Pressure induced phase transformation of semiconductor clathrates

Pressure induced phase transformation and amorphization for Ge-based type-I clathrates have been investigated by means of synchrotron XRD and Raman experiments under high pressure. The XRD results of Sr₈Ga₁₆Ge₃₀, Ba₈Ga₁₆Ge₃₀, and I₈Sb₈Ge₃₈ demonstrated volume collapse phase transitions at 18, 33, and 42 GPa, respectively. Reitveld analyses performed for I₈Sb₈Ge₃₈ reveal a deformation of six-member rings of 14-hedron cages with increasing pressure.     

Effect of heat treatment on the optical and electrical transport properties of Ge15Sb10Se75 and Ge25Sb10Se65 thin films

The effect of heat treatment on the optical and electrical properties of Ge₁₅Sb₁₀Se₇₅ and Ge₂₅Sb₁₀Se₆₅ thin films in the range of annealing temperature 373-723 K has been investigated. Analysis of the optical absorption data indicates that Tauc's relation for the allowed non-direct transition successfully describes the optical processes in these films. The optical band gap (E_g^opt.) as well as the activation energy for the electrical conduction (ΔE) increase with the increase of annealing temperature (T_a) up to the glass transition temperature (T_g). Then a remarkable decrease in both the E_g^opt. and ΔE values occurred with a further increase of the annealing temperature (T_a>T_g). The obtained results were explained in terms of the Mott and Davis model for amorphous materials and amorphous to crystalline structure transformations. Furthermore, the deduced value of E_g^opt. for the Ge₂₅Sb₁₀Se₆₅ thin film is higher than that observed for the Ge₁₅Sb₁₀Se₇₅ thin film. This behavior was discussed on the basis of the chemical ordered network model (CONM) and the average value for the overall mean bond energy 〈E〉 of the amorphous system Ge_xSb₁₀Se_90−x with x=15 and 25 at%. The annealing process at T_a>T_g results in the formation of some crystalline phases GeSe, GeSe₂ and Sb₂Se₃ as revealed in XRD patterns, which confirms our discussion of the obtained results.     

Magnetic-field-induced valence transition in EuNi2(Si1−x Gex)2 in fields up to 500 T

The critical fields of the valence transition induced by a magnetic field in the EuNi₂(Si_1?x Ge_x)₂ (x=0.5–0.75) compound in an intermediate valence state are measured. The magnetic-field-induced valence transition is observed in the low-concentration range down to x=0.5. It is demonstrated that the critical field increases linearly with a decrease in the germanium concentration.     

Electrical switching and thermal studies on Ge22Te78−xIx chalcohalide glasses: The effect of iodine on network-topology

Investigations on the electrical switching behavior and thermal studies using Alternating Differential Scanning Calorimetry have been undertaken on bulk, melt-quenched Ge₂₂Te_78−xI_x (3≤x≤10) chalcohalide glasses. All the glasses studied have been found to exhibit memory-type electrical switching. The threshold voltages of Ge₂₂Te_78−xI_x glasses have been found to increase with the addition of iodine and the composition dependence of threshold voltages of Ge₂₂Te_78−xI_x glasses exhibits a cusp at 5 at.% of iodine. Also, the variation with composition of the glass transition temperature (T_g) of Ge₂₂Te_78−xI_x glasses, exhibits a broad hump around this composition. Based on the present results, the composition x=5 has been identified as the inverse rigidity percolation threshold at which Ge₂₂Te_78−xI_x glassy system exhibits a change from a stressed rigid amorphous solid to a flexible polymeric glass. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy () of Ge₂₂Te_78−xI_x glasses at x=5, which is suggestive of a thermally reversing window at this composition.     

Calorimetric study of characteristic temperatures and crystallization behavior in Ge-As-Se-Te glass system

Results of differential scanning calorimetry of high purity Ge_xAs_40−xSe₄₀Te₂₀ (x=0-40) chalcogenide glasses are reported. The glass transition temperatures and crystallization behavior were studied under non-isothermal conditions at different heating rates (2.5-35 K/min). The glass transition temperature changes from 140 °C up to 320 °C with increasing the Ge content in Ge_xAs_40−xSe₄₀Te₂₀ glass. The studied glasses with x≤35 have no exothermal peaks of crystallization, indicating their high glass-forming ability. The glass of Ge₄₀Se₄₀Te₂₀ composition has one-stage glass transition and double-stage crystallization process during phase change. The activation energy of the glass transition (E_g), the activation energy of crystallization (E_c), the Avrami exponent (n), the frequency factor (K₀) and the crystallization criteria of Ge₄₀Se₄₀Te₂₀ glass were determined.     

