.e., optical modes of the guest ion Ba$^{2+}(2)$ with $T_{1u}$ symmetry in the oversized tetrakaidecahedral cage. The temperature dependence of the spectra from these modes are totally consistent with calculations based on a one-dimensional anharmonic potential model that, with decreasing temperature, the shape becomes asymmetrically sharp associated with a softening for the weight to shift to lower frequency. These temperature dependences are determined, without any interaction effects, by the Bose-factor for optical excitations of anharmonic phonons with the nonequally spaced energy levels.Comment: 4 pages, 4 figure

Anomalous infrared spectra of hybridized phonons in type-I clathrate Ba8_8Ga16_{16}Ge30_{30}

The optical conductivity spectra of the rattling phonons in the clathrate Ba$_8$Ga$_{16}$Ge$_{30}$ are investigated in detail by use of the terahertz time-domain spectroscopy. The experiment has revealed that the lowest-lying vibrational mode of a Ba(2)$^{2+}$ ion consists of a sharp Lorentzian peak at 1.2 THz superimposed on a broad tail weighted in the lower frequency regime around 1.0 THz. With decreasing temperature, an unexpected linewidth broadening of the phonon peak is observed, together with monotonic softening of the phonon peak and the enhancement of the tail structure. These observed anomalies are discussed in terms of impurity scattering effects on the hybridized phonon system of rattling and acoustic phonons.Comment: Submitted to JPS

Lattice instability and elastic dispersion due to the rattling motion in the type-I clathrate Ba_8Ga_<16>Sn_<30>

To investigate the off-center rattling motion and its charge-carrier dependence in type-I clathrate compounds, we carried out ultrasonic measurements on type-I Ba8Ga16Sn30 and a reference compound, K8Ga8Sn38. We found elastic softening of C44 originating from a lattice instability due to the off-center rattling motion of Ba atom in Ba8Ga16Sn30. Elastic softening below 1 K suggests that the lattice instability remains at very low temperatures. We also found ultrasonic dispersion which has no mode selectivity. No-mode-selective ultrasonic dispersion in Ba8Ga16Sn30 would be caused by a strong electron-phonon coupling. No charge-carrier dependence is observed between n-type and p-type Ba8Ga16Sn30. The significant softening on the bulk modulus in Ba8Ga16Sn30 contrasts to the continuous hardening in K8Ga8Sn38, indicating the central role of the rattling motion in the softening