Superconductivity and electrical resistivity in alkali metal doped fullerides: Phonon mechanism

We consider a two- peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. We first study the intercage interactions between the adjacent C₆₀ cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali- C₆₀ phonons. Electronic parameter as repulsive parameter and the attractive coupling strength are obtained within the random phase approximation. Transition temperature,T _c, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C₆₀ phonons as 5 K, which is much lower as compared to reportedT _c (≈ 20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. To illustrate the usefulness of the above approach, the carbon isotope exponent and the pressure effect are also estimated. Temperature dependence of electrical resistivity is then analysed within the same model phonon spectrum. It is inferred from the two- peak model for phonon density of states that high frequency intramolecular phonon modes play a major role in pairing mechanism with possibly some contribution from alkali-C₆₀ phonon to describe most of the superconducting and normal state properties of doped fullerides.     

Lattice Transformation from 2D to Quasi 1D and Phonon Properties of Exfoliated ZrS2 and ZrSe2

Recent reports on thermal and thermoelectric properties of emerging 2D materials have shown promising results. Among these materials are Zirconium-based chalcogenides such as zirconium disulfide (ZrS₂), zirconium diselenide (ZrSe₂), zirconium trisulfide (ZrS₃), and zirconium triselenide (ZrSe₃). Here, the thermal properties of these materials are investigated using confocal Raman spectroscopy. Two different and distinctive Raman signatures of exfoliated ZrX₂ (where X = S or Se) are observed. For 2D-ZrX₂, Raman modes are in alignment with those reported in literature. However, for quasi 1D-ZrX₂, Raman modes are identical to exfoliated ZrX₃ nanosheets, indicating a major lattice transformation from 2D to quasi-1D. Raman temperature dependence for ZrX₂ are also measured. Most Raman modes exhibit a linear downshift dependence with increasing temperature. However, for 2D-ZrS₂, a blueshift for A1g mode is detected with increasing temperature. Finally, phonon dynamics under optical heating for ZrX₂ are measured. Based on these measurements, the calculated thermal conductivity and the interfacial thermal conductance indicate lower interfacial thermal conductance for quasi 1D-ZrX₂ compared to 2D-ZrX₂, which can be attributed to the phonon confinement in 1D. The results demonstrate exceptional thermal properties for Zirconium-based materials, making them ideal for thermoelectric device applications and future thermal management strategies.     

Theoretical study of negative thermal expansion mechanism of ZnF2

ZnF₂ is reported to exhibit negative thermal expansion (NTE) at lower temperatures very recently. In this article, we present the electronic and NTE properties of ZnF₂ using a first-principles calculation. Our results show that ZnF₂ is an insulator with a direct band gap and a strong hybridization occurs between Zn-3p, 4s and F-2p states. The related calculations on NTE properties are obtained within the quasi-harmonic approximation. The resulting relationship between volume and temperature confirms the NTE properties. Besides, we discuss the NTE mechanism in accordance to phonon vibrational modes. The phonon vibrational modes contributing to the NTE are singled out by Grüneisen parameters and all these modes are low-frequency optical phonons. The lowest frequency rigid unit mode (RUM) of ZnF₆ causes a rotary coupling between two adjacent octahedrons and makes the Zn–Zn distance shorter, which is most responsible for the NTE properties of ZnF₂.     

Collective modes in Ca70Mg30 glass

The self-consistent phonon scheme given by Takeno and Goda, involving multiple scattering and phonon eigen frequencies which are expressed in terms of many-body correlation functions of atoms as well as of interatomic potential in the solids, has been used to generate the collective modes in the Ca₇₀Mg₃₀ glass. A model potential is proposed to describe the effective interaction in the glass. Three different forms of the local field correction functions viz. Hartree, Taylor and Ichimaru and Utsumi are used to examine relative influence of exchange and correlation effects. The phonon frequencies of the longitudinal and transverse modes are computed employing the theoretical formulation of Hubbard and Beeby. The elastic property of the glassy system is then studied using the long wavelength limits of the phonon modes. The theoretical computations reproduce much better dispersion curves (both for the longitudinal and transverse phonons) compared to earlier reports and are found to be in good agreement with the available experimental results due to neutron scattering. Paper presented at the 5th IUMRS-ICA 98, October 1998, Bangalore.     