High-precision measurements of the compressibility of chalcogenide glasses at a hydrostatic pressure up to 9 GPa

The volumes of glassy germanium chalcogenides GeSe₂, GeS₂, Ge₁₇Se₈₃, and Ge₈Se₉₂ are precisely measured at a hydrostatic pressure up to 8.5 GPa. The stoichiometric GeSe₂ and GeS₂ glasses exhibit elastic behavior in the pressure range up to 3 GPa, and their bulk modulus decreases at pressures higher than 2–2.5 GPa. At higher pressures, inelastic relaxation processes begin and their intensity is proportional to the logarithm of time. The relaxation rate for the GeSe₂ glasses has a pronounced maximum at 3.5–4.5 GPa, which indicates the existence of several parallel structural transformation mechanisms. The nonstoichiometric glasses exhibit a diffuse transformation and inelastic behavior at pressures above 1–2 GPa. The maximum relaxation rate in these glasses is significantly lower than that in the stoichiometric GeSe₂ glasses. All glasses are characterized by the “loss of memory” of history: after relaxation at a fixed pressure, the further increase in the pressure returns the volume to the compression curve obtained without a stop for relaxation. After pressure release, the residual densification in the stoichiometric glasses is about 7% and that in the Ge₁₇Se₈₃ glasses is 1.5%. The volume of the Ge₈Se₉₂ glass returns to its initial value within the limits of experimental error. As the pressure decreases, the effective bulk moduli of the Ge₁₇Se₈₃ and Ge₈Se₉₂ glasses coincide with the moduli after isobaric relaxation at the stage of increasing pressure, and the bulk modulus of the stoichiometric GeSe₂ glass upon decreasing pressure noticeably exceeds the bulk modulus after isobaric relaxation at the stage of increasing pressure. Along with the reported data, our results can be used to draw conclusions regarding the diffuse transformations in glassy germanium chalcogenides during compression.     

Influence of the germanium deposition rate on the growth and Photoluminescence of Ge(Si)/Si(001) self-assembled islands

The growth and photoluminescence of Ge(Si)/Si(001) self-assembled islands are investigated over a wide range of germanium deposition rates v_Ge = 0.1–0.75 Å/s at a constant growth temperature T _g = 600°C. Examination of the surface of the grown structures with an atomic force microscope revealed that, for all the germanium deposition rates used in the experiments, the dominant island species are dome islands. It is found that an increase in the deposition rate v_Ge leads to a decrease in the lateral size of the self-assembled islands and an increase in their surface density. The decrease in the lateral size is associated both with the increase in the germanium content in the self-assembled islands and with the increase in the fraction of the surface occupied by these islands. The observed shift in the position of the photoluminescence peak toward the low-energy range is also explained by the increase in the germanium content in the islands with an increase in the deposition rate v_Ge.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Neutron diffraction study of DyCu2Ge2

The DyCu₂Ge₂ compound was studied by neutron diffraction on the Grenoble Nuclear Research Center multicounter system. The compound is isostructural to the rare earth RCu₂Ge₂ compounds with space group I4/mmm. 19 superlattice lines were observed in the 3 K pattern which are consistent with a doubling of the unit cell in the a and c directions. The moment value is 8 μ_B making an angle of 30° with a and 70° with c axis. The structure consists of ferromagnetic (1 0 1) layers with antiferromagnetic coupling between them. The Néel and Curie paramagnetic temperature of this compound is 8 K and ? 15 K respectively.     

Pressure and temperature induced modification of luminescence from tetracene single crystals

Fluorescence spectra of crystalline tetracene have been recorded in the temperature range 120 to 300 K under hydrostatic pressure up to 600 MPa. From discontinuities in both emission spectra and spectral intensities it is concluded that two phase transitions occur. The room temperature phase is transformed to a low temperature phase/high pressure phase I at T^I_t (p = 0) = 182 K, the temperature coefficient being dT^I_t/dp = 0.395 K/MPa. The phase transition is induced by a decrease of the specific volume under pressure and/or upon cooling. Lack of a significant shift of the origin of the fluorescence band near T^I_t at constant pressure is an artifact resulting from the neglect of reabsorption effects. The Stokes shift is 260 cm^-1, independent of temperature and crystal modification. In accord with previous Raman data a second phase transition occurs at T^II_t (p) = 143 K, the pressure shift being dT^II_t/dp = 0.088 K/MPa.In addition, the shift of the triplet energy as a function of pressure as well as the pressure-dependence of the rate constants governing fission of a singlet exciton into a pair of triplets is discussed utilizing their magnetic field dependences.     

