Systematic study of the static electrical properties of the CO molecule: influence of the basis set size and correlation energy

The influence of the basis set size and the correlation energy in the static electrical properties of the CO molecule is assessed. In particular, we have studied both the nuclear relaxation and the vibrational contributions to the static molecular electrical properties, the vibrational Stark effect (VSE) and the vibrational intensity effect (VIE). From a mathematical point of view, when a static and uniform electric field is applied to a molecule, the energy of this system can be expressed in terms of a double power series with respect to the bond length and to the field strength. From the power series expansion of the potential energy, field-dependent expressions for the equilibrium geometry, for the potential energy and for the force constant are obtained. The nuclear relaxation and vibrational contributions to the molecular electrical properties are analyzed in terms of the derivatives of the electronic molecular properties. In general, the results presented show that accurate inclusion of the correlation energy and large basis sets are needed to calculate the molecular electrical properties and their derivatives with respect to either nuclear displacements or/and field strength. With respect to experimental data, the calculated power series coefficients are overestimated by the SCF, CISD, and QCISD methods. On the contrary, perturbation methods (MP2 and MP4) tend to underestimate them. In average and using the 6-311 + G(3df) basis set and for the CO molecule, the nuclear relaxation and the vibrational contributions to the molecular electrical properties amount to 11.7%, 3.3%, and 69.7% of the purely electronic μ, α, and β values, respectively

Cation distribution and magnetization of BaFe12-2xCoxSnxO19 (x=0.9,1.28) single crystals

The distribution of Sn4+ cations within the five crystallographic sites of the magnetoplumbite (M) ‐like compound BaFe12−2xCoxSnxO19 has been analyzed using single‐crystal x‐ray‐diffraction data. The species Fe3+ and Co2+ cannot be distinguished using x rays because of their very similar atomic numbers; however, the calculation of the apparent valencies for the different sites allows an insight into the Co2+ cation segregation. The use of previous data from neutron powder diffraction allows a precise picture of the cation distribution, which indicates a pronounced site selectivity for both Sn4+ and Co2+ cations. The Sn4+ cations prefer the 4f2 sites and to a much lower extent the 12k sites, while they do not enter the octahedral 2a sites at all. Co2+ cations are distributed among tetrahedral and octahedral sites displaying a clear preference for the tetrahedral 4f1 sites. Magnetic measurements indicate that the compound still exhibits uniaxial anisotropy with the easy direction parallel to the c axis. Nevertheless, the magnetic structure shows a considerable degree of noncolinearity. A strong reduction of the magnetic anisotropy regarding that of the undoped compound is also detected.

Optical response of Cu3Ge thin films

We report an investigation on the optical properties of Cu3Ge thin films displaying very high conductivity, with thickness ranging from 200 to 2000 Å, deposited on Ge substrates. Reflectance, transmittance, and ellipsometric spectroscopy measurements were performed at room temperature in the 0.01-6.0, 0.01-0.6, and 1.4-5.0 eV energy range, respectively. The complex dielectric function, the optical conductivity, the energy-loss function, and the effective charge density were obtained over the whole spectral range. The low-energy free-carrier response was well fitted by using the classical Drude-Lorentz dielectric function. A simple two-band model allowed the resulting optical parameters to be interpreted coherently with those previously obtained from transport measurements, hence yielding the densities and the effective masses of electrons and holes.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P) = I0¿exp(¿P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature.

Size dependence of refractive index of Si nanoclusters embedded in SiO2

he complex refractive index of SiO2 layers containing Si nanoclusters (Si-nc) has been measured by spectroscopic ellipsometry in the range from 1.5 to 5.0 eV. It has been correlated with the amount of Si excess accurately measured by x-ray photoelectron spectroscopy and the nanocluster size determined by energy-filtered transmission electron microscopy. The Si-nc embedded in SiO2 have been produced by a fourfold Si+ ion implantation, providing uniform Si excess aimed at a reliable ellipsometric modeling. The complex refractive index of the Si-nc phase has been calculated by the application of the Bruggeman effective-medium approximation to the composite media. The characteristic resonances of the refractive index and extinction coefficient of bulk Si vanish out in Si-nc. In agreement with theoretical simulations, a significant reduction of the refractive index of Si-nc is observed, in comparison with bulk and amorphous silicon. The knowledge of the optical properties of these composite layers is crucial for the realization of Si-based waveguides and light-emitting devices.

