Germanium Atoms Research Articles

X-RAY SPECTROSCOPY OF SILICON DOPED WITH GERMANIUM ATOMS

This paper presents X-ray diffraction results of p-Si doped with germanium and tin atoms. It was found that after heat treatment of the initial silicon sample at a temperature of 1100°C, a new energetically favorable direction of crystallites appears. It was determined that germanium and silicon atoms form bonds in high-potential regions of the silicon crystal lattice and this leads to a deterioration in its monocrystallinity, that is, to an increase in the number of polycrystalline regions. It has been discovered that tin atoms in silicon combine with oxygen atoms and form SnO2 crystallites in the crystal lattice and this leads to an improvement in the monocrystallinity of silicon.

Facile synthesis of GexSiO(1-x) alloys as a superior anode enables high-energy lithium-ion batteries

The large-scale development of low-cost silicon monoxide (SiO) anode is limited due to its low initial Coulombic efficiency (ICE) and poor cycle stability. Herein, the GexSiO(1-x) (0<x<1) composite anode has been facile synthesized by introducing germanium (Ge) atoms disrupted the structure of SiO matrix, which exhibits superior lithium storage performance. In particular, the optimized Ge0.5SiO0.5 electrode with nanoscale dispersion shows a high ICE of 80.2 % and a reversible capacity of 673.9 mAh g−1 after 100 cycles. To evaluate the effect of the Ge addition on the electrochemical properties, the lithium storage behaviors and structural evolution of the GexSiO(1-x) electrodes are investigated systematically. The in-situ electrochemical dilatometry reveals that the Ge0.5SiO0.5 electrode displays a better reversible thickness variation during cycling process. Density functional theory (DFT) calculation demonstrates that the SiGe domain can accommodate the volume expansion of Si and Ge domains. Moreover, the relationships between the electrochemical performance and morphology evolution demonstrate that the disordered structure and nanoscale distribution of Ge0.5SiO0.5 electrodes are the main reasons for improving ICE and cycle stability. This work provides a commercially available synthetic route for the design of advanced anode materials for large-scale energy storage applications.

Accelerated Electrons Transfer and Synergistic Interplay of Co and Ge Atoms (111 Crystal Plane) Activated by Anchoring Nano Spinel Structure Co2GeO4 onto Carbon Cloth Composite Electrocatalyst for Highly Enhanced Hydrogen Evolution Reaction

The electrochemical hydrogen evolution reaction (HER) was considered to be a promising strategy for future clean energy. In this work, a composite electrocatalyst (designated as CGO36@CC) was synthesized through anchoring of nano spinel structure Co2GeO4 onto carbon cloth fibers and exhibited outstanding electrocatalytic performance for HERs in an alkaline medium. The characterization outcome established that, after 36 h of hydrothermal reaction, nano spinel structure Co2GeO4 particles (exposed abundant 111 crystal planes) were stably loaded onto a carbon cloth fiber surface, and this structural configuration facilitated the electrons transferring between each other. In addition, the electrochemical analysis revealed that the incorporation of nano spinel structure Co2GeO4 and carbon cloth significantly augmented the electrochemical activity value of the composite and efficiently enhanced the HER performance. Notably, the overpotential was merely 96 mV at 10 mA·cm−2 current density, and the Tafel slope was only 48.9 mV·dec−1. Moreover, CGO36@CC displayed remarkable catalytic activity and sustained HER catalytic stability. The theoretical catalytic prowess of CGO36@CC stemmed from the collaborative influence of germanium and cobalt atoms within the exposed 111 crystal plane of the Co2GeO4 molecular framework. The amalgamation of Co2GeO4 with carbon cloth fiber conferred upon the composite electrocatalyst both superior theoretical catalytic activity and enhanced electron transfer capability. This work provides a novel strategy for exploring a highly efficient composite electrocatalyst combined transition metal with carbon material to accelerate the HER activity.

Synthesis, Structure, Electrochemical Properties, and Antioxidant Activity of Organogermanium(IV) Catecholate Complexes.

