Bi2Te3 Crystals Heavily Doped with Germanium Atoms

Elemental Bi, Te, and Ge of 5N purity were used to prepare Bi₂Te₃(GeTe) single crystals with germanium content varying from 0 up to 2.3 × 10²¹ cm⁻³. The samples were characterized by reflectivity measurements in the plasma resonance frequency range and by measurements of the electrical conductivity. Germanium content in the samples was determined by means of energy dispersive analysis. The reflectivity spectra were interpreted on the basis of the Drude-Zener theory in the aim to obtain information on the concentration of the free carriers in the samples. It was found that Ge atoms in the Be₂Te₃ crystal lattice behave as acceptors. A comparison of the hole concentration with the amount of germanium built into the crystal lattice revealed that only about 1/100 of the total number of Ge atoms act as acceptors. This effect is explained by two different ways of incorporation of Ge atoms into the Bi₂Te₃ lattice, viz: the formation of substitutional Ge'_Bi defects acting as acceptors and the formation of seven-layer-lamellae of the Te Bi Te Ge Te Bi Te composition, which corresponds to the structure of GeBi₂Te₄.     

Czochralski-growth of germanium crystals containing high concentrations of oxygen impurities

Oxygen-containing germanium (Ge) single crystals with low density of grown-in dislocations were grown by the Czochralski (CZ) technique from a Ge melt, both with and without a covering by boron oxide (B₂O₃) liquid. Interstitially dissolved oxygen concentrations in the crystals were determined by the absorption peak at 855 cm⁻¹ in the infrared absorption spectra at room temperature. It was found that oxygen concentration in a Ge crystal grown from melt partially or fully covered with B₂O₃ liquid was about 10¹⁶ cm⁻³ and was almost the same as that in a Ge crystal grown without B₂O₃. Oxygen concentration in a Ge crystal was enhanced to be greater than 10¹⁷ cm⁻³ by growing a crystal from a melt fully covered with B₂O₃; with the addition of germanium oxide powder, the maximum oxygen concentration achieved was 5.5×10¹⁷ cm⁻³. The effective segregation coefficients of oxygen in the present Ge crystal growth were roughly estimated to be between 1.0 and 1.4.     

Characterization of the structure of porous germanium layers by high-resolution X-ray diffractometry

The surface morphology and the structure of porous germanium layers obtained by chemical etching of n-type single-crystal Ge(111) substrates with their subsequent annealing in hydrogen atmosphere are studied by high-resolution X-ray diffractometry. It is established that upon etching a 1.5 to 2.0-μm-thick porous germanium layer is formed, which contains quasi-ordered microinhomogeneities in the form of elongated pits with characteristic dimensions of 1 μm and an average distance between them of 3–4 μm. The layer bulk has pores with radii ranging within 25–30 nm and nanocrystallites with an average size of 10 nm, with the average porosity being 56%.     

High temperature ESR study of Fe(III) in various vitreous matrices

The Raman spectra of binary high-silica glasses have been studied. The main peaks at 808 cm^?1 and 710 cm^?1 in vitreous B₂O₃ and vitreous P₂O₅, respectively, are greatly reduced in binary high-silica glass, whereas a peak at 425 cm^?1 due to GeOGe vibration and a peak at 1320 cm^?1 due to P = O vibration remain strong, increasing in intensity with decreasing SiO₂ concentration. In the stimulated Raman spectra of a P₂O₅-SiO₂ glass fiber pumped by a mode-locked and Q-switched Nd:YAG laser at 1.064 μm, strong Stokes emissions due to the P = O vibration have been observed at 1.24 μm and 1.48 μm. In the spectra for a GeO₂-SiO₂ glass fiber, four narrow-width Stokes emissions due to the GeOGe vibration have been observed at 1.115, 1.172, 1.235 and 1.305 μm.     

