Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

Effect of microstructure on the conductivity of a NASICON-type lithium ion conductor

Sintering temperature is used to control the microstructure of Li_{1 + x + y}Al_xTi_2 − xSi_yP_3 − yO₁₂ (x = 0.3, y = 0.2), a NASICON-type glass-ceramic. Scanning Electron Microscope imaging, X-Ray Diffraction, and Electrochemical Impedance Spectroscopy are employed to show that increase in sintering temperature increases conductivity while generating secondary crystalline phases. Total conductivity is as high as 3.81 × 10⁻⁴ S cm⁻¹ for sintering temperatures above 1000 °C. Crystallization of dielectric phases places the optimal sintering temperature in the 900 °C to 1000 °C range. Thermal analysis of the glass precursor reveals the glass transition, and crystallization temperatures.     

Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Transport properties and non-stoichiometry of La_1−xCa_xW_1/6O₂ and La_1−yW_1/6O₂ (x=0, 0.005, 0.05; y=0.05, 0.1) have been characterized by means of impedance spectroscopy, the EMF-technique, H⁺/D⁺ isotope exchange, and thermogravimetry in the temperature range 300-1200 °C as a function of oxygen partial pressure and water vapor partial pressure. The materials exhibit mixed ionic and electronic conductivities; n- and p-type electronic conduction predominate at high temperatures under reducing and oxidizing conditions, respectively. Protons are the major ionic charge carrier under wet conditions and predominates the conductivity below ∼750 °C. The maximum in proton conductivity is observed for LaW_1/6O₂ with values reaching 3×10⁻³ S/cm at approximately 800 °C. The high proton conductivity for the undoped material is explained by assuming interaction between water vapor and intrinsic (anti-Frenkel) oxygen vacancies.     

Influence of primary ion species on the secondary cluster ion emission process from SAMs of hexadecanethiol on gold

In order to investigate the secondary cluster ion emission process of organo-metallic compounds under keV ion bombardment, self-assembled monolayers (SAMs) of alkanethiols on gold are ideal model systems. In this experimental study, we focussed on the influence of the primary ion species on the emission processes of gold-alkanethiolate cluster ions from a hexadecanethiol SAM on gold. For this purpose, we carried out time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements using the following primary ion species and acceleration voltages: Ar⁺, Xe⁺, SF₅⁺ (10 kV), Bi⁺, Bi₃⁺(25 kV), Bi₃²⁺, Bi₅²⁺, Bi₇²⁺ (25 kV).It is well known that molecular ions M⁻ and gold-alkanethiolate cluster ions Au_xM_y⁻ with M = S-(CH₂)₁₅-CH₃, x − 3 ≤ y ≤ x + 1, x, y > 0, show intense peaks in negative mass spectra. We derived yields Y_SI exemplarily for the molecular ions M⁻ and the gold-hexadecanethiolate cluster ions Au_y+1M_y⁻ up to y = 8 and found an exponentially decreasing behaviour for increasing y-values for the cluster ions.In contrast to the well-known increase in secondary ion yield for molecular secondary ions when moving from lighter to heavier (e.g. Ar⁺ to Xe⁺) or from monoatomic to polyatomic (e.g. Xe⁺ to SF₅⁺) primary ions, we find a distinctly different behaviour for the secondary cluster ions. For polyatomic primary ions, there is a decrease in secondary ion yield for the gold-hexadecanethiolate clusters whereas the relative decrease of the secondary ion yield ξ_Y with increasing y remains almost constant for all investigated primary ions.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Elemental depth profiling of a-Si1−xGex:H films by elastic recoil detection analysis and secondary ion mass spectrometry

The hydrogen content in a-Si_1−xGe_x:H thin films is an important factor deciding the density and the optical band gap. We measured the elemental depth profiles of hydrogen together with Si and Ge by elastic recoil detection analysis (ERDA) combined with Rutherford backscattering (RBS) using MeV He²⁺ ions. In order to determine the hydrogen depth profiles precisely, the energy- and angle-dependent recoil cross-sections were measured in advance for the standard sample of a CH₃⁺-implanted Si substrate. The cross-sections obtained here are reproduced well by a simple expression based on the partial wave analysis assuming a square well potential (width: r₀ = 2.67 × 10⁻¹³ cm, depth: V₀ = −36.9 MeV) within 1%. For the a-Si_1−xGe_x:H films whose elemental compositions were determined by ERDA/RBS, we measured the secondary ions yields of HCs₂⁺, SiCs₂⁺, H⁻, Si⁻ and Ge⁻ as a function of Ge concentration x. As a result, it is found that the useful yield ratios of HCs₂⁺/SiCs₂⁺, H⁻/Si⁻ and Ge⁻/Si⁻ are almost constant and thus the elemental depth profiles of the a-Si_1−xGe_x:H films can be also determined by secondary ion mass spectrometry (SIMS) within 10% free from a matrix effect.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.     