Optical-geometrical effects on the photoluminescence spectra of Si nanocrystals embedded in SiO2

We demonstrate that thickness, optical constants, and details of the multilayer stack, together with the detection setting, strongly influence the photoluminescence spectra of Si nanocrystals embedded in SiO2. Due to multiple reflections of the visible light against the opaque silicon substrate, an interference pattern is built inside the oxide layer, which is responsible for the modifications in the measured spectra. This interference effect is complicated by the depth dependence of (i) the intensity of the excitation laser and (ii) the concentration of the emitting nanocrystals. These variations can give rise to apparent features in the recorded spectra, such as peak shifts, satellite shoulders, and even splittings, which can be mistaken as intrinsic material features. Thus, they can give rise to an erroneous attribution of optical bands or estimate of the average particle size, while they are only optical-geometrical artifacts. We have analyzed these effects as a function of material composition (Si excess fraction) and thickness, and also evaluated how the geometry of the detection setup affects the measurements. To correct the experimental photoluminescence spectra and extract the true spectral shape of the emission from Si nanocrystals, we have developed an algorithm based on a modulation function, which depends on both the multilayer sequence and the experimental configuration. This procedure can be easily extended to other heterogeneous systems.

The effect of substrate on high-temperature annealing of GaN epilayers: Si versus sapphire

We have studied the effects of rapid thermal annealing at 1300¿°C on GaN epilayers grown on AlN buffered Si(111) and on sapphire substrates. After annealing, the epilayers grown on Si display visible alterations with craterlike morphology scattered over the surface. The annealed GaN/Si layers were characterized by a range of experimental techniques: scanning electron microscopy, optical confocal imaging, energy dispersive x-ray microanalysis, Raman scattering, and cathodoluminescence. A substantial Si migration to the GaN epilayer was observed in the crater regions, where decomposition of GaN and formation of Si3N4 crystallites as well as metallic Ga droplets and Si nanocrystals have occurred. The average diameter of the Si nanocrystals was estimated from Raman scattering to be around 3¿nm. Such annealing effects, which are not observed in GaN grown on sapphire, are a significant issue for applications of GaN grown on Si(111) substrates when subsequent high-temperature processing is required.

Structural and functional characterization of (110)-oriented epitaxial La2/3Ca1/3MnO3 electrodes and SrTiO3 tunnel barriers

La2/3Ca1/3MnO3 (LCMO) films have been deposited on (110)-oriented SrTiO3 (STO) substrates. X-ray diffraction and high-resolution electron microscopy reveal that the (110) LCMO films are epitaxial and anisotropically in-plane strained, with higher relaxation along the [1¿10] direction than along the [001] direction; x-ray absorption spectroscopy data signaled the existence of a single intermediate Mn3+/4+ 3d-state at the film surface. Their magnetic properties are compared to those of (001) LCMO films grown simultaneously on (001) STO substrates It is found that (110) LCMO films present a higher Curie temperature (TC) and a weaker decay of magnetization when approaching TC than their (001) LCMO counterparts. These improved films have been subsequently covered by nanometric STO layers. Conducting atomic-force experiments have shown that STO layers, as thin as 0.8 nm, grown on top of the (110) LCMO electrode, display good insulating properties. We will show that the electric conductance across (110) STO layers, exponentially depending on the barrier thickness, is tunnel-like. The barrier height in STO (110) is found to be similar to that of STO (001). These results show that the (110) LCMO electrodes can be better electrodes than (001) LCMO for magnetic tunnel junctions, and that (110) STO are suitable insulating barriers.

Raman microprobe characterization of electrodeposited S-rich CuIn(S,Se)2 for photovoltaic applications: Microstructural analysis

This article reports a detailed Raman scattering and microstructural characterization of S-rich CuIn(S,Se)2 absorbers produced by electrodeposition of nanocrystalline CuInSe2 precursors and subsequent reactive annealing under sulfurizing conditions. Surface and in-depth resolved Raman microprobe measurements have been correlated with the analysis of the layers by optical and scanning electron microscopy, x-ray diffraction, and in-depth Auger electron spectroscopy. This has allowed corroboration of the high crystalline quality of the sulfurized layers. The sulfurizing conditions used also lead to the formation of a relatively thick MoS2 intermediate layer between the absorber and the Mo back contact. The analysis of the absorbers has also allowed identification of the presence of In-rich secondary phases, which are likely related to the coexistence in the electrodeposited precursors of ordered vacancy compound domains with the main chalcopyrite phase, in spite of the Cu-rich conditions used in the growth. This points out the higher complexity of the electrodeposition and sulfurization processes in relation to those based in vacuum deposition techniques.

Effects of SrTiO3 capping in La2/3Ca1/3MnO3 electrodes of different orientations

We report on the study of the structural, magnetic, and electronic properties of SrTiO3 capped La2/3Ca1/3MnO3 electrodes grown on (001) and (110) SrTiO3 substrates. Magnetic properties of the (001) and (110) capped electrodes evolve differently when the capping layer thickness increases, revealing a reduction of the saturation magnetization for the (001) ones. Electronic properties are studied combining 55Mn nuclear magnetic resonance (NMR) and x-ray photoemission spectroscopy (XPS). NMR experiments highlight that electronic phase separation in the (001) electrodes is enhanced by the presence of the SrTiO3 capping layer and XPS measurements show that the electronic state of interfacial Mn ions from (001) electrode is more sensitive to the capping layer.