Methods for measuring light scattering in germanium and paratellurite crystals

Methods for studying the scattered light in germanium and paratellurite (α-TeO₂) crystals are considered. Investigations of the light scattering in Ge crystals were performed in the infrared wavelength range by the photometric-sphere method (in the range 2–3 μm) and by measuring the line-scattering functions (at 10.6 μm). In the visible range, the paratellurite single crystals were investigated by recording and analyzing images of laser beams transmitted through the samples. It is shown that small-angle Mie scattering is characteristic of both materials. Some conclusions about the sizes and the physical nature of scattering inhomogeneities are drawn. The effect of high-temperature annealing on the scattering intensity is studied.     

Microcrystalline silicon–germanium thin films prepared by the chemical transport process using hydrogen radicals

We propose microcrystalline silicon–germanium (μc-SiGe) as a bottom cell material of triple-junction solar cells in order to improve the conversion efficiency of thin film solar cells. The μc-SiGe thin films were prepared by the chemical transport process using Si and Ge targets exposed to hydrogen radicals. We successfully produced highly photosensitive μc-SiGe films with relatively low Ge composition by increasing the gas pressure, and observed the photovoltaic effect in pin solar cell structures. However, it was difficult to produce μc-SiGe films with higher Ge composition. We found that a small amount of argon introduction into the chemical transport process enables us to increase Ge composition at the high pressure. Moreover, the argon introduction seems effective to maintain the electrical properties in relatively high Ge composition. The results suggest that the μc-SiGe thin films prepared by the chemical transport process are one of the candidates for new photovoltaic materials.     

Preparation of Ge-Si epitaxial alloys by sputtering

Ge-Si alloy layers have been epitaxially grown throughout the whole range of composition onto Ge substrates by the simultaneous getter sputtering from elemental Ge and Si sources. The epitaxial temperature was 550 to 830° C at growth rates of about 1 μm/h, depending on the Si atomic fraction in the range of 0.05 to 0.88. As the Si content in the alloy increases, the crystallinity of the layer decreases: Si-rich alloy layers contained microtwins. Hall measurements of alloy layers without intentional doping indicated p-type conductivity with Hall mobility of 600 cm²/V·sec at carrier concentration of 2 × 10¹⁶ cm^-3 for 25 at% Si in the alloy at room temperature. The observed temperature dependence of the hole mobility is indicative of alloy scattering.     

High resolution patterning of silica aerogels

Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag⁺ ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 × 70 μm, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed by Ag clusters with a size of several μm, separated by thin layers of silica.     

Modeling the distribution of Ga and Sb impurities in Ge‒Si single crystals grown by double feeding of the melt: Growth conditions for homogeneous single crystals

Mathematical modeling of the distribution of Ga and Sb impurities in homogeneous (with respect to the content of the main components) single crystals of Ge–Si alloys, grown by double feeding of the melt, has been performed in the Pfann approximation. It is shown that the axial gradient of impurity concentration in Ge–Si crystals can be controlled in wide limits by changing the ratio of crystallization rate and the rates of feeding of the melt by silicon and germanium rods. The conditions for growing alloy single crystals, homogeneous both with respect to the content of the main components and to the impurity concentration distribution, have been determined.     

Infrared absorption of some high-purity chalcogenide glasses

New compouning techniques were devised to prepare high-purity Ge₂₈Sb₁₂Se₆₀ (TI 1173)and Ge₃₃As₁₂Se₅₅ TI 20). The methods were based on the combination of the reactant purification and compounding steps. The goal of the program was to establish the absorption limit for the glasses and to lower the absorption at 10.6 μm. At the present purity level, the GeSbSe glass is found to have an absorption level of about 0.01 cm^?1 at 10.6 μm while the absorption level for the GeAsSe glass is 0.05 cm^?1. Underlying causes for the limits are discussed along with the possibilities for improvement.     

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.     

Refractive index of chalcogenide glasses over a wide range of compositions

The refractive index frequency dependence in the 1–11 μm range for AsSe, GeSe and AsGeSe glassforming systems and for three- and four-component systems obtained by substitution of antimony, bismuth, tin, lead, sulphur and tellurium for arsenic, germanium and selenium, being their periodic system counterparts, is investigated. A comparison of optical constants of chalcogenide glasses with those for other optical materials by means of constructing of an Abbe-type diagram in n_2.0 ? v_2.0 coordinates is considered. The possibility of chalcogenide glass refraction calculation by means of additive formulas is discussed. It is shown that critical points on the property-composition curves coincide with structural region boundaries in all of the investigated systems. These data are considered as further experimental support for the polymer nature of chalcogenide glasses.     

