X-ray diffraction measurements for liquid Ge–Si alloys using synchrotron radiation

Energy dispersive X-ray diffraction measurements have been carried out for liquid Ge_1−xSi_x alloys (x = 0.0, 0.3, 0.5, 1.0) using synchrotron radiation at SPring-8. We measured the X-ray diffraction spectra of liquid Ge and Si up to a high temperature range, (liquid Ge from 1270 to1870 K and liquid Si from 1680 to 2020 K), liquid Ge_0.7Si_0.3 at 1620 K, and liquid Ge_0.5Si_0.5 at 1540, 1590, 1670 and 1720 K. The total structure factors of the liquid Ge–Si alloys have a characteristic shoulder on the high-wave-vector side of the first peak. We deduced a pair distribution function from the Fourier transform of the observed structure factor, which was weakly dependent on the temperature. The nearest-neighbor coordination number of liquid Ge–Si alloys is close to that of pure liquid Ge and Si. The first peak of the pair distribution function moved to a shorter distance with increasing Si concentration. These results may indicate that the atomic radii of the Si and Ge atoms in the pure liquid are preserved in the liquid alloys.     

Photoluminescence of Si or Ge nanocrystallites embedded in silicon oxide

This paper presents the results of photoluminescence, its temperature dependence and Raman scattering investigations on magnetron co-sputtered silicon oxide films with (or without) embedded Si (or Ge) nanocrystallites. It is shown the oxide related defect origin of the visible PL centers peaked at 1.7, 2.06 and 2.30 eV. The infrared PL band centered at 1.44–1.58 eV in Si–SiO_x, system has been analyzed within a quantum confinement PL model. Comparative PL investigation of Ge–SiO_x system has confirmed that high energy visible PL bands (1.60–1.70 and 2.30 eV) are connected with oxide related defects in SiO_x. The PL band in the spectral range of 0.75–0.85 eV in Ge–SiO_x system is attributed to exciton recombination inside of Ge NCs.     

Composition of Ge+ and Si+ implanted SiO2/Si layers: Role of oxides in nanocluster formation

X-ray photoelectron spectroscopy (XPS) has been used to examine the atomic content of implanted SiO₂/Si layers. In particular, an XPS analysis permits to identify elemental Ge and Si, as well as GeO₂ precipitations in SiO₂ matrices. The XPS results reveal valuable information not only about the formation mechanism of Ge and Si nanoclusters but also on the annealing kinetics of SiO₂ whose properties are known to be significantly altered during the process of ion implantation and subsequent annealing. The composition of ion beam-modified SiO₂ layers strongly depends on the annealing temperature. With respect to germanium implanted samples a possibility of Ge nanocrystals formation appears at high (above 1000 °C) annealing temperatures. It has been shown that an intermediate step in the Ge oxide formation is necessary for the creation of Ge nanoclusters. Additionally, the presence of a subsurface zone GeO_x (about 100 nm thick) predicted in kinetic three-dimensional lattice simulations has been confirmed. In the case of Si⁺ implanted samples substoichiometric silicon oxide lines in the XPS spectra of a SiO₂ layer for all samples have been observed. No evidence of a line connected to the Si–Si bonding has been observed even at the highest annealing temperatures, at which only stoichiometric SiO₂ has been detected.     

Optical investigations of germanium nanoclusters – Rich SiO2 layers produced by ion beam synthesis

