Ge Alloys Research Articles

First-principles study of magnetic disordering and alloying effects on phase stability and elastic constants of Co<sub>2</sub>Cr<i>Z</i> (<i>Z</i> = Ga, Si, Ge) alloys

Using the exact Muffin-Tin orbital method combined with the coherent potential approximation, the effects of magnetic disordering and alloying effects on the phase stability of L2<sub>1</sub>- and D0<sub>22</sub>-Co<sub>2</sub>Cr<i>Z</i> (<i>Z</i> = Ga, Si, Ge) alloys are systematically investigated at 0 K in the present work. It is shown that at 0 K, the lattice parameter, bulk modulus, magnetic moments, and elastic constants of the studied L2<sub>1</sub> alloys are in line with the available theoretical and experimental data. In the ferromagnetic state, these alloys possess L2<sub>1</sub> structure; with the magnetic disordering degree (<i>y</i>) increasing, the energy of the phase increases relatively and finally turns from lower than D0<sub>22</sub> phase to higher than D0<sub>22</sub> phase. As a result, when <i>y</i> ≥ 0.1 (0.2), then <i>Z</i> = Si and Ge (<i>Z</i> = Ga) alloys are stabilized by the D0<sub>22</sub> phase. With <i>y</i> increasing, the tetragonal shear elastic modulus (<i>C</i><i>'</i> = (<i>C</i><sub>11</sub>–<i>C</i><sub>12</sub>)/2) also turns soft, indicating that the magnetic disorderingis conducive to the lattice tetragonal deformation in the three alloys from both the energetic view and the mechanical view. The electronic origination of the magnetic disordering effect on the stabilities of the L2<sub>1</sub> and D0<sub>22</sub> phases can be ascribed to the Jahn-Teller instability effect. In the FM L2<sub>1</sub>-Co<sub>2</sub>CrGa<sub>1–<i>x</i></sub>Si<sub><i>x</i></sub> and L2<sub>1</sub>-Co<sub>2</sub>CrGa<sub>1–<i>x</i></sub>Ge<sub><i>x</i></sub> quaternary alloys, with <i>x</i> increasing, the total magnetic moment increases monotonically according to the Slater-Pauling rule, and <i>C</i><i>'</i> also stiffens, reflecting that the adding of Si and Ge can promote the mechanical stability of L2<sub>1</sub>-Co<sub>2</sub>CrGa alloy, thereby depressing the lattice tetragonal deformation.

Infrared analysis of catalytic CO2 reduction in hydrogenated germanium.

The oxidation and carbisation kinetics of porous amorphous and nano-crystalline hydrogenated germanium (a-Ge:H and nc-Ge:H) films exposed to ambient air and deionized water have been studied using vibration modes observed by infrared spectroscopy. Based on infrared analysis, a two-step process of first oxidation by water and secondly carbisation by carbon dioxide (CO2) is proposed that partly mimics the (photo-)catalytic processes in artificial (photo)synthesis. It is shown that water acts like the precursor for oxidation of porous a-Ge:H and nc-Ge:H in the first step. The incorporation of oxygen in a-Ge:H and nc-Ge:H alloys occurs preferentially at Ge-dangling bonds and not at the Ge–Ge back bonds like in hydrogenated silicon alloys (next of kin IV-valence element). The formation of germanium oxide (GeO) tissue at void surfaces locally creates Ge alloys with significantly lower energy levels for the valence band that can align with the half reaction for water reduction. The heterogeneous nature of a-Ge:H and nc-Ge:H oxidation will result in local catalytic generation of electrons and protons. It is proposed that these charge carriers and ions act as precursors for the second-step reaction based on carbisation that includes both the adsorption of CO2 and formation of CO and formaldehyde.

A review on single crystal and thin film Si–Ge alloy: growth and applications

Dual application of Si–Ge alloy in thermoelectric and BICMOS in the semiconductor industry.

