Structural stability and theoretical strength of the single crystal Ag under uniaxial loading

The structural stability and theoretical strength of FCC crystal Ag under uniaxial loading have been investigated by combining MAEAM with Wang modified Born stability criteria. The results reveal that, under sufficient compression, there exists a stress-free BCC phase, which is unstable and slips spontaneously to a stress-free mBCT phase by consuming internal energy. The stable region ranges from −2.076 to 4.390 GPa in the theoretical strength or from −7.972% to 8.721% in the strain correspondingly. The calculated structural energy difference between the BCC and FCC phase is in good agreement with the experimental value.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

Structural stability and theoretical strength of Cu crystal under equal biaxial loading

Cu has been used extensively to replace Al as interconnects in ULSI and MEMS devices. However, because of the difference in the thermal expansion coefficients between the Cu film and the Si substrate, large biaxial stresses will be generated in the Cu film. Thus, the Cu film becomes unstable and even changes its morphologies which affects the device manufacturing yield and ultimate reliability. The structural stability and theoretical strength of Cu crystal under equal biaxial loading have been investigated by combining the MAEAM with Milstein-modified Born stability criteria. The results indicate that, under sufficient tension, there exists a stress-free BCC phase which is unstable and slips spontaneously to a stress-free metastable BCT phase by consuming internal energy. The stable region ranges from −15.131 GPa to 2.803 GPa in the theoretical strength or from −5.801% to 4.972% in the strain respectively.     

Characterization of lead free (K0.5Na0.5)NbO3-LiSbO3 piezoceramic

(K_0.5Na_0.5)NbO₃ (KNN) based lead free ceramics have been fabricated by a solid state reaction. In this work, LiSbO₃ (LS) modified KNN based ceramics were sintered at atmospheric pressure and high density (>96% theoretical) was obtained. The detailed elastic, dielectric, piezoelectric and electromechanical properties were characterized by using the resonance technique combined with the ultrasonic method. The full set of material constants for the obtained polycrystalline ceramics were determined and compared to the pure hot pressed KNN counterpart. KNN-LS polycrystalline ceramic was found to have higher elastic compliance, dielectric permittivity and piezoelectric strain coefficients, but lower mechanical quality factor, when compared to pure KNN, exhibiting a “softening” behavior. However, a high coercive field (∼17 kV/cm) was found for the LS modified KNN material. The properties as a function of temperature were determined in the range of −50-250 ^°C, showing a polymorphic phase transition near room temperature, giving rise to improved piezoelectric behavior.     

Electronic band gap of SrSe at high pressure

The electronic band gap of SrSe, in the CsCl-stuctured phase, was measured to 42 GPa via optical absorption studies. The indirect electronic band gap was found to close monotonically with pressure for the range of pressures studied. The change in band gap with respect to pressure, dE_gap/dP, was determined to be −6.1(5)×10⁻³ eV/GPa. By extrapolation of our line fit, we estimate band gap closure to occur at 180(20) GPa.     

Synthesis and optical properties of single crystalline GaN nanorods with a rectangular cross-section

GaN nanorods were synthesized from the reaction of a Ga/Ga₂O₃ mixture with NH₃ on Si substrates by chemical vapor deposition. The synthesized products were characterized by scanning and transmission electron microscopy, X-ray diffraction, photoluminescence and Raman spectroscopy. The nanorods are highly single crystalline and possess uniform smooth surfaces. PL revealed only a strong emission at 3.268 eV, ascribed to free exciton (FX) transitions, at room temperature; while the well-known yellow luminescence band centered at 2.2-2.3 eV was not detected. Four first-order phonon modes, corresponding to the A₁(TO), E₁(TO), E₂(high), and A₁(LO) at ∼531, 554, 564, and 721 cm⁻¹, respectively, were observed by Raman backscattering. The red-shift of the FX emission peak and the down-shifts of the Raman modes by a few wave numbers are attributed to the presence of tensile strain inside GaN nanorods.     