Nanoscale intrinsic heterogeneities in Ag-Ge-Se glasses and their correlation with physical properties

Ag-Ge-Se glass forming system is dominated by liquid immiscibility. Glasses in the Se-GeSe₂-Ag₂Se triangle may have different morphologies according to their composition. In this work inhomogeneous morphology is observed in Ag_x(Ge_ySe_1−y)_100−x bulk glasses with y = 0.20, 0.25 at.% fraction. Electron microscopy reveals that the scale of heterogeneity strongly depends on the sample composition. The physical properties of these glasses are also dependent on their composition and can be easily correlated to their morphology. Accordingly, the electric conductivity evolves from semiconducting to ionic conductivity whereas a percolation transition occurs in a narrow Ag concentration range.Mössbauer spectrometry let us to analyse the local order of these intrinsically heterogeneous glasses employing ⁵⁷Fe as a probe.     

ESR of Cu doped cadmium (II) formate dihydrate

Electron spin resonance (ESR) of Cu²⁺ doped cadmium formate dihydrate single crystal was studied at room temperature. Copper enters the lattice substitutionally and is trapped at two magnetically inequivalent sites. The observed spectra are fitted to a spin-Hamiltonian of rhombic symmetry with the following values of the spin-Hamiltonian parameters, Cu²⁺(I): g_x=2.097±0.002, g_y=2.1166±0.002, g_z=2.2887±0.002 and A_x=(140±2)×10⁻⁴ cm⁻¹, A_y=(151±2)×10⁻⁴ cm⁻¹, A_z=(239±2)×10⁻⁴ cm⁻¹, Cu²⁺(II): g_x=2.0843±0.002, g_y=2.1045±0.002, g_z=2.2742±0.002 and A_x=(141±2)×10⁻⁴ cm⁻¹, A_y=(158±2)×10⁻⁴ cm⁻¹, A_z=(267±2)×10⁻⁴ cm⁻¹. The ground state wave function of the Cu²⁺ ion in this lattice is evaluated. It is found that the ground state is predominantly |x²−y²〉. The g-factor anisotropy is also calculated and compared with the experimental value. With the help of the optical absorption study, the nature of bonding in the complex has been discussed.     

Causal particle detectors and topology

We investigate particle detector responses in some topologically non-trivial spacetimes. We extend a recently proposed regularization of the massless scalar field Wightman function in four-dimensional Minkowski space to arbitrary dimension, to the massive scalar field, to quotients of Minkowski space under discrete isometry groups and to the massless Dirac field. We investigate in detail the transition rate of inertial and uniformly accelerated detectors on the quotient spaces under groups generated by (t, x, y, z) ? (t, x, y, z + 2a), (t, x, y, z) ? (t, −x, y, z), (t, x, y, z) ? (t, −x, −y, z), (t, x, y, z) ? (t, −x, −y, z + a) and some higher dimensional generalizations. For motions in at constant y and z on the latter three spaces the response is time dependent. We also discuss the response of static detectors on the RP³ geon and inertial detectors on RP³ de Sitter space via their associated global embedding Minkowski spaces (GEMS). The response on RP³ de Sitter space, found both directly and in its GEMS, provides support for the validity of applying the GEMS procedure to detector responses and to quotient spaces such as RP³ de Sitter space and the RP³ geon where the embedding spaces are Minkowski spaces with suitable identifications.     

(Mo + N) codoped TiO2 for enhanced visible-light photoactivity

A series of Ti_1−xMo_xO_2−yN_y samples were prepared by using sol-gel method and characterized by X-ray diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. All Ti_1−xMo_xO_2−yN_y samples are anatase phase. It is found that Mo, N mono-doping can increase visible light absorption, while (Mo + N) co-doping can greatly enhance absorption in whole visible region. Results of our first-principles band structure calculations reveal that (Mo + N)-doping, especially passivated co-doping can increase the up-limit of dopant concentration and create more impurity bands in the band gap of TiO₂, which leads to a greatly increase of its visible-light absorption without a decrease of its redox potential. It reveals that (Mo + N) co-doped TiO₂ is promising for a photocatalyst with high photocalystic activity under visible light.     

Synthesis, microstructure and photoluminescence of Eu/Tb activated Y2SiO5 nanophosphors by new silicate sources

Y_2−xTb_xSiO₅ and Y_2−xEu_xSiO₅ nanophosphors with seven different kinds of silicate sources were synthesized by sol-gel method. The structures have been investigated to be composed of nanometer-size grains of 30-60 nm through X-ray diffraction (XRD) and scanning electron microscopy (SEM) was used to compare the different morphology of patterns from seven different silicon sources. The photoluminescence of Y_2−xTb_xSiO₅ was investigated as a function of silicate sources and the results revealed that these nanometer materials showed the characteristic emission ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) of Tb ions. The characteristic emission ⁵D₀ → ⁷F_J (J = 1, 2, 4) of Eu ions was also found in the materials of Y_2−xEu_xSiO₅.     