In this work, refractive index and extinction coefficient spectra of germanium nanoclusters – rich SiO₂ layers have been determined using variable angle spectroscopic ellipsometry (VASE) in the 250–1000 nm range. The samples were produced by Ge⁺ ion implantation into SiO₂ layers on Si substrates and subsequent annealing at temperatures from 700 to 1100 °C. It is known from previous investigations of similar samples that the Ge nanoclusterization process starts already at 800 °C and spherical Ge nanocrystallites 5–8 nm in diameter are observed in the SiO₂ layers after annealing for 1 h at even higher temperatures of 1000–1100 °C. Rutherford backscattering spectrometry (RBS) was employed to measure the Ge atom concentration depth profiles in the studied samples. The RBS results helped us choose realistic models for the VASE analysis which were necessary for a proper interpretation of the VASE data. It has been found that the refraction index value for the SiO₂/Si layer increases after Ge implantation. This effect can be explained by a defect-dependent compaction of ion-bombarded layers. A band’s tail in the extinction coefficient spectra for all the samples is observed which originates from a strong ultraviolet absorption band at 6.8 eV due to a Germanium Oxygen-Deficiency Center (GeODC) and/or a Ge-E’center in SiO₂. The annealing process results in the emergence of weaker extinction coefficient bands in the 400–600 nm region, associated with direct band-to-band transitions in Ge nanostructures. Transformation of these bands, including their blue-shift with the increasing annealing temperature could be explained via a quantum-confinement mechanism, by size and structural changes in Ge nanostructures.     

Network structure of multi-component sodium borosilicate glasses by neutron diffraction

Neutron diffraction structure study has been performed on multi-component sodium borosilicate based waste glasses with the composition of (65 − x)SiO_2. · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂, x = 5–15 mol%. The maximum momentum transfer of the experimental structure factor was 30 Å⁻¹, which made available to determine the distribution function with high r-space resolution. Reverse Monte Carlo modelling was applied to calculate several partial atomic pair correlation functions, nearest neighbor distances and coordination numbers have been revealed. The characteristic features of Si–O and Si–Si distributions are similar for all glassy samples, suggesting that the Si–O network consisting of tetrahedral SiO₄ units is highly stable even in the multi-component glasses. The B–O correlations proved to be fairly complex, two distinct first neighbor distances are present at 1.40 Å and 1.60 Å, the latter equals the Si–O distance. Coordination number distribution analyzes has revealed 3 and four-coordinated boron atoms. The O–O distribution suggests a network configuration consisting of boron rich and silicon rich regions. Our findings are consistent with a structure model where the boron rich network contains mostly trigonal BO₃ units, and the silicon rich network is formed by a mixed continuous network of ^[4]Si–O–Si^[4] with several different ^[4]B–O–Si^[4] and ^[3]B–O–Si^[4] linkages.     

Structural,electrical and optical properties of in-situ phosphorous-doped Ge layers

We have studied the impact of temperature and pressure on the structural and electronic properties of Ge:P layers grown with GeH₄+PH₃ on thick Ge buffers, themselves on Si(0 0 1). The maximum phosphorous atomic concentration [P] exponentially decreased as the growth temperature increased, irrespective of pressure (20 Torr, 100 Torr or 250 Torr). The highest values were however achieved at 100 Torr (3.6×10²⁰ cm^?3 at 400 °C, 2.5×10¹⁹ cm^?3 at 600 °C and 10¹⁹ cm^?3 at 750 °C). P atomic depth profiles, “box-like” at 400 °C, became trapezoidal at 600 °C and 750 °C, most likely because of surface segregation. The increase at 100 Torr of [P] with the PH₃ mass-flow, almost linear at 400 °C, saturated quite rapidly at much lower values at 600 °C and 750 °C. Adding PH₃ had however almost no impact on the Ge growth rate (be it at 400 °C or 750 °C). A growth temperature of 400 °C yielded Ge:P layers tensily-strained on the Ge buffers underneath, with a very high concentration of substitutional P atoms (5.4×10²⁰ cm^?3). Such layers were however rough and of rather low crystalline quality in X-ray Diffraction. Ge:P layers grown at 600 °C and 750 °C had the same lattice parameter and smooth surface morphology as the Ge:B buffers underneath, most likely because of lower P atomic concentrations (2.5×10¹⁹ cm^?3 and 10¹⁹ cm^?3, respectively). Four point probe measurements showed that almost all P atoms were electrically active at 600 °C and 750 °C (1/4th at 400 °C). Finally, room temperature photoluminescence measurements confirmed that high temperature Ge:P layers were of high optical quality, with a direct bandgap peak either slightly less intense (750 °C) or more intense (600 °C) than similar thickness intrinsic Ge layers. In contrast, highly phosphorous-doped Ge layers grown at 400 °C were of poor optical quality, in line with structural and electrical results.     