THEORETICAL STRENGTH AND PHASE STABILITY OF Cu AND Ni UNDER [100] UNIAXIAL LOADING

Based on Born's criteria we studied phase stability and theoretical strength of fcc crystals of copper and nickel under [100] uniaxial loading. The calculation was carried out using a simple and completely analytical embedded atom method(EAM) potential proposed by the present authors. For Cu, the calculated value of its theoretical strength (0.33×10¹¹ dyn·cm^-2) agrees well with the experimental value (0.30×10¹¹ dyn·cm^-2), while the calculated strain (9.76%) is somewhat larger than the experimental one (2.8%). For Ni, its theoretical strength and strain predicted using the EAM potential are found smaller than those predicted using a pair potential. It is worthy to note that unlike previous calculations, in which pair potentials were used and three unstressed fcc, bcc, and fct structures included (for Ni only fcc state is found stable, while for Cu both fcc and bcc states are predicted stable), in present calculations using EAM potential the [100] primary loading path passes through only two zeroes (a stable unstressed fcc structure and an unstable stress-free bcc structure) either for Cu or for Ni.     

The influence of interface states and bulk carrier lifetime on the minority carrier behavior in an illuminated metal/insulator/GaN structure

An influence of electronic states at an insulator/GaN interface on the behavior of excess holes in an ultraviolet-illuminated metal/ SiO₂/n-GaN structure has been studied by numerical simulations for weak (gate bias of −0.1 V ) and strong (−1 V ) depletion, in a wide range of excitation light intensities (from 10¹⁰ to 10²⁰ photons cm⁻² s⁻¹) and for various bulk carrier lifetimes (from 1 to 100 ns). It has been found that the interface states with densities of 10¹² eV ⁻¹ cm⁻² dramatically reduce the total (integrated in the whole GaN layer) density of photogenerated holes and thus degrade the sensitivity of the metal/insulator/GaN-based photodetector.     

Theory of collective dynamics of liquid polyvalent metal: Hg

Recently suggested microscopic theory of collective dynamics of a liquid has been used to successfully explain the detailed experimental dynamic structure factor of liquid mercury at room temperature, observed experimentally recently using high resolution inelastic X-ray scattering for various momentum transfers lying in the range 3 nm⁻¹–37.1 nm⁻¹.     

Electrochemical properties of LiFe0.9Mg0.1PO4 / carbon cathode materials prepared by ultrasonic spray pyrolysis

The LiFe_0.9Mg_0.1PO₄/C powder of pure olivine phase can be prepared with the duplex process of spray pyrolysis synthesis (at 450 ^°C) and subsequent heat treatment (at 700 ^°C for 2, 4 and 8 h). From scanning electron microscopy observation with corresponding elemental mapping images of iron, phosphorous and magnesium, it could be found that the LiFe_0.9Mg_0.1PO₄ powders are covered with fine pyrolyzed carbon. Raman spectra indicate that the phase of carbon with higher electronic conductive phase is predominant when prolonged subsequent heat treatment is carried out. The carbon coatings on the LiFe_0.9Mg_0.1PO₄ surface can improve the conductivity of the LiFe_0.9Mg_0.1PO₄ powder (3.8×10⁻⁵ S cm⁻¹) to about a factor of ∼10⁴ higher than the conductivity of LiFePO₄. The stability and cycle life of a charge/discharge cycle test of lithium ion secondary batteries are also enhanced. The results indicate that the LiFe_0.9Mg_0.1PO₄ powder, prepared at a pyrolysis temperature of 450 ^°C and with post-heat-treatment at 700 ^°C for 8 h, exhibits a specific initial discharge capacity of about 132 mA h g⁻¹ at C/10 rate, 105 mA h g⁻¹ at 1C, and 87 mA h g⁻¹ at 5C.     

Resonant Raman scattering in single crystal of congruent LiTaO3 : Effect of excitation energy

Large dispersion in the peak position of the OH⁻ stretching mode (∼687.9 and ∼2167.7 cm⁻¹/eV for fundamental and 3rd harmonic, respectively) is observed by Resonance Raman studies in congruent lithium tantalate single crystal under varying excitation energies. This is explained by considering the involvement of multiple LO phonons in the interaction with OH⁻ stretching vibration and the resonantly excited electrons. The intensity of the peaks is also found to vary with the excitation energy. FWHM increases with the increase in excitation energy because of individual contributions of the increasing number of resonance steps to the broadening.     