Nd-laser irradiations effects and AFM-investigations on structural and surface features of optimally lutetium thorium-co-doped-2212-BSCCO

Lutetium-thorium optimally co-doped sample with general formula Bi_2−x−yLu_xTh_ySr₂Ca₁Cu₂O₈ where x = y = 0.15 mol was selected to be the target for three different doses of Nd-laser beam irradiations the 1st 15 W/cm² for 60 min, 2nd 30 W/cm² for 120 min and 3rd 45 W/cm² for 240 min, respectively. Nd-Laser irradiations doses were monitoring as function of micro-structure, superconducting and structural features of Lu-Th-optimally co-doped 2212-BSCCO. AFM and SE-microscopy were applied to investigate changes occurred in the surface's layers after each Nd-laser irradiation dose. Both of bulk superconductivity and surface resistivity were measured to establish the promotion occurred on the superconducting features due to Nd-laser irradiation doses.     

High-temperature electrical properties of magnesiowustite Mg1 − xFexO and spinel Fe3 − x − yMgxCryO4 ceramics

Phase relationships, thermal expansion and electrical properties of Mg_1 − xFe_xO (x = 0.1-0.45) cubic solid solutions and Fe_{3 − x − y}Mg_xCr_yO_4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O₂)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10^− 6 K^− 1 at 300-500 K and (13.2-16.1) × 10^− 6 K^− 1 at 1050-1370 K. Mg_1 − xFe_xO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.     

Enhanced photoluminescence properties of Zn2SiO4:Mn co-activated with Y/Li under VUV excitation

A series of green phosphors Zn_1.92−2xY_xLi_xSiO₄:0.08Mn²⁺ (0≤x≤0.03) were prepared by solid-state synthesis method. Phase and lattice parameters of the synthesized phosphors were characterized by powder X-ray diffractometer (XRD) and the co-doped effects of Y³⁺/Li⁺ upon emission intensity and decay time were investigated under 147 nm excitation. The results indicate that the co-doping of Y³⁺/Li⁺ has favorable influence on the photoluminescence properties of Zn₂SiO₄:Mn²⁺, and the optimal photoluminescence intensity of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 103% of that of commercial phosphor when the doping concentration of Y³⁺/Li⁺ is 0.01 mol. Additionally, the decay time of phosphor is much shortened and the decay time of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 3.39 ms, shorter by 1.83 ms than that of commercial product after Y³⁺/Li⁺ co-doping.     

Thermal entanglement in the XYZ model for a two-qutrit system

The negativity as a measure of thermal entanglement was studied for a two-qutrit spin-1 anisotropic Heisenberg XYZ chain with Dzyaloshinskii-Moriya (DM) interaction in a homogeneous magnetic field in detail. An analytical expression was found for the negativity and then the thermal variations of negativity were investigated in full detail for given values of the DM interaction parameter D_z, the external magnetic field B, the measure of the anisotropy on the xy-plane γ = (J_x − J_y)/(J_x + J_y), a parameter J = (J_x + J_y)/2 and the bilinear interaction parameter J_z along the z-axis.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Synthesis and characterization of hexakis(acetonitrile)chromium(III) tetrafluoroborate, [Cr(NCMe)6][BF4]3. A nonaqueous Cr source

Oxidation of [Cr^II(NCMe)₄][BF₄]₂ with thianthrinium tetrafluoroborate forms [Cr^III(NCMe)₆][BF₄]₃ exhibiting two ν_CN absorptions at 2331 and 2301 cm⁻¹, and has been structurally characterized with an average Cr-N distance of 1.999 Å. From the electronic absorption spectra the ligand field splitting, Δ₀, is 20,160 cm⁻¹, which is slightly larger than [Cr^III(OH₂)₆]³⁺ in accord with the divalent chromium analogues. The 298 K ESR has a resonance at g=1.9884, and the magnetic susceptibility has a 300 K moment of 3.85μ_B characteristic of S=3/2 Cr(III). The field dependence of the magnetization can be fit to the Brillouin function also characteristic of S=3/2.     

Control of luminescence and conductivity of delafossite-type CuYO2 by substitution of rare earth cation (Eu, Tb) and/or Ca cation for Y cation

Delafossite-type oxides of CuTb_yY_1−yO₂, CuEu_yY_1−yO₂, CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ have been prepared by solid state reactions. The lattice-parameter dependence on the composition implies substitution of the Tb³⁺, Eu³⁺ and Ca²⁺ cations for the Y³⁺ site. Noticeable sharp emission lines due to the f-f transitions (⁵D₄→⁷F_J, J=3-6) of Tb³⁺ or due to the f-f transitions (⁵D₀→⁷F_J, J=0-4) of Eu³⁺ are observed at room temperature. Electrical conductivities of CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ are larger than those of CuTb_yY_1−yO₂ and CuEu_yY_1−yO₂, indicating the increase of the hole concentration caused by the substitution of Ca²⁺ for the Y³⁺ site. These results indicate the controllability of the luminescence and conductivity in CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ delafossite-type oxides by simultaneous substitution of the rare earth Tb³⁺ or Eu³⁺ cation and the Ca²⁺ cation for the Y³⁺ site.