Growth optimization and characterization of lattice-matched Al0.82In0.18N optical confinement layer for edge emitting nitride laser diodes

We present the growth optimization and the doping by the metal organic chemical vapor deposition of lattice-matched Al_0.82In_0.18N bottom optical confinement layers for edge emitting laser diodes. Due to the increasing size and density of V-shaped defects in Al_1?xIn_xN with increasing thickness, we have designed an Al_1?xIn_xN/GaN multilayer structure by optimizing the growth and thickness of the GaN interlayer. The Al_1?xIn_xN and GaN interlayers in the multilayer structure were both doped using the same SiH₄ flow, while the Si levels in both layers were found to be significantly different by SIMS. The optimized 8×(Al_0.82In_0.18N/GaN=54/6 nm) multilayer structures grown on free-standing GaN substrates were characterized by high resolution X-ray diffraction, atomic force microscopy and transmission electron microscopy, along with the in-situ measurements of stress evolution during growth. Finally, lasing was obtained from the UV (394 nm) to blue (436 nm) wavelengths, in electrically injected, edge-emitting, cleaved-facet laser diodes with 480 nm thick Si-doped Al_1?xIn_xN/GaN multilayers as bottom waveguide claddings.     

Microcrystalline silicon–germanium alloys for solar cell application: Growth and material properties

Microcrystalline silicon–germanium (μc-Si_1−xGe_x:H) alloy films have been grown by 100-MHz glow-discharge of a SiH₄/GeH₄/H₂ gas mixture. Alloys over a full range of compositions were prepared to gain a comprehensive understanding of their growth and material properties. With increasing GeH₄ concentration in the gas-phase, we observed a preferential Ge incorporation behavior in the solid. Growth rate studies revealed that the Ge incorporation efficiency from source gas to solid is about five times greater than for Si at growth temperature of 200 °C, which accounts for the variation of alloy composition. With increasing Ge incorporation in the solid, on the other hand, we find a monotonic decrease in photoconductivity, followed by an electrical transition from weak n-type to strong p-type conduction at x > 0.7. At x ≈ 0.4, however, we obtained relatively high photoconductivity gains by a factor of 20 and strong infrared response in the solar cell structure. The Ge incorporation behavior and its effect on charge carrier transport are discussed.     

Electron spin resonance study of hydrogenated microcrystalline silicon–germanium alloy thin films

Paramagnetic defects of undoped hydrogenated microcrystalline silicon–germanium alloys (μc-Si_1?xGe_x:H) grown by low temperature (200 °C) plasma-enhanced chemical vapor desposition (PECVD) have been measured by electron spin resonance (ESR) and compared with those of hydrogenated amorphous silicon–germanium (a-Si_1?xGe_x:H). The spin density of μc-Si_1?xGe_x:H increases with Ge content and shows a broad maximum of ～10¹⁷ cm^?3 at x ～ 0.5, which reasonably accounts for the decreased photoconductivity. While the Ge dangling bond defects prevail in a-Si_1?xGe_x:H for Ge-rich compositions, we detected no ESR signal in μc-Si_1?xGe_x:H for x > 0.75 where an electrical change occurs from weak n- to strong p-type conduction. These results indicate that dangling bonds are charged in large densities due to the presence of the acceptor-like states in undoped μc-Si_1?xGe_x:H.     

Organometallic vapor phase epitaxy growth of upright metamorphic multijunction solar cells

We demonstrate an integrated metamorphic AlGaInP/AlGaInAs/GaInAs/Ge 4 J solar cell on Ge substrate using organometallic vapor phase epitaxy (OMVPE). A step graded GaInAs buffer was grown right after the Ge subcell was formed to change the lattice constant from that of Ge to that of Ga_0.8In_0.2As lattice constant followed by a 1.14 eV Ga_0.8In_0.2As subcell, a 1.5 eV (AlGa)_0.8In_0.2As subcell, and a 1.85 eV Al_xGa_0.32?xIn_0.68P subcell. Transmission electron microscope (TEM) study shows the threading dislocation density (TDD) is about 6×10⁶ cm^?2. The X-ray diffraction reciprocal space map (RSM) shows that the structure is 100% relaxed. Bandgap dependent (Al_xGa_1?x)_0.32In_0.68P subcell performance is systematically investigated. As the Al_xGa_0.32?xIn_0.68P cell bandgap goes up to 1.9 eV, the external quantum efficiency (EQE) goes down significantly. Theoretical simulation shows that the decrease of diffusion length causes the lower EQE, which indicates the material quality degrades with the increasing Al content. Integrated 4 J solar cells are fabricated and characterized with spectral response and tested under the AM1.5D terrestrial spectrum at both 1 sun and 2000 suns.     