Dielectric properties of perovskite crystals

The soft mode dynamical model has been used to study the dielectric properties of Perovskite-type crystals. The model Hamiltonian proposed by Pytte has been modified and designed in terms of creation and annihilation operators. The correlations appearing in the dynamical equation have been evaluated using double time thermal retarded Green’s function and Dyson’s equation. Without any decoupling the higher order correlations have been evaluated using the renormalized Hamiltonian and thus, all possible interactions among phonons have been taken into account. The expressions for phonon frequencies and widths have beenMcalculated. Using appropriate parameters the softening of different modes at different transition temperatures give rise to a series of transitions from cubic to tetragonal, orthorhombic or trigonal phases. The significantly temperature-dependent modes are considered responsible for damping constant, dielectric constant, tangent loss and attenuation constant for these crystals. The dielectric properties are directly related to the optical phonon frequencies and widths and acoustic attenuation to the acoustic and optical phonon widths. Using suitable approximations, the model explains the experimental results on dielectric properties and acoustic attenuation reported for LiNbO₃, SrTiO₃, BaTiO₃ and LaAlO₃.     

Breaking the Minimum Limit of Thermal Conductivity of Mg3Sb2 Thermoelectric Mediated by Chemical Alloying Induced Lattice Instability

Thermal properties strongly affect the applications of functional materials, such as thermal management, thermal barrier coatings, and thermoelectrics. Thermoelectric (TE) materials must have a low lattice thermal conductivity to maintain a temperature gradient to generate the voltage. Traditional strategies for minimizing the lattice thermal conductivity mainly rely on introduced multiscale defects to suppress the propagation of phonons. Here, the origin of the anomalously low lattice thermal conductivity is uncovered in Cd-alloyed Mg₃Sb₂ Zintl compounds through complementary bonding analysis. First, the weakened chemical bonds and the lattice instability induced by the antibonding states of 5p-4d levels between Sb and Cd triggered giant anharmonicity and consequently increased the phonon scattering. Moreover, the bond heterogeneity also augmented Umklapp phonon scatterings. Second, the weakened bonds and heavy element alloying softened the phonon mode and significantly decreased the group velocity. Thus, an ultralow lattice thermal conductivity of ≈0.33 W m⁻¹ K⁻¹ at 773 K is obtained, which is even lower than the predicated minimum value. Eventually, Na_0.01Mg_1.7Cd_1.25Sb₂ displays a high ZT of ≈0.76 at 773 K, competitive with most of the reported values. Based on the complementary bonding analysis, the work provides new means to control thermal transport properties through balancing the lattice stability and instability.     

Low-Temperature Thermal Conductivity and Specific Heat of Plastically Deformed High-Purity Tantalum Single Crystals

The thermal conductivity and the specific heat of plastically deformed, high-purity tantalum single crystals have been measured together with an amorphous SiO₂ specimen in the temperature range between 50 mK and about 2 K. After plastic deformation, the thermal conductivity was reduced by a factor of more than 100 and had a magnitude comparable to that of the amorphous SiO₂ specimen. However, the specific heat measurements revealed a T³-relationship for the phonon contribution down to the lowest temperatures with a magnitude as in the case of undeformed crystalline solids. Thus, it must be concluded that the scattering of thermal phonons introduced by the plastic deformation has to be attributed to intrinsic properties of dislocations rather than to the interaction of phonons with tunneling systems. In the present paper the scattering mechanism is related to oscillations of geometrical kinks in non-screw dislocations.     

Avoided crossing of rattler modes in thermoelectric materials

Engineering of materials with specific physical properties has recently focused on the effect of nano-sized 'guest domains' in a 'host matrix' that enable tuning of electrical, mechanical, photo-optical or thermal properties. A low thermal conductivity is a prerequisite for obtaining effective thermoelectric materials, and the challenge is to limit the conduction of heat by phonons, without simultaneously reducing the charge transport. This is named the 'phonon glass-electron crystal' concept and may be realized in host-guest systems. The guest entities are believed to have independent oscillations, so-called rattler modes, which scatter the acoustic phonons and reduce the thermal conductivity. We have investigated the phonon dispersion relation in the phonon glass-electron crystal material Ba(8)Ga(16)Ge(30) using neutron triple-axis spectroscopy. The results disclose unambiguously the theoretically predicted avoided crossing of the rattler modes and the acoustic-phonon branches. The observed phonon lifetimes are longer than expected, and a new explanation for the low kappa(L) is provided.     

Effect of oxygen incorporation on the vibrational properties of Al0.2Ga0.3In0.5P:Be films

The vibrational properties of Al_0.2Ga_0.3In_0.5P:Be films grown on (100) GaAs substrates by solid source molecular beam epitaxy varying the phosphorous cracking-zone temperature (PCT) were studied by Raman spectroscopy. The Raman-intensity ratio between the allowed longitudinal optical and the forbidden transverse optical (TO) phonons, and the full width at half maximum of their Lorentzian fits were used to characterize the crystalline quality of the films. The Raman spectra from the samples show changes in the shape and intensity of phonon resonances depending on the PCT variation, indicating that the disorder in the lattice increases with PCT. The increasing disorder is related to the inclusion of oxygen, which act as a non-intentional perturbing impurity in the lattice. In addition, a vibrational mode located at 598 cm^− 1 related to a forbidden InP-like TO phonon resonance was correlated with oxygen-induced disorder. Photoluminescence at room temperature shows that the high inclusion of oxygen also deteriorates the optical properties of the samples, by introducing non-radiative recombination centers.     