Influence of Ho substitution for Nd on magnetic properties of the Nd1−xHoxMn2Ge2 germanides

The structure and magnetic properties of Nd_1−xHo_xMn₂Ge₂ (0.0≤x≤1.0) germanides were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) techniques and AC magnetic susceptibility measurements. All compounds crystallize in the ThCr₂Si₂-type structure with the space group I4/mmm. Substitution of Ho for Nd leads to a linear decrease in the lattice constants and the unit cell volume, and the magnetic interactions in the Mn sublattice cross over from a ferromagnetic character to an antiferromagnetic one. A typical SmMn₂Ge₂-like behavior is observed for x=0.6 and 0.8. The results are collected in a phase diagram.     

A magnetic study of the ThCr2Si2-type RPd2Ge2 (R=Pr, Nd) compounds. Magnetic structure of PrPd2Ge2 from powder neutron diffraction

The magnetic properties of the PrPd₂Ge₂ and NdPd₂Ge₂ compounds have been investigated by magnetic measurements, specific heat measurements and neutron diffraction experiments. The PrPd₂Ge₂ compound orders antiferromagnetically below T_N=5.0(2) with an original modulated magnetic structure characterized by a magnetic cell three times larger than the chemical one by tripling of the c parameter. The palladium atom is non magnetic and the Pr moments are parallel to the c-axis with a value of ≈2.0 μ_B at 2 K. The specific heat measurements clearly detect a low temperature transition for the NdPd₂Ge₂ compound, interpreted as a Nd sublattice antiferromagnetic ordering below 1.3(2) K.     

β-C3N4,β-Si3N4和β-Ge3N4的能带结构

采用基于密度泛函理论的线性丸盒轨道原子球近似(LMTO-ASA)从头计算方法,研究了β-C₃N₄,β-Si₃N₄和β-Ge₃N₄的能带结构,得到了它们的能隙分别为:4.1751,5.1788和4.0279eV。对于β-C₃N₄,由于N的部分2p电子占据了非键轨道,禁带宽度较窄;对于β-Si₃N_{4关键词：}     

Force constant variation from crystalline to amorphous germanium

The phonon density of states for crystalline germanium (cz.sbnd;Ge) and amorphous germanium (aGe) have been computed by means of de Launay angular force model, considering only the first nearest neighbour interactions. The relevancy of computed phonon density of states to the interpretation of infrared and Raman spectra of az.sbnd;Ge are discussed, and the decrease in force constants of the order of 10% has been observed when the phase changes from crystalline to amorphous state.     

Transitions de phase destructive et non destructive dans le cristal moleculaire bromo-2 naphtalene

The polymorphism of 2-bromonaphthalene has been studied by both crystallographic and energetical methods. Three crystalline forms have been characterized, respectively denoted Br_III, Br_II and Br_I. The first one is the stable form up to 319 K. At this temperature a first order phase transition occurs which breaks the single crystal and leads to a disordered structure Br_I isotypic with the naphthalene one. The Br_II form is a metastable one which appears when cooling the Br_I, form; when so formed, the Br_II phase can give again the Br_I one by annealing; so that the Br_I-Br_II transition is reversible. This second order transition extends over a large temperature range (275–319 K), it does not destroy the single crystal and corresponds to a substructural modification along the c axis of the monoclinic cell. The anomalies of the Cp curve and the variations of the principal components of the thermal expansion tensor suggest that there are two competitive temperature dependent molecular reorientations. The transition Br_II→Br_III which leads to the stable ordered form is spontaneous at room temperature, it takes place sluggishly and destroys the single crystal.Cell parameters of the Br_III form have been determined from powder data using an automatic indexing method: a = 9.578(1) Å, B = 9.601(1) Å, c = 10.303(1) Å, α = 100.79(1)°, β = 109.06(1)°, γ = 101.77(1)°. (Figure of merit M₂₀ = 86.)     

Valence fluctuation in Ce2Co3Ge5 and crystal field effect in Pr2Co3Ge5

Polycrystalline samples of ternary rare-earth germanides R₂Co₃Ge₅ (R=La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U₂Co₃Si₅ structure (space group Ibam). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce₂Co₃Ge₅ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment (μ_eff≈0.95 μ_B) compared to that expected for trivalent Ce ions further supports valence-fluctuating nature of Ce in Ce₂Co₃Ge₅. The observed temperature dependence of magnetic susceptibility is consistent with the ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr₂Co₃Ge₅. An analysis of C_mag data suggests a singlet ground state in Pr₂Co₃Ge₅ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.     