A series of novel organogermanium(IV) catecholates 1-9 of the general formula R'2Ge(Cat), where R' = Ph, Et, have been synthesized. Compounds were characterized by 1H, 13C NMR, IR spectroscopy, and elemental analysis. The molecular structures of 1-3, 6, and 8 in crystal state were established using single-crystal X-ray analysis. The complexes are tetracoordinate germanium(IV) compounds containing a dioxolene ligand in a dianion (catecholato) form. Electrochemical transformations of target germanium(IV) complexes have been studied by cyclic voltammetry. The electro-oxidation mechanism of complexes 1-5, 7, and 10 (the related complex Ph2Ge(3,5-Cat) where 3,5-Cat is 3,5-di-tert-butylcatecholate) involves the consecutive formation of mono- and dicationic derivatives containing the oxidized forms of redox-active ligands. The stability of the generated monocations depends both on the hydrocarbon groups at the germanium atom and on the substituents in the catecholate ring. Compounds 6, 8, and 9 are oxidized irreversibly under the electrochemical conditions with the formation of unstable complexes. The radical scavenging activity and antioxidant properties of new complexes were estimated in the reaction with DPPH radical, ABTS radical cation, and CUPRACTEAC assay. It has been found that compounds 8 and 9 with benzothiazole or phenol fragments are more active in DPPH test. The presence of electron-rich moieties in the catecholate ligand makes complexes 5 and 7-9 more reactive to ABTS radical cation. The value of CUPRACTEAC for organogermanium(IV) catecholates varies from 0.23 to 1.45. The effect of compounds 1-9 in the process of lipid peroxidation of rat liver (Wistar) homogenate was determined in vitro. It was found that most compounds are characterized by pronounced antioxidant activity. A feature of complexes 1, 3, and 5-9 is the intensification of the antioxidant action with the incubation time. In the presence of additives of complexes 3, 5, 6, and 8, an induction period was observed during the process of lipid peroxidation.

ATI Stabilized Germylene Cation as a Cyanosilylation Catalyst for Aldehydes and Ketones.

The aminotroponiminate (ATI) ligand stabilized germylene cation [(i-Bu)2ATIGe][B(C6F5)4] (2) is found to be an efficient low-valent main-group catalyst for the cyanosilylation of aldehydes and ketones (ATI=aminotroponiminate). It was synthesized by reacting [(i-Bu)2ATIGeCl] (1) with Na[B(C6F5)4]. The catalytic cyanosilylation of diverse aliphatic and aromatic carbonyl compounds (aldehydes and ketones) using 0.075-0.75 mol% of compound 2 was completed within 5-45 min. The catalytic efficiency seen with aliphatic aldehydes was around 15,800 h-1, making compound 2 a capable low-valent main-group catalyst for the aldehyde and ketone cyanosilylation reactions. Further, DFT calculations reveal a pronounced charge localization at the germanium atom of compound 2, leading to its superior catalytic performance.

Wide and ultrawide-bandgap semiconductor surfaces: A full multiscale model

Germanium, gallium, nitrogen, and oxygen deposition on both GaN(0001) and GaN(0001̄) surfaces were investigated. A multiscale simulation framework was implemented. The DFT simulations were employed to reveal the interactions among the species and GaN surface. Energy diffusion barriers were obtained by the Nudged Elastic Band approach. A Poisson–Nernst–Planck model was implemented to calculate the concentration of each atomic species near GaN surface. The kinetic and unimolecular collision gas theories were incorporated to determine adsorption rates. These outcomes were integrated into a nanoscale kinetic Monte Carlo model. This model allowed to generate data on the surface diffusion and clustering of adsorbed atoms on GaN surfaces. As a result, an enhanced understanding of the deposition and agglomeration mechanisms was achieved. In particular, of the roles played by germanium and oxygen. Due to the relatively high diffusion energy barriers, germanium atoms act as pins around to which gallium atoms tend to cluster. The results align with both experimental observations and existing simulation literature. To the best of our knowledge, no previous DFT simulation results on germanium deposition on GaN have been reported.