Synergetic Enhancement of the Power Factor and Suppression of Lattice Thermal Conductivity via Electronic Structure Modification and Nanostructuring on a Ni- and B-Codoped p-Type Si–Ge Alloy for Thermoelectric Application

Synergetic Enhancement of the Power Factor and Suppression of Lattice Thermal Conductivity via Electronic Structure Modification and Nanostructuring on a Ni- and B-Codoped <i>p</i>-Type Si–Ge Alloy for Thermoelectric Application

Mathematical modeling of dendrite growth in an Al–Ge alloy with convective flow

A theory of stable dendrite growth in an undercooled binary melt is developed for the case of intense convection. Conductive heat and mass transfer boundary conditions are replaced by convective conditions, where the flux of heat (or solute) is proportional to the temperature or concentration difference between the surface of the dendrite and far from it. The marginal mode of perturbation wavelengths is calculated using the linear morphological stability analysis. Combining this analysis with the solvability theory, we have derived a selection criterion that represents the first condition to define a combination of dendrite tip velocity and tip diameter. The second condition—the undercooling balance—is derived for intense convection. The theory under consideration determines the dendrite tip velocity and tip diameter for low undercooling. This convective theory is combined with the classical theory of dendritic growth (conductive boundary conditions), which is valid for moderate and high undercooling. Thus, the entire range of melt undercooling is covered. Our results are in good agreement with experiments on Al–Ge crystallization.

Investigation on tribological behaviors of biodegradable pure Zn and Zn-X (Li, Cu, Ge) binary alloys

As a potential biodegradable implant material, zinc (Zn) alloys have attracted increasing attention due to their good biocompatibility and moderate degradation rate. Zn and its alloys are expected to become candidate materials for medical devices. The metals implanted in the human body will inevitably undergo friction in the human body before it is completely degraded. Friction and wear are essential factors which may cause medical devices’ service failure. However, there are still few studies on the friction and wear properties of biodegradable Zn-based alloys in the human body, and most studies just focus on the mechanical properties, degradation properties and biocompatibility of the alloys. Thus, it is crucial to study the friction and wear properties of Zn and its alloys. In the present work, we investigated the tribological properties of biodegradable pure Zn and Zn-X (Li, Cu, Ge) alloys. Our study found that under simulated body fluid and dry friction conditions, the addition of alloying elements Li and Cu can improve the friction properties of Zn. Among the four metals, Zn-0.5Li alloy has the lowest friction coefficient and the best wear resistance. Hank’s solution has lubricating and corrosive effects. That is to say, when the alloy is rubbed in Hank’s solution, it can not only be protected by the lubrication of the solution, but also tribocorrosion will occur as well.

Surface boundary-dendrite interactions in thin metallic Al-alloy samples

Crystallographic orientations and growth directions of dendrites in thin Al-15 wt.%Cu (200 µm) and Al-29 wt.%Ge (500 µm) alloys were investigated employing in situ X-radiography and post-mortem X-ray tomography and electron backscatter diffraction. The Al-Cu alloy was solidified under microgravity conditions, while the Al-Ge sample was processed horizontally on ground. It was found that (i) dendrites nucleate on both sides of the surface in microgravity, but accumulate under normal gravity near the top surface due to buoyancy, (ii) dendrites grow along preferred in-plane crystallographic directions, which are 〈100〉 for Al-15 wt.%Cu and 〈100〉, 〈110〉 and 〈210〉 for Al-29 wt.%Ge, indicating that the solid-liquid interfacial anisotropy of this Al-Ge composition is similar for these 〈xy0〉 directions, (iii) slightly inclined dendrite arms in Al-Cu grow along the sample boundary after contact, whereas tips of inclined dendrite arms in Al-Ge never touch the boundary, but develop new primary tips originating from secondary branches.