Novel RCo5Ga7 intermetallic compound

The novel RCo₅Ga₇ (R=Y, Tb, Dy, Ho and Er) intermetallic compounds have been synthesized, and their crystallographic and magnetic properties have been studied using X-ray diffraction and magnetic measurement. RCo₅Ga₇ crystallizes in an orthorhombic structure with ScFe₆Ga₆ type. The space group is Immm, and Z=2. According to the structural refinement result, the 2a, 4e, 4f, 4g, 4h, and 8k crystal positions are occupied by 2R, 4Ga^I, 4(Ga^II, Co^I), 4Ga^III, 4(Ga^IV,Co^II), and 8(Co^III,Ga^V), respectively. The RCo₅Ga₇ intermetallic compound can be stabilized in the range of the radius ratio of R_Re/R_(Co,Ga)<1.36. The RCo₅Ga₇ compound exhibits a paramagnetic behavior. The magnetization at 5 K ranges from 28.93 to 40.62 emu/g.     

Growth features at competing nucleation of quantum dots and nanopits in Si-Ge-C ternary system

The continuum elasticity model is applied to quantitatively investigate the growth features and nucleation mechanism of quantum dots (QDs), nanopits, and joint QDs-nanopits structures in SiGeC ternary systems. We determined the critical concentrations of carbon, x = 0.08 for Si_1?x C _x and y = 0.0033 for Si_1?x?y Ge _x C _y at the concentration of germanium x = 0.467, when the growth mode changes from, respectively, nucleation of QDs to formation of nanopits. We have shown that the increase in the carbon concentration in a SiC binary system and of germanium concentration in a SiGeC ternary system leads to a decrease in the critical size of QD. The free energy of mixing for Si_1?x?y Ge _x C _y ternary system was calculated and studied and its 3D sketch plotted. It is demonstrated that incorporation of carbon into Si and Ge up to background impurity concentration is energetically preferable, which explains the experimentally detected ??contamination?? of silicon and germanium crystals by carbon during the growth in the graphite crucible.     

Effects of germanium incorporation on optical performances of silicon germanium passive devices for group-IV photonic integrated circuits

Optical interconnect in integrated optoelectronic circuits is one of the promising next-generation technologies for replacing metalized interconnect. Efforts have been made to use silicon (Si)-compatible materials such as germanium (Ge) and Ge-buffered III–V compound semiconductors, along with Si, as optical sources for Si and group-IV integrated optoelectronic systems. This opens the possibility that higher fraction of Ge with its high refractive index (n) can be incorporated in Si waveguide for optical interconnect and the graftability between Si and group-IV or III–V materials would be improved in silicon photonics. In this work, advantageous features of nano-structured silicon germanium (Si_1−xGe_x) optical waveguide with different Ge fraction (x) were evaluated by both optical simulations and theoretical calculations, which are mainly found in the enhanced optical confinement and better interfacing capability. Along with the SiGe waveguide, performance of Si_1−xGe_x microring resonator under material loss in the effect of extinction coefficient (k) has been investigated to suggest the necessity of optimizing the Ge content in Si_1−xGe_x passive devices. While carrying out the establish design criteria, n and k have been modelled in closed-form functions of Ge fraction at 1550 nm. Furthermore, by examining high-resolution transmission electron microscopy (HR-TEM) images, process compatibility of Ge with either group-IV alloys or III–V compound semiconductors is confirmed for the monolithically integrated photonic circuits.     

Reflection and vibrational spectra of SbSCl0.1I0.9 crystals in the ferroelectric phase-transition region

SbSCl_0.1I_0.9 crystals were grown from the vapor phase and reflection spectra were recorded using a Fourier-transform IR spectrometer. The optical parameters and optical functions along the c axis were calculated using an improved Kramers–Kronig technique with two confining spectral limits. The reflection spectra were analyzed using the oscillator parameter fitting technique for comparison of results. The vibrational frequencies ω_L and ω_T were evaluated. The ferroelectric phase-transition temperature was estimated as 330 K for SbSCl_0.1I_0.9 from experimental reflection measurements and theoretical investigation of the potential energy of Sb atoms for B_1u soft normal modes of SbSI and SbSCl_0.1I_0.9 crystals.