Quadratic electro-optic effect in the nonconjugated conductive polymer iodine-doped trans-polyisoprene, an organic nanometallic system

Thin films of 1,4-trans-polyisoprene have been prepared on various substrates from toluene solution and characterized using Fourier transform infrared (FTIR) spectroscopy, optical absorption spectroscopy and X-ray diffraction before and after doping with iodine. The optical absorption spectrum at low doping shows two peaks: one at 4.2 eV and the other at 3.2 eV. X-ray diffraction indicates an increase of (111) and (122) peak intensities upon doping. Quadratic electro-optic measurements have been made using field-induced birefringence. The Kerr coefficients as measured (3.5×10⁻¹⁰ m/V ² at 633 nm and 2.5×10⁻¹⁰ m/V ² at 1.55 μm) are exceptionally large, and they have been attributed to the subnanometer-size metallic domains formed upon doping and charge transfer.     

Effects of nickel doping on structural and optical properties of spinel lithium manganate thin films

Spinel LiNi_xMn_2−xO₄ (x≤0.9) thin films were synthesized by a sol-gel method employing spin-coating. The Ni-doped films were found to maintain cubic structure at low x but to exhibit a phase transition to tetragonal structure for x≥0.6. Such cubic-tetragonal phase transition can be explained in terms of Ni³⁺(d⁷) ions with low-spin (t_2g⁶,e_g¹) configuration occupying the octahedral sites of the compound, thus being subject to the Jahn-Teller effect. By X-ray photoelectron spectroscopy both Ni³⁺ and Ni²⁺ ions were detected where Ni²⁺ is more populated than Ni³⁺. Optical properties of the LiNi_xMn_2−xO₄ films were investigated by spectroscopic ellipsometry in the visible-ultraviolet range. The measured dielectric function spectra mainly consist of broad absorption structures attributed to charge-transfer transitions, O²⁻(2p)→Mn⁴⁺(3d) for 1.9 (t_2g) and 2.8-3.0 eV (e_g) structures and O²⁻(2p)→Mn³⁺(3d) for 2.3 (t_2g) and 3.4-3.6 eV (e_g) structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as being due to d-d crystal-field transitions within the octahedral Mn³⁺ ion. In terms of these transitions, the evolution of the optical absorption spectrum of LiMn₂O₄ by Ni doping could be explained and the related electronic structure parameters were obtained.     

Preparation of pulse plated GaAs films

Thin GaAs films were prepared by pulse plating from an aqueous solution containing 0.20 M GaCl₃ and 0.15 M As₂O₃ at a pH of 2 and at room temperature. The current density was kept as 50 mA cm⁻² the duty cycle was varied in the range 10-50%. The films were deposited on titanium, nickel and tin oxide coated glass substrates. Films exhibited polycrystalline nature with peaks corresponding to single phase GaAs. Optical absorption measurements indicated a direct band gap of 1.40 eV. Photoelectrochemical cells were made using the films as photoelectrodes and graphite as counter electrode in 1 M polysulphide electrolyte. At 60 mW cm⁻² illumination, an open circuit voltage of 0.5 V and a short circuit current density of 5.0 mA cm⁻² were observed for the films deposited at a duty cycle of 50%.     

Refractive index, oscillator parameters and temperature-tuned energy band gap of Tl4In3GaS8-layered single crystals

Transmission and reflection measurements in the wavelength region 450-1100 nm were carried out on Tl₄In₃GaS₈-layered single crystals. The analysis of the room temperature absorption data revealed the presence of both optical indirect and direct transitions with band gap energies of 2.32 and 2.52 eV, respectively. The rate of change of the indirect band gap with temperature dE_gi/dT=-6.0×10⁻⁴ eV/K was determined from transmission measurements in the temperature range of 10-300 K. The absolute zero value of the band gap energy was obtained as E_gi(0)=2.44 eV. The dispersion of the refractive index is discussed in terms of the Wemple-DiDomenico single-effective-oscillator model. The refractive index dispersion parameters: oscillator energy, dispersion energy, oscillator strength and zero-frequency refractive index were found to be 4.87 eV, 26.77 eV, 8.48×10¹³ m⁻² and 2.55, respectively.     