Study of structural, electronic and magnetic properties of Ti doped Co2FeGe Heusler alloy: Co2Fe1−x Ti x Ge (x = 0, 0.5, and 0.75)

Tunability of structural, magnetic and electronic properties of Co2FeGe Heusler alloy is experimentally demonstrated by doping Ti in the Fe site (i.e. Co2Fe1−x Ti x Ge), followed by in-depth first principle calculations. Co2FeGe in its pure phase shows very high saturation magnetization, Curie temperature and spin-wave stiffness constant which were reported in our earlier work. With gradual increase in Ti doping concentration (x = 0.5 and 0.75), the experimental saturation magnetization is found to be decreased to 4.3 μ B/f.u. and 3.1 μ B/f.u. respectively as compared to the parent alloy (x = 0) having the saturation magnetization of 6.1 μ B/f.u. Variation of spinwave stiffness constant is also studied for different x and found to be decreasing from peak value of 10.4 nm2 meV (for x = 0) to the least value of 2.56 nm2 meV for x = 0.5. Justification of the experimental results is given with first principle calculations. Computational phase diagram of the alloys is found in terms of formation energy showing that the doping in Fe site (i.e. Co2Fe1−x Ti x Ge) is more stable rather than in Co site (i.e. Co2−x FeTi x Ge). The change in magnetic moment and half-metallicity with Ti doping concentration is better explained under GGA + U approach as compared to GGA approach signifying that the electron–electron correlation (U) has a distinct role to play in the alloys. Effect of variation of U for Ti atom is studied and optimized with reference to the experimental results. The dynamical stability of the Co2Fe1−x Ti x Ge alloy crystal structure is explained in terms of phonon dispersion relations and the effect of U on the phonon density of states is also explored. Close agreement between the experimental and theoretical results is observed.

A Review of Self-Seeded Germanium Nanowires: Synthesis, Growth Mechanisms and Potential Applications.

Ge nanowires are playing a big role in the development of new functional microelectronic modules, such as gate-all-around field-effect transistor devices, on-chip lasers and photodetectors. The widely used three-phase bottom-up growth method utilising a foreign catalyst metal or metalloid is by far the most popular for Ge nanowire growth. However, to fully utilise the potential of Ge nanowires, it is important to explore and understand alternative and functional growth paradigms such as self-seeded nanowire growth, where nanowire growth is usually directed by the in situ-formed catalysts of the growth material, i.e., Ge in this case. Additionally, it is important to understand how the self-seeded nanowires can benefit the device application of nanomaterials as the additional metal seeding can influence electron and phonon transport, and the electronic band structure in the nanomaterials. Here, we review recent advances in the growth and application of self-seeded Ge and Ge-based binary alloy (GeSn) nanowires. Different fabrication methods for growing self-seeded Ge nanowires are delineated and correlated with metal seeded growth. This review also highlights the requirement and advantage of self-seeded growth approach for Ge nanomaterials in the potential applications in energy storage and nanoelectronic devices.

Theoretical investigation of ternary semiconductors half-Heusler RhTaZ (Z = Si, Ge and Sn) for thermoelectric applications

The structural, electronic, elastic, thermodynamic and thermoelectric properties of RhTaZ (Z = Si, Ge and Sn) half-Heusler materials have been studied using density functional theory. We have found that the compounds studied can be experimentally synthesized. Also, RhTaZ (Z = Si, Ge and Sn) alloys exhibit a semiconductor behavior following the Slater–Pauling rule. The elastic properties calculated confirm that our compounds are mechanically stable. Using Debye’s quasi-harmonic model, the thermodynamic properties of these half-Heusler alloys were investigated. For the study of thermoelectric properties, the semi-classical Boltzmann theory, as implemented in the BoltzTraP code, has been used. The high values obtained from the figure of merit for RhTaZ (Z = Si, Ge and Sn) compounds suggest that they are promising candidates for thermoelectric applications at low and high temperatures.