A combined 77Se NMR and Raman spectroscopic study of the structure of GexSe1-x glasses: Towards a self consistent structural model

The short-range structures of stoichiometric and Se-deficient binary Ge_xSe_100 ?x glasses with 42 ≥ x ≥ 33.33 have been investigated using a combination of Raman and ⁷⁷Se Car–Purcell–Meiboom–Gill (CPMG) spikelet nuclear magnetic resonance (NMR) spectroscopy. When taken together, these spectroscopic results allow for self-consistent assignment of average ⁷⁷Se NMR isotropic chemical shifts to Se atoms in various coordination environments in Ge_xSe_100 ?x glasses. Analysis of the compositional variation of the relative concentrations of these Se environments indicates considerable violation of chemical order in the nearest-neighbor coordination environments of the constituent atoms in the stoichiometric Ge_33.33Se_66.67 glass. On the other hand, the presence of a random distribution of Ge―Ge bonds can be inferred in the Se-deficient glasses. Simulations of the previously published ⁷⁷Se NMR line shapes of Se-excess glasses on the basis of the revised structural assignments of ⁷⁷Se NMR chemical shifts obtained in this study conclusively indicate that the structure of these glasses is intermediate between a randomly connected and a fully clustered network of GeSe₄ tetrahedra and Se chains.     

Effect of germanium on the microstructure and the magnetic properties of Fe–B–Si amorphous alloys

In this work, we present a systematic study on the crystallization kinetics and the magnetic properties of melt-spun Fe₈₀B₁₀Si_10 ? xGe_x (x = 0.0 ? 10.0) amorphous alloys. The activation energy for crystallization, determined by differential scanning calorimetry, displayed a strong dependence on the Ge content, reflecting a deleterious effect on the alloys' thermal stability and their glass forming ability with increasing Ge concentration. On the other hand, the alloys exhibited excellent soft magnetic properties, i.e., high saturation magnetization values (around 1.60 T), alongside Curie temperatures of up to 600 K. Complementary, for increasing Ge substitution, the ferromagnetic resonance spectra showed a microstructural evolution comprising at least two different magnetic phases corresponding to a majority amorphous matrix and to Fe(Si, Ge) nanocrystallites for x ≥ 7.5.     

Germanosilicate and alkali germanosilicate glass structure: New insights from high-resolution oxygen-17 NMR

We present here triple-quantum, magic-angle spinning (3QMAS) NMR spectra for ¹⁷O in a SiO₂–GeO₂ binary glass, and for two sodium germanosilicate glasses, all with Si/Ge ratios of 1. In the binary germanosilicate, three NMR peaks are partially resolved, and correspond to the three types of bridging oxygens, Si–O–Si, Si–O–Ge, and Ge–O–Ge. Peak areas indicate that the relative abundances of these species are close to those expected for random mixing of the Si and Ge in the network. In a sodium germanosilicate glass with a relatively low Na content (Na₂O ≈ 8 mol%), the spectra demonstrate the formation of significant fractions of both nonbridging oxygens bonded to Si, and of oxygens bonded to Ge in five- or six-coordination. At higher Na content (Na₂O ≈ 31%), most or all Ge is four-coordinated and network modification is dominated by the formation of NBO on Si and on Ge. Models of physical properties of alkali germanosilicates, in which modifier oxides are distributed between the Si and Ge components of the network in proportion to the Si/Ge ratio, are thus supported, as is extensive mixing of Si and Ge.     

