Energy spectrum and phase transitions in C70 fullerite crystals at high pressure

Measurements have been made of the Raman, optical absorption, and luminescence spectra of single crystals and pellets of the fullerite C₇₀ at T=300 K and at pressures up to 12 GPa. The baric shift dω/dP and the Grüneisen parameters of the Raman-active intramolecular phonon modes have been determined. It has been established that the d ω/dP value for certain phonon modes abruptly changes at pressures of P ₁≈2 GPa and P ₂≈5.5 GPa, as do the half-widths of the Raman lines. These features in the Raman spectrum are associated with phase transitions at high pressure. The baric shifts of the absorption and luminescence edges of C₇₀ crystals have been determined and are −0.12 eV/GPa and −0.11 eV/GPa, respectively, for absorption and luminescence. The baric shift of the absorption edge decreases significantly with increasing pressure and is −0.03 eV/GPa at 10 GPa. These data have been used to determine the deformation potential of the fullerite C₇₀, which is about 2.1±0.1 eV. Zh. éksp. Teor. Fiz. 111, 262–273 (January 1997)     

Electronic structure of half-metallic ferromagnet Co<Subscript>2</Subscript>MnSi at high-pressure

In this study, first principles calculation results of the half-metallic ferromagnetic Heusler compound Co₂MnSi are presented. All calculations are based on the spin-polarized generalized gradient approximation (σ-GGA) of the density functional theory and ultrasoft pseudopotentials with plane wave basis. Electronic structure of related compound in cubic L2₁ structure is investigated up to 95 GPa uniform hydrostatic pressure. The half-metal to metal transition was observed around ~70 GPa together with downward shift of the conduction band minimum (CBM) and a linear increase of direct band gap of minority spins at Γ-point with increasing pressure. The electronic density of states of minority spins at Fermi level, which are mainly due to the cobalt atoms, become remarkable with increasing pressure resulting a sharp decrease in spin polarization ratio. It can be stated that the pressure affects minority spin states rather than that of majority spins and lead to a slight reconstruction of minority spin states which lie below the Fermi level. In particular, energy band gap of minority spin states in equilibrium structure is obviously not destroyed, but the Fermi level is shifted outside the gap.     

Pressure induced phase transformations and band structure of different high pressure phases in tellurium

We report here high-pressure x-ray diffraction (XRD) studies on tellurium (Te) at room temperature up to 40 GPa in the diamond anvil cell (DAC). The XRD measurements clearly indicate a sequence of pressure-induced phase transitions with increasing pressure. The data obtained in the pressure range 1 bar to 40 GPa fit five different crystalline phases out of Te: hexagonal Te (I) → monoclinic Te(II) → orthorhombic Te (III) → Β-Po-type Te(IV) → body-centered-cubic Te(V) at 4, 6.2, 11 and 27 GPa, respectively. The volume changes across these transitions are 10%, 1.5%, 0.3% and 0.5%, respectively. Self consistent electronic band structure calculations both for ambient and high pressure phases have been carried out using the tight binding linear muffin tin orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Reported here apart from the energy band calculations are the density of states (DOS), Fermi energy (E _f) at various high-pressure phases. Our calculations show that the ambient pressure hexagonal phase has a band gap of 0.42 eV whereas high-pressure phases are found to be metallic. We also found that the pressure induced semiconducting to metallic transition occurs at about 4 GPa which corresponds to the hexagonal phase to monoclinic phase transition. Equation of state and bulk modulus of different high-pressure phases have also been discussed.     