Inelastic tunneling of Cooper pairs in c-direction in BSCCO single Josephson junctions and stacks

A reproducible fine structure at subgap voltages in the I(U)-characteristics of BSCCO single Josephson junctions and stacks has been observed and investigated. The structure is detectable only in the presence of an AC Josephson current. The overall form of the fine structure is in good agreement with the Raman scattering spectra of the optical phonon modes in this material. We attribute this structure to an inelastic (phonon assisted) tunneling of Cooper pairs, which is accompanied by the emission of coherent Raman-active optical phonons at resonance voltages U _res = _phon/2e. The observed structure can be explained in terms of a theoretical model developed by Maksimov, Arseyev and Maslova.     

Effect of Hyperbolic Band Structure on the Energy Loss Rate of Hot Electrons with Non-equilibrium Phonon Distribution in the Extreme Quantum Limit at Low Temperatures in n-Hg0.8Cd0.2Te

The energy loss rate of hot electrons with the non-equilibrium phonons in narrowgap semiconductors with hyperbolic band structures has been investigated in the extreme quantum limit condition in the low temperature region. The calculation is done for n-Hg_0.8Cd_0.2Te sample considering electron scattering by acoustic phonons via piezoelectric coupling to be the dominant loss mechanism. The value of the energy loss rate with hyperbolic band is compared with the results of parabolic and non-parabolic band structures and at the same time all the results are also compared with the experimentally observed data. It is found that with the inclusion of hyperbolic band structure, the value of energy loss rate is found to be close to the experimental values. The dependence of energy loss rate on magnetic field and lattice temperature has been studied. Using the experimental value of the energy loss rate, the phonon life time is evaluated. The value of the phonon life time is found to be of the order of the phonon boundary relaxation time indicating that phonon boundary scattering is the dominant phonon dissipation mechanism. The dependence of the phonon life time on magnetic field, and lattice temperature has also been studied. The phonon life time is also found to decrease with increase in electron temperature.     

Photon control of phonons in mixed crystal quantum dots

Coherent phonon oscillations in solids can be excited impulsively by a single femtosecond laser pulse whose duration is shorter than a phonon period. In the impulsive stimulated Raman scattering (ISRS) experiment, scattering of probe is monitored as a function of time with respect to pump to generate time domain spectra of coherent phonons. In this paper, we present one such study of CdSe_0.68Te_0.32 (d∼80 A) quantum dots in glass matrix, i.e semiconductor-doped glass (SDG) RG780 from Schott, USA and the experiment was performed at Prof. Merlin's laboratory at the University of Michigan, USA. Here, we present first report of selectively driving only CdSe-like modes in these mixed crystal quantum dots using photon control with two pump beams.     

Site and sample dependent electron-phonon coupling of Eu ions in epitaxial-grown GaN layers

The incorporation of Eu ions into GaN has been studied using combined excitation-emission spectroscopy for samples that were in situ doped during organometallic vapor-phase epitaxy (OMVPE) growth. The obtained fingerprints of characteristic emission spectra are subsequently used to determine the coupling of the Eu ions to the crystal lattice. We find a majority site, which exhibits coupling to bulk-like phonon modes as well as a localized phonon mode. For this site, we also find that the zero-phonon line of the ⁷F₀ to ⁵D₀ transition, which is forbidden, is much weaker than the phonon-coupled excitation transitions. The ratio of zero-phonon to phonon-coupled transition strength depends on the crystalline quality of the layer. These observations are consistent with the assignment of the majority site to an unperturbed Eu ion on Ga position. We find that the relative abundance of the majority site is strongly underestimated whenever the zero-phonon ⁷F₀ to ⁵D₀ excitation transition is used as a measure.     

Electrothermal Control of Graphene Plasmon–Phonon Polaritons

Graphene plasmons are known to offer an unprecedented level of confinement and enhancement of electromagnetic field. They are hence amenable to interacting strongly with various other excitations (for example, phonons) in their surroundings and are an ideal platform to study the properties of hybrid optical modes. Conversely, the thermally induced motion of particles and quasiparticles can in turn interact with electronic degrees of freedom in graphene, including the collective plasmon modes via the Coulomb interaction, which opens up new pathways to manipulate and control the behavior of these modes. This study demonstrates tunable electrothermal control of coupling between graphene mid‐infrared (mid‐IR) plasmons and IR active optical phonons in silicon nitride. This study utilizes graphene nanoribbons functioning as both localized plasmonic resonators and local Joule heaters upon application of an external bias. In the latter role, they achieve up to ≈100 K of temperature variation within the device area. This study observes increased modal splitting of two plasmon–phonon polariton hybrid modes with temperature, which is a manifestation of increased plasmon–phonon coupling strength. Additionally, this study also reports on the existence of a thermally excited hybrid plasmon–phonon mode. This work can open the door for future optoelectronic devices such as electrically switchable graphene mid‐infrared plasmon sources.     