Si-capping-induced surface roughening on the strip structures of Ge selectively grown on an Si substrate

Si-capping-induced surface roughening, accompanying Si–Ge alloying, is reported for strip structures of Ge selectively grown on Si via ultrahigh vacuum chemical vapor deposition. A 0.7-μm-wide strip structure of Ge running in the [110] direction, as well as a 100-μm-wide mesa structure, is selectively grown on an Si (001) surface exposed in an SiO2-masked Si substrate. In contrast to a wide mesa structure with a Ge thickness of 0.5 μm, composed of a (001) plane at the top and {113} facet planes at the sidewalls, the (001) top plane almost disappears for the narrow strip structure. The strip is mainly surrounded with inclined {113} planes near the top and adjacent {111} planes at the side, while the structure near the bottom edges depends on the growth temperature (600/700 °C). An Si cap layer with a thickness of 10 nm or larger is subsequently grown at 600 °C to protect the fragile Ge surface. The scanning electron microscopy observations reveal a roughened surface on the {113} planes, with depressions specifically induced near the boundary with the {111} planes. The Raman spectra indicate that an SiGe alloy is formed on the strip and the wide mesa sidewalls due to the Si–Ge interdiffusion. There is no such SiGe alloy on the (001) plane of the wide mesa top. The Si cap layer with a misfit strain probably works as a stressor for the underlying Ge, applying stress concentrated around the facet boundaries and inducing a mass transport alongside the Si–Ge interdiffusion for strain relaxation. In terms of the fabrication of practical devices, it is important to suppress the roughening and alloying significantly by decreasing the growth temperature for the Si cap layer from 600 to 530 °C.

Phase Change Material of Copper–Germanium Alloy as Solar Latent Heat Storage at High Temperatures

A copper–germanium alloy (Cu–Ge alloy) was examined as a phase change material, at temperatures exceeding 600°C, for latent heat storage in solar thermal applications. First, the thermo-physical properties of the Cu–Ge alloy were examined using differential scanning calorimetry, thermomechanical analysis, and laser flash analysis. Second, to evaluate the thermal response and reliability of the Cu–Ge alloy, the cyclic properties of thermal charge/discharge were examined under various thermal conditions. The alloys obtained after the tests were examined for their chemical compatibility with the stainless steel container using an electron probe micro analyzer. The elemental distribution of each Cu–Ge alloy was evaluated using cyclic performance tests. Finally, the chemical compatibility of the Cu–Ge alloy was evaluated using a high-temperature test with candidate materials of a phase change material container vessel [stainless steel (SUS310S), Inconel625, silicon carbide (SiC), and alumina (Al2O3)]. The Cu–Ge alloy exhibited significant potential as a latent heat storage material in next-generation solar thermal power plants because it demonstrates various advantages, including a superior storage capacity at a temperature of 644°C, temperature coherence to the phase diagram, a quick thermal response, satisfactory cyclic behavior of charge/discharge modes, a thermodynamically stable metallographic structure, and non-reactivity with container ceramic materials (SiC and Al2O3).

Structure of levitated Si–Ge melts studied by high-energy x-ray diffraction in combination with reverse Monte Carlo simulations

The short-range order in liquid Si, Ge and binary Si x –Ge1−x alloys (x = 0.25, 0.50, 0.75) was studied by x-ray diffraction and reverse Monte Carlo simulations. Experiments were performed in the normal and supercooled liquid states by using the containerless technique of aerodynamic levitation with CO2 laser heating, enabling deeper supercooling of liquid Si and Si–Ge alloys than previously reported. The local atomic structure of liquid Si and Ge resembles the β-tin structure. The first coordination numbers of about 6 for all compositions are found to be independent of temperature indicating the supercooled liquids studied retain this high-density liquid (HDL) structure. However, there is evidence of developing local tetrahedral ordering, as manifested by a shoulder on the right side of the first peak in S(Q) which becomes more prominent with increasing supercooling. This result is potentially indicative of a continuous transition from the stable HDL β-tin (high pressure) phase, towards a metastable low-density liquid phase, reminiscent of the diamond (ambient pressure) structure.

Spontaneous shape transition of Mn x Ge1- x islands to long nanowires.