Realization of a heavily doped and fully compensated semiconductor state in a crystalline semiconductor with a deep impurity band

We use the data on the pressure (up to P=1.5 GPa) and field (up to H=17 kOe) dependence of the Hall coefficient and the resistivity at 77.6 and 300 K in p-CdSnAs₂〈Cu〉 to calculate the effective kinetic characteristics of the charge carriers, the density and mobility of the conduction electrons and the holes of the deep acceptor and valence bands, in an interval of excess-acceptor densities N _ext ranging from 10¹⁰–10¹⁷ cm⁻³. We establish that in a heavily doped semiconductor with a deep impurity band at the tail of the density of states of the intrinsic band, with unequal donor and acceptor densities, a a heavily doped and fully compensated semiconductor state is realized under hydrostatic compression. The threshold value of the pressure that initiates the transition into such a state, P _c, depends on the extent to which the impurity band is populated. In p-CdSnAs₂〈Cu〉 at N _ext=N _A, where N _A is the density of deep acceptors, and T⩽77.6 K the value of P _c amounts to 10⁻⁴ GPa. As the population of the deep acceptor band grows, P _c increases and in the limit becomes infinite. We discuss the special features of the electrophysical properties of p-CdSnAs₂〈Cu〉 arising from the absence of an energy gap between the states of the conduction band and those of the deep acceptor band. Zh. éksp. Teor. Fiz. 111, 562–574 (February 1997)     

Pressure and photo-induced phase transitions in sulphur investigated by Raman spectroscopy

Abstract

The phase transition of orthorhombic sulphur α-S₈ to a high pressure amorphous sulphur allotrope (a-S) has been investigated by Raman spectroscopy. The conversion is found to be induced by the absorption of laser light and can be discussed in terms of ring opening followed by cis-trans conversion of the dihedral angle of S₈ molecules. Laser energy and transition pressure are correlated due to the pressure tuned red shift of the absorption edge of α-S₈. The amorphous (a-S) phase is observed up to 15 GPa at laser intensities below 30μW/μm² at 514.5 and 488.0 nm. Above this threshold power a-S transforms into a second photo-induced phase (p-S), whose discrete Raman spectrum implies an ordered molecular and crystalline structure. By further increasing pressure crystalline S₆ can be created which is found to be the dominant molecular species at pressures above 10 GPa and low temperatures. A phase diagram in the range T < 300 K and p < 15 GPa is also presented.     

Superconductivity in the Ti-D system under pressure

The pressure dependence of the superconducting transition temperature in TiD_0.74 has been measured up to 30 GPa in a diamond high-pressure chamber. It is found that the deuteride TiD_0.74 becomes a superconductor at pressures corresponding to the transition to the high-pressure ζ phase, with a transition temperature that increases from 4.17 to 4.43 K in the interval P=14–30 GPa. The value extrapolated to atmospheric pressure T _c (0)=4.0 K is significantly lower than the superconducting transition temperature (T _c =5.0 K) measured earlier in the metastable state obtained by quenching TiD_0.74 under pressure. It is assumed that the significant difference of the extrapolated value from the superconducting transition temperature in the metastable state after quenching under pressure is caused by a phase transition on the path from the stability region of the ζ phase under pressure to the region of the metastable state at atmospheric pressure. Fiz. Tverd. Tela (St. Petersburg) 40, 2153–2155 (December 1998)     

Crystal-field induced mixing of electron states in C60 crystals at high pressure

Optical absorption spectra of thin fullerene (C₆₀) crystals in the range 1.7 to 3.8 eV have been measured at T=300 K and at pressures up to 2.5 GPa. The spectrum shifts toward the red with pressure, and the electron absorption intensity is redistributed among its bands. The intensity of the band associated with the lowest direct electron interband transition monotonically increases with pressure, whereas the intensity of the upper interband feature decreases. Bands related to weak edge absorption in the range between 1.7 and 2.2 eV gradually merge with the band associated with the lowest interband transition, whose intensity rises with pressure. A similar redistribution of intensity among electron transition bands has been observed when comparing the spectrum of an isolated C₆₀ molecule and that of a C₆₀ crystal. The results indicate that the crystal-field induced mixing of electron states is present in solid C₆₀, and they can be discussed in terms of the Craig-McClure model, which was suggested to describe crystal-field induced mixing of electron states in anthracene and naphthalene molecular crystals. Zh. éksp. Teor. Fiz. 113, 313–322 (January 1998)     