Low-Temperature Internal Friction and Thermal Conductivity of Plastically Deformed, High-Purity Monocrystalline Niobium

The low-temperature internal friction Q ^–1 and thermal conductivity of plastically deformed, high-purity niobium monocrystals have been investigated and compared with measurements on an amorphous SiO₂ (a-SiO₂) specimen. After plastic deformation at intermediate temperatures, an approximately temperature independent internal friction Q ^–1 was observed with a magnitude comparable to that of the a-SiO₂ specimen. Plastic deformation at low temperatures leads to an internal friction Q ^–1 with a considerably smaller magnitude. In the temperature range between about 0.3 and 1.5K, the lattice thermal conductivity k of the deformed specimens decreases with increasing deformation. It is, however, nearly independent of the amount of deformation at the lowest temperatures investigated. In this temperature regime, the lattice thermal conductivity of the specimens varies proportional to T ³ and has a magnitude as would be expected for an undeformed sample. Additional heat release experiments on an undeformed sample clearly show no long-time energy relaxation effects. We conclude that the defects introduced by plastic deformation cannot be described with the tunneling model which had been proposed to describe the low temperature elastic and thermal properties of amorphous solids. The phonon scattering mechanisms observed in deformed niobium are tentatively related to the dynamic interaction of phonons with geometrical kinks in dislocations.     

Effects of CaTiO3 on crystal structures and dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics via X-ray diffraction and Raman spectroscopy

Ba(Zn_1/3Nb_2/3)O₃–CaTiO₃ (BZN–CT) ceramics were synthesized at 1,395 °C for 4 h using a conventional solid-state sintering technique, with CT contents of 0, 30, 60, 75, and 90 wt%. Crystal structures were analyzed by X-ray diffraction, and vibrational modes were obtained by Raman spectroscopy to evaluate the correlation between crystal structures, dielectric properties, and phonon modes of these ceramics. Increasing CT content can remarkably affect the crystal structures and dielectric properties of BZN–CT ceramics. Crystal symmetries decrease with CT concentration from cubic to hexagonal structure. The lattice constant and the degree of order also change accordingly. The ordered phases transform from 1:1 to 1:2 ordered structure with changing crystal structures. The relationship between the Raman shifts, the FWHM values, and the dielectric properties were obtained by Raman spectral analyses.     

Lattice dynamics and Raman spectrum of rutile TiO2: The role of soft phonon modes in pressure induced phase transition

Using the plane-wave pseudopotential technique based on the first-principles density functional perturbation theory (DFPT), we have studied the vibrational properties and Raman susceptibility tensor at ambient and high pressure of rutile phase of TiO₂. Full phonon dispersion curves and phonon densities of states with projected phonon density of states and Raman tensors at high pressures are calculated and given. It is found that rutile TiO₂ shows a pressure induced phase transition, especially when lattice dynamical instabilities are involved, like the soft phonon modes, at a hydrostatic pressure lower than 10 GPa. An analyses of the vibrational displacements is given. The possibility to use Raman line intensities as an additional tool in the study of phase transitions is also discussed.     

A Comprehensive Investigation of Superconductor KBi<Subscript>2</Subscript> via First-Principles Calculations

The electronic properties, lattice vibration, and electron-phonon interaction properties of KBi₂ are studied systematically by first-principles calculations. The agreement of calculated Debye temperature, electron-phonon coupling constant, and transition temperature with latest experiments validates the reliability of our work. Our results provide evidence that the superconducting transition of KBi₂ originates from isotropical coupling of all phonon modes according to isotropical Migdal-Eliashberg theory.     

Lattice dynamic study on 3d transition metal intercalates M x TiS2 (M=Mn,Fe, Co,and Ni) using point-contact spectroscopy

The derivatives of the current-voltage characteristics of a homojunction point contact of 1T-CdI₂-type layered crystal TiS₂ and its intercalation compounds M_1/4TiS₂ (M=Mn, Fe, Co, and Ni) have been measured at 1.4 K. With reference to the available data on lattice dynamics, we have identified various inter- and intralayer acoustic and optical phonon modes. The acoustic phonon modes are strongly anisotropic compared with the optical ones in these materials. The variations of the acoustic phonon energies upon intercalation of 3d metals are strongly correlated with those of the interlayer spacingc, for which qualitative discussions are given.