Linear and nonlinear optical properties of Si nanocrystals in SiO2 deposited by plasma-enhanced chemical-vapor deposition

Linear and nonlinear optical properties of silicon suboxide SiOx films deposited by plasma-enhanced chemical-vapor deposition have been studied for different Si excesses up to 24¿at.¿%. The layers have been fully characterized with respect to their atomic composition and the structure of the Si precipitates. Linear refractive index and extinction coefficient have been determined in the whole visible range, enabling to estimate the optical bandgap as a function of the Si nanocrystal size. Nonlinear optical properties have been evaluated by the z-scan technique for two different excitations: at 0.80¿eV in the nanosecond regime and at 1.50¿eV in the femtosecond regime. Under nanosecond excitation conditions, the nonlinear process is ruled by thermal effects, showing large values of both nonlinear refractive index (n2 ~ ¿10¿8¿cm2/W) and nonlinear absorption coefficient (ß ~ 10¿6¿cm/W). Under femtosecond excitation conditions, a smaller nonlinear refractive index is found (n2 ~ 10¿12¿cm2/W), typical of nonlinearities arising from electronic response. The contribution per nanocrystal to the electronic third-order nonlinear susceptibility increases as the size of the Si nanoparticles is reduced, due to the appearance of electronic transitions between discrete levels induced by quantum confinement.

Nucleation and growth of GaN nanorods on Si (111) surfaces by plasma-assisted molecular beam epitaxy - The influence of Si- and Mg-doping

The self-assembled growth of GaN nanorods on Si (111) substrates by plasma-assisted molecular beam epitaxy under nitrogen-rich conditions is investigated. An amorphous silicon nitride layer is formed in the initial stage of growth that prevents the formation of a GaN wetting layer. The nucleation time was found to be strongly influenced by the substrate temperature and was more than 30 min for the applied growth conditions. The observed tapering and reduced length of silicon-doped nanorods is explained by enhanced nucleation on nonpolar facets and proves Ga-adatom diffusion on nanorod sidewalls as one contribution to the axial growth. The presence of Mg leads to an increased radial growth rate with a simultaneous decrease of the nanorod length and reduces the nucleation time for high Mg concentrations.

Influence of the (111) twinning on the formation of diamond cubic/diamond hexagonal heterostructures in Cu-catalyzed Si nanowires

The occurrence of heterostructures of cubic silicon/hexagonal silicon as disks defined along the nanowire (111) growth direction is reviewed in detail for Si nanowires obtained using Cu as catalyst. Detailed measurements on the structural properties of both semiconductor phases and their interface are presented. We observe that during growth, lamellar twinning on the cubic phase along the (111) direction is generated. Consecutive presence of twins along the (111) growth direction was found to be correlated with the origin of the local formation of the hexagonal Si segments along the nanowires, which define quantum wells of hexagonal Si diamond. Finally, we evaluate and comment on the consequences of the twins and wurtzite in the final electronic properties of the wires with the help of the predicted energy band diagram.

Nanoscale capacitance microscopy of thin dielectric films

We present an analytical model to interpret nanoscale capacitance microscopy measurements on thin dielectric films. The model displays a logarithmic dependence on the tip-sample distance and on the film thickness-dielectric constant ratio and shows an excellent agreement with finite-element numerical simulations and experimental results on a broad range of values. Based on these results, we discuss the capabilities of nanoscale capacitance microscopy for the quantitative extraction of the dielectric constant and the thickness of thin dielectric films at the nanoscale.

Analysis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Influence of the sulfurization temperature on the crystalline properties of electrodeposited and sulfurized CuInSe2 precursors

This paper reports the microstructural analysis of S-rich CuIn(S,Se)2 layers produced by electrodeposition of CuInSe2 precursors and annealing under sulfurizing conditions as a function of the temperature of sulfurization. The characterization of the layers by Raman scattering, scanning electron microscopy, Auger electron spectroscopy, and XRD techniques has allowed observation of the strong dependence of the crystalline quality of these layers on the sulfurization temperature: Higher sulfurization temperatures lead to films with improved crystallinity, larger average grain size, and lower density of structural defects. However, it also favors the formation of a thicker MoS2 interphase layer between the CuInS2 absorber layer and the Mo back contact. Decreasing the temperature of sulfurization leads to a significant decrease in the thickness of this intermediate layer and is also accompanied by significant changes in the composition of the interface region between the absorber and the MoS2 layer, which becomes Cu rich. The characterization of devices fabricated with these absorbers corroborates the significant impact of all these features on device parameters as the open circuit voltage and fill factor that determine the efficiency of the solar cells.