The under-pressure behaviour of mechanical,electronic and optical properties of calcium titanate and its ground state thermoelectric response

Abstract

In this study, the elastic, electronic, optical and thermoelectric properties of CaTiO₃ perovskite oxide have been investigated using first-principles calculations. The generalised gradient approximation (GGA) has been employed for evaluating structural and elastic properties, while the modified Becke Johnson functional is used for studying the optical response of this compound. In addition to ground state physical properties, we also investigate the effects of pressure (0, 30, 60, 90 and 120 GPa) on the electronic structure of CaTiO₃. The application of pressure from 0 to 90 GPa shows that the indirect band gap (Γ-M) of CaTiO₃ increases with increasing pressure and at 120 GPa it spontaneously decreases transforming cubic CaTiO₃ to a direct (Γ-Γ) band gap material. The complex dielectric function and some optical parameters are also investigated under the application of pressures. All the calculated optical properties have been found to exhibit a shift to the higher energies with the increase of applied pressure suggesting potential optoelectronic device applications of CaTiO₃. The thermoelectric properties of CaTiO₃ have been computed at 0 GPa in terms of electrical conductivity, thermal conductivity and Seebeck coefficient.     

Evolution of the optical properties of single-crystal La1−x SrxMnO3

An ellipsometric method is used to study the dispersion of the real ɛ ₁(ω) and imaginary ɛ ₂(ω) parts of the complex dielectric permittivity of single-crystal La_1−x Sr_xMnO₃ (x=0.1, 0.2, and 0.3) for energies from 100 meV to 5 eV at room temperature. It is found that, when lanthanum is replaced by strontium, the optical spectrum changes fundamentally. A shift in the main features of the spectrum of initial LaMnO₃ at 1.9 and 4.7 eV to lower energies takes place, as well as a partial redistribution of the optical-conductivity spectral weight in the band gap region E<1.7 eV. For compositions with x=0.2 and 0.3, a fine structure of the interband absorption is observed against a background of non-Drude optical conductivity at low energies. Fiz. Tverd. Tela (St. Petersburg) 41, 1445–1449 (August 1999)     

Optical spectroscopy of europium molybdate in the crystalline and amorphous States

Comparative spectroscopic studies of crystalline and amorphous samples of Eu₂(MoO₄)₃ were carried out. Amorphous samples were obtained through exposure of the β' crystal phase to a high pressure of ∼9 GPa. It was established that the transition to the amorphous state is accompanied by substantial changes both in the luminescence spectrum and the luminescence excitation spectrum. The long-wavelength absorption edge is estimated to shift by ∼0.8 eV, which is much more significant than in the case of amorphization of classical semiconductors.     

High volumetric hydrogen density phases of magnesium borohydride at high-pressure: A first-principles study

The previously proposed theoretical and experimental structures,bond characterization,and compressibility of Mg(BH 4) 2 in a pressure range from 0 to 10 GPa are studied by ab initio density-functional calculations.It is found that the ambient pressure phases of meta-stable I4 1 /amd and unstable P-3m1 proposed recently are extra stable and cannot decompose under high pressure.Enthalpy calculation indicates that the ground state of F 222 structure proposed by Zhou et al.[2009 Phys.Rev.B 79 212102] will transfer to I4 1 /amd at 0.7 GPa,and then to a P-3m1 structure at 6.3 GPa.The experimental P 6 1 22 structure(α-phase) transfers to I4 1 /amd at 1.2 GPa.Furthermore,both I4 1 /amd and P-3m1 can exist as high volumetric hydrogen density phases at low pressure.Their theoretical volumetric hydrogen densities reach 146.351 g H 2 /L and 134.028 g H 2 /L at ambient pressure,respectively.The calculated phonon dispersion curve shows that the I4 1 /amd phase is dynamically stable in a pressure range from 0 to 4 GPa and the P-3m1 phase is stable at pressures higher than 1 GPa.So the I4 1 /amd phase may be synthesized under high pressure and retained to ambient pressure.Energy band structures show that they are both always ionic crystalline and insulating with a band-gap of about 5 eV in this pressure range.In addition,they each have an anisotropic compressibility.The c axis of these structures is easy to compress.Especially,the c axis and volume of P-3m1 phase are extraordinarily compressible,showing that compression along the c axis can increase the volumetric hydrogen content for both I4 1 /amd and P-3m1 structures.     