We report experimental evidence for a spontaneous shape transition, from regular islands to elongated nanowires, upon high-temperature annealing of a thin Mn wetting layer evaporated on Ge(111). We demonstrate that 4.5 monolayers is the critical thickness of the Mn layer, governing the shape transition to wires. A small change around this value modulates the geometry of the nanostructures. The Mn–Ge alloy nanowires are single-crystalline structures with homogeneous composition and uniform width along their length. The shape evolution towards nanowires occurs for islands with a mean size of ≃170 nm. The wires, up to ≃1.1 μm long, asymptotically tend to ≃80 nm of width. We found that tuning the annealing process allows one to extend the wire length up to ≃1.5 μm with a minor rise of the lateral size to ≃100 nm. The elongation process of the nanostructures is in agreement with a strain-driven shape transition mechanism proposed in the literature for other heteroepitaxial systems. Our study gives experimental evidence for the spontaneous formation of spatially uniform and compositionally homogeneous Mn-rich GeMn nanowires on Ge(111). The reliable and simple synthesis approach allows one to exploit the room-temperature ferromagnetic properties of the Mn–Ge alloy to design and fabricate novel nanodevices.

New p-type sp-based half-Heusler compounds LiBaX(X = Si, Ge) for spintronics and thermoelectricity via ab-initio calculations

We have investigated the structural, electronic, magnetic, elastic and thermoelectric properties of the sp-based half-Heusler LiBaX (X = Si and Ge) alloys using the full-potential linearized augmented plane wave method of density functional theory. Two approaches are employed to approximate the correlation-exchange potential, namely the generalized-gradient approximation and the modified Becke–Johnson. Both compounds free of transition metals are ferromagnetic, half metallic with a large spin-flip gaps which are appropriate for Spintronic applications. Their half-metallicity is preserved under large lattice constant and pressure change which make them promising candidates for spintronic devices. The transport properties reveal high figure of merit values making these compounds great thermoelectric candidates. Moreover, the studied half-Heuslers are mechanically stable and both of them exhibit negative formation energy and cohesion which indicate the possibility of synthesizing and stabilizing these cheap and available materials. Up to date, no experimental or theoretical studies have been carried out regarding LiBaSi, while for LiBaGe, thermoelectric properties have not been investigated yet.

Study of thermal properties and microstructure of the Ag–Ge alloys

Microstructure, phase transitions and thermal properties including thermal diffusivity and thermal conductivity of four Ag–Ge alloys with 20, 40, 60 and 80 at % of Ge were experimentally investigated in this study. Observation and analysis of the alloy microstructures and morphologies of (Ge) phase in the hypereutectic alloys were carried out using optical microscopy and scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM–EDS). Phase transitions of the alloys were studied using differential scanning calorimetry (DSC). Experimentally determined temperature of the eutectic reaction was 650.9 °C. The xenon flash method was used for thermal diffusivity measurements in the temperature range from 25 to 400 °C. Based on the measured values of thermal diffusivity, thermal conductivity of the solid Ag–Ge alloys was determined. It was found that both thermal diffusivity and thermal conductivity show a minimum at 20 at % Ge which is close to the eutectic composition. The obtained results were compared with the results of thermodynamic calculation and literature data, and a close agreement was observed.

Low-field induced topological Hall effect in chiral cubic Cr0.82Mn0.18Ge alloy

The topological Hall effect (THE) in general arises from the Berry phase acquired by conduction electrons moving in a noncoplanar spin textures such as skyrmions. In this paper, low-field induced THE is realized in a chiral-lattice B20-ordered Cr0.82Mn0.18Ge alloy. The maximum topological Hall resistivity of ρxyT ≈ −0.048 μΩ cm at T = 10 K is achieved under a low magnetic field of about μ0H = 0.04 T, which reaches up to ~20% of the anomalous Hall effect. Dip/peak anomalies are observed in the field dependence of AC-susceptibility, which indicates the field evolution of the topologically protected nontrivial spin textures. The results manifest that the Cr0.82Mn0.18Ge alloy should host skyrmions and pave the way for searching new skyrmions materials.