Enhanced spectral response by silicon nitride index matching layer in amorphous silicon thin-film solar cells

We employed the low temperature hydrogenated amorphous silicon nitride (a-SiN_x:H) prepared by plasma-enhanced chemical vapor deposition as a refractive index (n) matching layers in a silicon-based thin-film solar cell between glass (n = 1.5) and the transparent conducting oxide (n = 2). By varying the stoichiometry, refractive index and thickness of the a-SiN_x:H layers, we enhanced the spectral response and efficiency of the hydrogenated amorphous silicon thin-film solar cells. The refractive index of a-SiN_x:H was reduced from 2.32 to 1.78. Optimizing the a-SiN_x:H thickness to 80 nm increased the J_SC from 8.3 to 9.8 mA/cm² and the corresponding cell efficiency increased from 4.5 to 5.3%, as compared to the cell without the a-SiN_x:H index-matching layer on planar substrate. The a-SiN_x:H layers with graded refractive indices were effective for enhancing the cell performance.     

Crystallization of barium magnesium phosphate glasses determined by differential thermal analysis and X-rays diffraction

The scope of this work is to determine the crystalline phases of devitrified barium magnesium phosphate glasses and the glass composition which presents the best resistance to crystallization. Barium magnesium phosphate glasses with composition xMgO · (1 ? x)(60P₂O₅ · 40BaO) mol% (x = 0, 0.15, 0.3, 0.4, 0.5, and 0.6) were analyzed by differential thermal analysis (DTA) to evaluate the thermal stability against crystallization, and X-ray diffraction (XRD) to identify the crystalline phases formed after devitrification. The glass transition temperature (T_g) increases as the MgO content increases. The maximum temperature attributed to the crystallization peak in the DTA curve (T_c) increases when x increases in the range 0 ? x ? 0.3, and it decreases for x > 0.3. The most thermally stable glass composition against crystallization is for x = 0.3. After the devitrification, the number of coexisting crystalline phases increases as the MgO content increases. For x = 0.3 there is the coexistence of γBa(PO₃)₂ and Ba₂MgP₄O₁₃ phases for devitrified glasses. The trend of the T_c is explained based on the assumptions of changes in the Mg²⁺ coordination number and the amphoterical features of MgO.     

Topology and chemical order in AsxGexSe1 − 2x glasses: A high-resolution X-ray photoelectron spectroscopy study

The evolution of topology and chemical order along the As_xGe_xSe_1 ? 2x composition-line within the As–Ge–Se glass-forming region is studied by high-resolution X-ray photoelectron spectroscopy. It is shown that cation–cation bond formation becomes a dominant process for the compositions with x > 0.09. The results explain the peculiarities observed around this composition recently in the temperature-modulated differential scanning calorimetry data. Substitution of two selenium atoms within constituent structural units (pyramids and/or tetrahedra) by corresponding cations explains a second peculiarity point at x > 0.16 compositions observed recently with the above technique. The present observations show segregation of As and then Ge at high concentrations of cations in the system (x > 0.20).     

Properties of high nitrogen content mixed alkali earth oxynitride glasses (AExCa1−x)1.2(1)SiO1.9(1)N0.86(6), AE = Mg,Sr, Ba

Mixed alkali earth element containing high nitrogen content oxynitride glasses (Ca_1?xAE_x)_1.2(1)SiO_1.9(1)N_0.86(6), with AE = Mg, Sr, Ba, x ≤ 0.30 for Mg and x ≤ 0.46 for Sr and Ba, and nominally constant (Ca/AE):Si:O:N ratios were prepared in order to investigate the compositional dependencies of physical properties on alkali earth element composition. The glasses were prepared by melting mixtures of AEH₂, CaH₂, SiO₂ and Si₃N₄ powders in nitrogen atmosphere at 1600–1700 °C and characterized by X-ray powder diffraction and scanning and transmission electron microscopy. Cation and anion glass compositions were determined by respectively energy dispersive X-ray analysis and combustion analysis. The determined physical properties were density, glass transition temperature, Vickers hardness, and refractive index. The physical properties were found to vary linearly with the degree of substitution of Ca by the AE elements. The density of the glasses increases substantially upon substitution by Sr and Ba, up to 3.99 g/cm³. Glass transition temperatures are found to be higher for Mg and Sr substituted glasses, ca. 900 °C, in comparison with Ba substituted glasses, ca. 850 °C. The hardness increases upon substitution by Mg, up to 12.2 GPa at x = 0.46, and decreases upon substitution by Sr and Ba. The refractive index increases upon substitution by Sr and Ba, up to 1.97 for Ba at x = 0.46, and decreases upon substitution by Mg. The transparency of the glasses was found to increase upon increasing substitution by Mg and completely transparent glasses were obtained for x = 0.24.     