New ferromagnetic compound CaCo2 (C15) synthesized at high pressure

The compound CaCo₂ with the C15 cubic Laves phase structure and an estimated density of 5.21 g/cm³ has been synthesized at 8.0 GPa pressure. Magnetization measurements showed that the compound CaCo₂ is a ferromagnet with Curie temperature 528 K and magnetic moment per Co atom 1.75 μ_B at T=4.2 K. LMTO calculations of the electronic band structure showed that CaCo₂ forms as a result of an s-d electronic transition of Ca and in the ground state it is a ferromagnet with a high magnetic moment per Co atom. Pis'ma Zh. éksp. Teor. Fiz. 68, No. 12, 864–869 (25 December 1998)     

Effect of pressure and mechanical stress on the electronic properties of AlN and GaN

The fundamental properties of the AlN and GaN compounds with a wurtzite structure under external hydrostatic pressure, uniaxial mechanical stress σ_⊥ along the hexagonal axis, and biaxial mechanical stress σ_⊥ in the basal plane of the unit cell have been considered in terms of first-principles calculations in the frame-work of the density functional theory. The pressures of the phase transitions from the structures of wurtzite and zinc blende to the structure of rock salt have been obtained. The behavior of the structural parameters, interband transitions, and positions of the charge neutrality level has been investigated. The calculated pressure coefficients of the band gap are as follows: ∂E _g /∂p = 40.9 meV/GPa, −∂E _g /∂σ _| = −4.2 meV/GPa, and −∂E _g /∂σ _⊥ = 45.2 meV/GPa for AlN and ∂E _g /∂p = 33.0 meV/GPa, −∂E _g /∂σ _| = 23.6 meV/GPa, and −∂E _g /∂σ _⊥ = 9.6 meV/GPa for GaN. The pressure coefficients of the charge neutrality level in almost all cases are substantially smaller than the corresponding values obtained for the band gap E _g .     

Spectroscopic study ofβ-Ni(OH)2 under pressure

Infrared absorption and Raman study ofβ-Ni(OH)₂ has been carried out up to 25 GPa and 33 GPa, respectively. The frequency ofA _2u internal antisymmetric stretching O-H mode decreases linearly with pressure at a rate of −0.7 cm⁻1/GPa. The FWHM of this mode increases continuously with pressure and reaches a value of ∼ 120 cm⁻¹ around 25 GPa. There was no discernible change observed in the frequency and width of the symmetric stretchingA _1g O-H Raman mode up to 33 GPa. The constancy of the Raman mode is taken as a signature of the repulsion produced by H-H contacts in this material under pressure. Lack of any discontinuity in these modes suggests that there is no phase transition in this material in the measured pressure range.     

Different path of pressure-induced oxygen ordering and disordering processes in YBa2Cu3O6+x near a metal-insulator transition

The relaxation of the superconducting transition temperature T _c in YBa₂Cu₃O_6.38 is investigated with increasing oxygen order in the CuO_x plane under 1 GPa pressure and with decreasing oxygen order after the pressure is relieved. It is established that the oxygen disordering process is more rapid than the pressure-induced ordering process: The ratio of the relaxation times of T _c in these processes τ _ord/τ _disord≈5. This behavior could be caused by different mechanisms of the pressure-induced increase in the Cu-O chain length and decrease of this length after pressure relief. Fiz. Tverd. Tela (St. Petersburg) 40, 1968–1973 (November 1998)     

Observation of a shift of the mobility threshold in the D − band of silicon in an electric field according to the photoconductivity spectra