Ga segregation during Czochralski-Si crystal growth with Ge codoping

The segregation of Ga during the growth of Czochralski-Si crystals with Ge codoping was investigated. The effective segregation coefficient of Ga in Ga/Ge-codoped Si crystal growth was nearly constant over a wide Ge concentration range, even at high Ge concentrations of about 10²¹ cm⁻³. In contrast, the effective segregation coefficient increased at high B concentrations in Ga/B-codoped CZ-Si crystal growth. The segregation behavior of Ga in Ga/Ge- and Ga/B-codoped CZ-Si crystal growth was theoretically compared. The difference in the segregation coefficients of Ga as a function of the codoped impurity (Ge or B) between the two Si crystals was attributed to a difference in the excess enthalpy due to impurity incorporation into the Si crystal between Ga–Ge pairs and Ga–B pairs     

Characterization of a Czochralski grown silicon crystal doped with 1020 cm‐3 germanium

A dislocation‐free silicon single crystal doped with 10²⁰ cm^‐3 germanium (Ge) has been grown using the Czochralski (CZ) growth technique. The Ge concentration in the seed‐end and tang‐end of the crystal was 8×10¹⁹cm^‐3and 1.6×10²⁰ cm^‐3, respectively. The effective segregation coefficient of Ge, the distribution of flow pattern defects (FPDs) and the wafer warpage have been characterized. Both the effective segregation coefficient and the equilibrium segregation coefficient of Ge in silicon were evaluated. Then, the density of FPDs was traced from seed‐end to tang‐end of the ingot, a suppression of FPDs by Ge doping was shown. That is probably because the Ge atoms consume free vacancies and thus a higher density of smaller voids is formed. Furthermore, the mechanical strength of wafers has also been characterized by batch warpage analysis. The warpage in the seed‐end was larger than that in the tang‐end of the ingot, showing that the mechanical strength of wafers is enhanced by Ge doping. Such improvement is interpreted by an enhanced dislocation pinning effect associated with the enhanced nucleation of grown‐in oxygen precipitates in the Ge‐doped silicon wafers. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dichroism and birefringence of natural violet diamond crystals

Investigation of the optical properties of natural violet diamonds from the Yakutian kimberlites is performed. A red shift of the absorption edge is revealed in the absorption spectra of these crystals. This shift is indicative of the presence of a high concentration of nitrogen in the diamonds studied. Along with the strong band at 0.550 μm, weaker bands at 0.390, 0.456 and 0.496 μm are revealed. It is shown that violet diamond crystals have birefringence and dichroism of about 10^?5 and 10^?6, respectively. When a light beam propagates perpendicularly to colored lamellas, the dichroism is much larger and the birefringence is smaller than in the case where the beam direction is parallel to lamellas.     

Paramagnetic germanium-related centers induced by energetic radiation in optical fibers and preforms

We investigated the creation processes of Ge-related paramagnetic point defects in silica fibers and preforms, doped with different amounts of germanium, and X-ray irradiated at several radiation doses. Different paramagnetic defect species, like GeE′, Ge(1) and Ge(2), were revealed by electron paramagnetic resonance measurements and their concentration was studied as a function of the irradiation dose. The comparison with the optical absorption spectra points out the main role of Ge(1) on the optical transmission loss of fibers in the UV region.     