Ab initio study of the chemical states of water on Cr2O3(0 0 0 1): From the isolated molecule to saturation coverage

The reactivity of the (0 0 0 1)-Cr–Cr₂O₃ surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H₂O/nm² to 14.1H₂O/nm², corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr₂O₃ surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H₂O/nm²), 5 (9.4H₂O/nm²) and 6 (14.1H₂O/nm²). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H₂O/nm², the Cr–O_s (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H₂O/nm², molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H₂O/nm², 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)₂ and –Cr(OH)₃– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t_2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)₃-like, –Cr(OH)₂ and anhydrous surfaces may be stabilized depending on (T, P) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.     

Physical properties of the delafossite LaCuO2

High-quality LaCuO₂, elaborated by solid-state reaction in sealed tube, crystallizes in the delafossite structure. The thermal analysis under reducing atmosphere (H₂/N₂: 1/9) revealed a stoichiometric composition LaCuO_2.00. The oxide is a direct band-gap semiconductor with a forbidden band of 2.77 eV. The magnetic susceptibility follows a Curie-Weiss law from which a Cu²⁺ concentration of 1% has been determined. The oxygen insertion in the layered crystal lattice induces p-type conductivity. The electrical conduction occurs predominantly by small polaron hopping between mixed valences Cu^+/2+ with an activation energy of 0.28 eV and a hole mobility (μ_300 K=3.5×10⁻⁷ cm² V⁻¹ s⁻¹), thermally activated. Most holes are trapped in surface-polaron states upon gap excitation. The photoelectrochemical study, reported for the first time, confirms the p-type conduction. The flat band potential (V_fb=0.15 V_SCE) and the hole density (N_A=5.8×10¹⁷ cm⁻³) were determined, respectively, by extrapolating the curve C⁻² versus the potential to their intersection with C⁻²=0 and from the slope of the linear part in the Mott-Schottky plot. The valence band is made up of Cu-3d orbital, positioned at 4.9 eV below vacuum. An energy band diagram has been established predicting the possibility of the oxide to be used as hydrogen photocathode.     

Band gap energy and bowing parameter of In-rich InAlN films grown by magnetron sputtering

The crystal structure, band gap energy and bowing parameter of In-rich In_xAl_1−xN (0.7 < x < 1.0) films grown by magnetron sputtering were investigated. Band gap energies of In_xAl_1−xN films were obtained from absorption spectra. Band gap tailing due to compositional fluctuation in the films was observed. The band gap of the as-grown InN measured by optical absorption method is 1.34 eV, which is larger than the reported 0.7 eV for pure InN prepared by molecular beam epitaxy (MBE) method. This could be explained by the Burstein-Moss effect under carrier concentration of 10²⁰ cm⁻³ of our sputtered films. The bowing parameter of 3.68 eV is obtained for our In_xAl_1−xN film which is consistent with the previous experimental reports and theoretical calculations.     

High-conductive nanocrystalline silicon with phosphorous and boron doping

Intrinsic, P- and B-doped hydrogenated amorphous silicon thin films were prepared by plasma-enhanced chemical vapor deposition technique. As-deposited samples were thermally annealed at the temperature of 800 °C to obtain the doped nanocrystalline silicon (nc-Si) films. The microstructures, optical and electronic properties have been evaluated for the undoped and doped nanocrystalline films. X-ray photoelectron spectroscopy (XPS) measurements demonstrated the presence of the substitutional boron and phosphorous in the doped films. It was found that thermal annealing can efficiently activate the dopants in films accompanying with formation of nc-Si grains. Based on the temperature-dependent conductivity measurements, it was shown that the activation of dopant by annealing increased the room temperature dark conductivity from 3.4 × 10⁻⁴ S cm⁻¹ to 5.3 S cm⁻¹ for the P-doped films and from 1.28 × 10⁻³ S cm⁻¹ to 130 S cm⁻¹ for the B-doped films. Meanwhile, the corresponding value of conductivity activation energies was decreased from 0.29 eV to 0.03 eV for the P-doped films and from 0.3 eV to 5.6 × 10⁻⁵ eV for the B-doped films, which indicated the doped nc-Si films with high conductivity can be achieved with the present approach.