We have discovered that the extrinsic photoconductivity spectrum of doped, uncompensated crystalline Si at liquid-helium temperatures is qualitatively different in electric fields E above a critical value E _c . Specifically, the red edge of the photoconductivity, associated with photoionization of a neutral impurity, is shifted strongly to lower frequencies. This result is explained by the appearance of a mobility threshold in the D ⁻-band (upper Hubbard band) and the shift of this threshold as E increases. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 2, 89–94 (25 January 1996)     

Thermoelectric properties of p-Bi2 ? xSbxTe3 solid solutions under pressure

This paper reports on a study of the Seebeck coefficient and power factor κ of p-Bi_{2 − x} Sb _x Te₃ solid solutions with different contents of antimony atoms in the bismuth sublattice for x = 0, 1.4, 1.5, and 1.6 under variation of pressure of up to 15 GPa. The magnitude of κ has been found to grow nonmonotonically within the pressure region of 2–4 GPa. The effective mass of the density of states m/m ₀ and the mobility μ₀ have been calculated with due account of degeneracy within the parabolic model of the energy spectrum assuming isotropic charge carrier scattering. It has been shown that application of pressure brings about a decrease of the effective mass m/m ₀ and an increase of carrier mobility. The power factor κ of the p-Bi_0.6Sb_1.4Te₃ composition exhibits at the pressure P ≈ 4 GPa the largest increase of the power factor κ as a result of a weak decrease of the effective mass m/m ₀ and an increase of carrier mobility as compared to the other solid solution compositions. The specific feature of the variation of the power factor κ with a change of the pressure in bismuth telluride near P ≈ 3 GPa, which is accompanied by formation of a knee in the m/m ₀ vs. P dependence, can be assigned to an electronic topological transition.     

Tunneling investigations of the phonon spectrum of a Bi 2223 metal oxide at high pressures

Pronounced softening of the high-frequency part of the phonon spectrum at high pressures is observed by means of tunneling spectroscopy. As the pressure is increased, the characteristic frequencies of the spectrum at ħΩ>60 mV decrease at the rate d ln(ħΩ)/dP≈(−6.5±0.5)×10⁻³ kbar⁻¹. On the other hand, hydrostatic pressure causes the low frequencies of the phonon spectrum of Bi 2223 metal oxide to shift very slightly toward higher energies, consistent with Raman spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 1764–1766 (October 1997)     

Topological Berry phase and semiclassical quantization of cyclotron orbits for two dimensional electrons in coupled band models

The semiclassical quantization of cyclotron orbits for two-dimensional Bloch electrons in a coupled two band model with a particle-hole symmetric spectrum is considered. As concrete examples, we study graphene (both mono and bilayer) and boron nitride. The main focus is on wave effects – such as Berry phase and Maslov index – occurring at order (^h/_2p)\hbar in the semiclassical quantization and producing non-trivial shifts in the resulting Landau levels. Specifically, we show that the index shift appearing in the Landau levels is related to a topological part of the Berry phase – which is basically a winding number of the direction of the pseudo-spin 1/2 associated to the coupled bands – acquired by an electron during a cyclotron orbit and not to the complete Berry phase, as commonly stated. As a consequence, the Landau levels of a coupled band insulator are shifted as compared to a usual band insulator. We also study in detail the Berry curvature in the whole Brillouin zone on a specific example (boron nitride) and show that its computation requires care in defining the “k-dependent Hamiltonian” H(k), where k is the Bloch wavevector.     

A high pressure Raman study of terbium molybdate

Abstract

Tb₂(MoO₄)₃ has been studied by Raman spectroscopy under hydrostatic pressure up to 9 GPa at room temperature. The measurements reveal two phase transitions, one at around 2 GPa and another one above 5 GPa. The first phase transition is associated with an increase in the coordination number of Mo while the second is probably a transition to an amorphous phase in which only a wide band originating from Mo-O vibrations remains. This behaviour is irreversible as the Raman spectrum of the initial structure is not recovered at atmospheric pressure.