X-ray photoelectron spectroscopy of erbium-activated-silica–hafnia waveguides

X-ray photoelectron spectroscopy (XPS) has been used in the study of sol gel-derived Er³⁺-activated xHfO₂–(100 − x)SiO₂ (x = 10, 20, 30, 40, 50 mol) planar waveguides. The analysis of Si 2p and O 1s core lines were related to the Hf/Si molar ratio to assess the role of hafnia in modifying the silica network. Increasing the HfO₂ content brings about a change of the Si 2p and O 1s binding energy respect to those from pure silica. This trend is explained with a formation of hafnium silicate in the matrix with successive phase separation between HfO₂ and SiO₂ rich phases. XPS results show that hafnia is well dispersed in the silica matrix for molar concentration below 30%. Formation of pure HfO₂ domains was detected at higher hafnia concentrations in agreement with previous spectroscopic analyses.     

Bulk glassy (Fe0.474Co0.474Nb0.052)100 − x(B0.8Si0.2)x alloys prepared using commercial raw materials

The alloy compositions have been optimized by modifying the B and Si contents in (Fe_0.474Co_0.474Nb_0.052)_100 ? x(B_0.8Si_0.2)_x alloy system with commercial materials. The thermal stability of the supercooled liquid improves with the increased B and Si contents from x = 22 to 28. The composition of the alloy with x = 26 is close to a eutectic point. By copper mold casting, (Fe_0.474Co_0.474Nb_0.052)_100 ? x(B_0.8Si_0.2)_x bulk glassy alloys with diameters up to 5 mm were synthesized for the composition range of x from 22 to 28. In addition to high glass-forming ability (GFA), the (Fe_0.474Co_0.474Nb_0.052)_100 ? x(B_0.8Si_0.2)_x glassy alloys exhibit good soft magnetic properties as well, i.e., rather high saturation magnetization of 0.84–1.07 T, low coercive field of 1.8–3.2 A/m, high initial permeability of 10100–24100 at 1 kHz under a field of 1 A/m and Curie temperature of 620–730 K.     

Monte Carlo simulations of the dissolution of borosilicate glasses in near-equilibrium conditions

Monte Carlo simulations were performed to investigate the mechanisms of glass dissolution as equilibrium conditions are approached in both static and flow-through conditions. The glasses studied are borosilicate glasses in the compositional range (80 ? x)% SiO₂ (10 + x / 2)% B₂O₃ (10 + x / 2)% Na₂O, where 5 < x < 30%. In static conditions, dissolution/condensation reactions lead to the formation, for all compositions studied, of a blocking layer composed of polymerized Si sites with principally 4 connections to nearest Si sites. This layer forms atop the altered glass layer and shows similar composition and density for all glass compositions considered. In flow-through conditions, three main dissolution regimes are observed: at high flow rates, the dissolving glass exhibits a thin alteration layer and congruent dissolution; at low flow rates, a blocking layer is formed as in static conditions but the simulations show that water can occasionally break through the blocking layer causing the corrosion process to resume; and, at intermediate flow rates, the glasses dissolve incongruently with an increasingly deepening altered layer. The simulation results suggest that, in geological disposal environments, small perturbations or slow flows could be enough to prevent the formation of a permanent blocking layer. Finally, a comparison between predictions of the linear rate law and the Monte Carlo simulation results indicates that, in flow-through conditions, the linear rate law is applicable at high flow rates and deviations from the linear rate law occur under low flow rates (e.g., at near-saturated conditions with respect to amorphous silica). This effect is associated with the complex dynamics of Si dissolution/condensation processes at the glass–water interface.