The carbon state in dilute germanium carbides

Conduction and valence band states for the highly mismatched alloy (HMA) Ge:C are projected onto Ge crystal states, Ge vacancy states, and Ge/C atomic orbitals, revealing that substitutional carbon not only creates a direct bandgap but also the new conduction band is optically active. Overlap integrals of the new Ge:C conduction band state with states from unperturbed Ge show that the new band cannot be attributed to any single Ge band but is a mixture of multiple Ge states. The Ge Γ conduction band valley state plays the largest single role, but L and X valley states collectively contribute a larger share than Γ due to the multiplicity of degenerate states. C sites structurally resemble uncharged vacancies in the Ge lattice, similar to Hjalmarson's model for other HMAs. C also perturbs the entire Ge band structure even at the deepest crystal core energy levels, particularly if staggered supercells are used to mimic a disordered alloy. Projection onto atomic sites shows a relatively weak localization compared with other HMAs, but it does show a strong anisotropy in probability distribution. L-valley conduction band states in Ge contribute to the conduction band minimum in Ge:C, but the optical transition strength in Ge:C remains within a factor of 2 of the direct gap transition in Ge.

Microstructural analysis and surface studies on Ag-Ge alloy coatings prepared by electrodeposition technique

Among the main characteristics of silver and its alloys, tarnish resistance as well as surface brightness is essential. Alloying these materials with germanium has been shown to have considerable potential in providing tarnish protection. However, studies regarding the electrodeposited silver-germanium (Ag–Ge) alloy coatings are limited. The main objective of this study is to investigate the electrodeposition process of Ag-Ge alloy coatings with different Ge contents. In this regard, co-electrodeposition of Ag and Ge as an alloy coating was performed on pure copper substrates from a cyanide-based electrolyte. The effect of Ge incorporation on alloy composition, surface morphology, topography, texture, crystalline structure and cathodic efficiency of the obtained electrodeposits was investigated. Also corrosion properties of coatings were perused by polarization curves. Evaluation of the coatings was performed using different characterization techniques including XPS, SEM, FESEM, EDS, XRD, AFM, ICP, GIXRD, XRF, FTIR and electrochemical analysis. Results indicated that the optimum content of Ge in the coating was found to be 6 wt% regarding dense and uniform microstructure along with the best corrosion resistance. In addition, the X-ray diffraction patterns exhibited a shift in lattice parameter of Ag that was attributed to the Ag-Ge biphasic alloy formation. Moreover, the surface studies revealed a morphological transformation from nodular to cauliflower-like by increasing the Ge content of coating. The obtained polarization curves represent a remarkable decrease in Ag-6Ge alloy corrosion current density, about 20 times compared to Ag-0.5Ge and about 6 to pure silver. Discrepancies in characteristics between the Ag-Ge and pure Ag coatings were addressed and discussed.

Novel high-performance anodic materials for lithium ion batteries: two-dimensional Sn-X (X = C, Si, and Ge) alloy monolayers.

Lithium-ion batteries (LIBs) have always been the focus of researchers for energy storage applications. Here, the first-principles density functional theory method was used to explore the possibility of using stanene derived structures as LIB anodes. And such two-dimensional structures are similar to graphene or stanene, but half of the Sn atoms are replaced by group-IV atoms to form new structures, which are called Sn-X (X = C, Si, and Ge). Our calculation results showed that the optimized structure, lattice constant and other parameters are consistent with those reported in previous studies. Meanwhile, we found out that the semiconductor properties of pristine Sn-X transform into metal properties after the adsorption of Li. Then, by calculating the adsorption concentration of Li ions on the Sn-X monolayers, we found that these kinds of materials can meet the requirements of battery anodes very well, not only in terms of their open-circuit voltage, but also storage capacity. For Sn-Si and Sn-Ge, their theoretical capacities can be as high as 1095.78 mA h g-1 (Li6Sn-Si) and 840.88 mA h g-1 (Li6Sn-Ge). At last, based on the investigation of their diffusion path, Sn-X has been found to have high charge and discharge rates because of its low barrier. By reason of the foregoing, 2D Sn-X monolayers will be excellent battery anodes.