Local structure around phosphorus and silicon in the CaO–SiO2–PO2.5 system

The local structure of phosphorus and silicon in the molten CaO–SiO₂–PO_2.5 slag system was investigated by magic angle spinning nuclear magnetic resonance (MAS-NMR). The ³¹P MAS-NMR spectra revealed that phosphorus was present primarily as the monophosphate complex ion PO₄^3?, with a small amount of diphosphate ion also present. Their relative ratio to total phosphorus was independent of the phosphate concentration of the sample. In the case of the ²⁹Si MAS-NMR, the mean number of the non-bridging oxygen atoms associated with tetrahedrally coordinated silicon decreased as the phosphate concentration increased at a fixed CaO/SiO₂ ratio. This indicates that the nonbridging oxygen atoms around the silicon were replaced by bridging oxygen atoms around the phosphorus as the phosphate concentration in the samples increased.To elucidate the basicity dependence of the structure of slag, the relationship between the structure and optical basicity was also investigated. The relative ratio of Qⁿ (Qⁿ means the silicon atoms tetrahedrally bonded with “n” number of bridging oxygen atoms) strongly depends on the optical basicity. These optical basicity dependencies of the structures of phosphorus and silicon can be explained clearly by the basicity equalization concept (Duffy and Ingram, 1976) [12].     

The possibility of identifying the spatial location of single dislocations by topo-tomography on laboratory setups

The spatial arrangement of single linear defects in a Si single crystal (input surface {111}) has been investigated by X-ray topo-tomography using laboratory X-ray sources. The experimental technique and the procedure of reconstructing a 3D image of dislocation half-loops near the Si crystal surface are described. The sizes of observed linear defects with a spatial resolution of about 10 μm are estimated.     

Growth kinetics and boron doping of very high Ge content SiGe for source/drain engineering

We have studied the in-situ boron doping of high Ge content Si_1?xGe_x layers (x=0.3, 0.4 and 0.5). These layers have been grown at low pressure (20 Torr) and low temperature (600–650 °C) with a heavily chlorinated chemistry on blanket Si(0 0 1) substrates. Such a chemistry yields a full selectivity versus SiO₂ (isolation) and Si₃N₄ (sidewall spacers) on patterned wafers with gate stacks. We have quantified the impact of the diborane flow on the SiGe layer crystalline quality, its resistivity, the SiGe:B growth rate and the apparent Ge concentration. Resistivity values lower than 1 mΩ cm are easily achieved, all the more so for high Ge content layers. The SiGe growth rate increases and the apparent Ge concentration (from X-ray diffraction) decreases as the diborane flow increases. B atoms (much smaller than Si or Ge) indeed partially compensate the compressive strain in the SiGe:B layers. We have also probed the in-situ boron and phosphorus doping of Si at 750 °C, 20 Torr with a heavily chlorinated chemistry. The B ions concentration increases linearly with the diborane flow, then saturates at a value close to 4×10¹⁹ cm^?3. By contrast, the P ions concentration increases sub-linearly with the phosphine flow, with a maximum value close to 9×10¹⁸ cm^?3. Adding diborane (phosphine) to the gaseous mixture leads to a sharp increase (decrease) of the Si:B (the Si:P) growth rates, which has to be taken into account in device layers. All the know-how acquired will be most handy for the formation of in-situ doped recessed or raised sources and drains in metal-oxide semiconductor devices.     

Sodium germanate glasses and crystals: NMR constraints on variation in structure with composition

We present new results from high-resolution ¹⁷O and ²³Na NMR spectroscopy on sodium germanate glasses ranging from 4 to 36 mol% Na₂O, and on crystalline sodium digermanate (Na₂Ge₂O₅). Combined with previously published results, these provide a more complete, direct view of changes in oxygen speciation with composition, and the corresponding changes in Ge coordination. Until about 15–20% Na₂O, non-bridging oxygens are not detected (<2% of oxygens). At higher Na contents, NBO begin to form in significant quantities and, by 36% Na₂O, are at the level expected for a ‘silicate-like’ speciation reaction, with all four-coordinated Ge (^[4]Ge). At intermediate compositions, a clear NMR signal is seen for oxygens bridging between one ^[4]Ge and one ^[5]Ge or ^[6]Ge. Estimated mean Ge coordination numbers are consistent with previous X-ray and neutron scattering results. We observe systematic, monotonic changes in the NMR parameters for both Na⁺ cations and ^[4]Ge–O–^[4]Ge bridging oxygens, suggesting a lack of clustering. This behavior is analogous to that of alkali borate glasses, where network cation coordination is well-known to shift with composition, but is quite distinct from that of alkali silicates, where coordination changes are large only at high pressures.