Structure, bonding, and properties of RCr6Ge6 intermetallics (R[dbnd]Gd–Lu)

We report the discovery and characterization of three novel ternary compounds: TmCr6Ge6, YbCr6Ge6, and LuCr6Ge6, which complete the series of RCr6Ge6 intermetallics with kagome lattice. Energy dispersive X-ray analysis revealed the off-stoichiometric composition of RCr6Ge6 (RGd, Tb, Dy, Ho, Er, Tm, Yb, and Lu). The powder XRD analysis with subsequent Rietveld refinement showed that investigated compounds crystallize in the SmMn6Sn6 structure type (space group P6/mmm), a disordered variant of the MgFe6Ge6-type, with a small number of vacancies at the rare earth (1a) and germanium (2e) sites and two additional 1b and 2e sites partially occupied by additional rare earth and germanium atoms, respectively. A tendency to structure ordering is observed with decreasing rare earth ionic radii. Electrical resistivity measurements indicate a metallic conductivity type for all studied compounds. Magnetic characterization reveals paramagnetic behavior for TmCr6Ge6 and LuCr6Ge6, respectively, and suggests YbCr6Ge6 as a ferrimagnetic material. The DFT modeling of RCr6Ge6 shows a distinct high electron localization between Ge1 atoms, corresponding to strong covalent bonding. The calculated enthalpies of formation range from −18.56 kJ/mol for Gd to −19.60 for Tm compounds, while the distribution of the density of electronic states (DOS) confirms the metallic type of conductivity for all the series. The calculated elastic properties show brittle behavior and a high hardness level for the whole series. DFT modeling allowed us to reveal mechanisms of RCr6Ge6 formation and the origin of disorder in their crystal structure.

SYNTHESIS AND STRUCTURE OF SUPRAMOLECULAR GLUCONATOGERMANATES(IV) WITH NITROGEN-CONTAINING ORGANIC CATIONS

Optimal methods of synthesis of germanium(IV) complexes with gluconic acid (H6Gluc) and exo-ligands niacin (Nic), niamide (Nad) and isoniazid (Ind) in aqueous solution were developed. The structure and stereochemistry of the presented complexes were stated by elemental analyses, thermal analysis, IR spectroscopy and single crystal X-ray analysis. It was shown the formation of supramolecular salts of the composition (NicH)2[Ge2(OH)2(μ-H2Gluc)2]·3H2O (1), (NadH)2[Ge2(OH)2(μ-H2Gluc)2]·3H2O (2), (IndH)2[Ge2(OH)2 (μ-H2Gluc)2] (3). It was established that complex 2 consists of two protonated niamide molecules and a complex anion in which two germanium atoms are coordinated by two bridging ligands of deprotonated gluconic acid H2Gluc4-. The trigonal-bipyramidal polyhedron of Ge(IV) is additionally formed by the coordination of the hydroxyl group. In the crystalline phase, the complex exists as a trihydrate.

A theoretical investigation on MgB11N12, GeB11N12, GaB11N12, SiB11N12, AlB11N12, and pristine B12N12 clusters for sensing Memantine and its drug delivery for Alzheimer’s disease

As an important problem, Alzheimer disease has resulted in thousands of deaths in the human society. Thus, researches around drug design and drug delivery methods for treating this illness is crucial. The MgB11N12, GeB11N12, GaB11N12, SiB11N12, AlB11N12 and pristine B12N12 clusters were designed to investigate effective modes of transporting memantine (MMT) nanoparticles as anti-Alzheimer agents.The results showed that among all considered heteroatoms, the Germanium, and Gallium atoms have the highest effect on decreasing the Eg of the system albeit by making the B12N12 clusters, a semiconductor-like nanoparticle. Due to these results, GeB11N12 derivate with the Eg of 2.76182 eV, is a suitable semiconductor cluster. Also, after adsorption of MMT, the Ge nanoparticles enhances Eg to 3.32533 eV, resulting in a strong signal. Thus, between all studied clusters, the GeB11N12, is the best choice to be used as a sensor for detection of MMT residues. Additionally, the energy surface data indicated that the SiB11N12 is a suitable nanoparticle for delivering memantine, better than the pristine B12N12 cluster. We hope this work will be useful for future experimental studies about the adsorption and sensing of MMT drug residues.

Structural and bonding characteristics in Au2Ge9ˉ and Au2Ge10ˉ clusters: Insights from photoelectron spectroscopy and theoretical calculations

Germanium-based materials exhibit promising properties for applications in electronics, sensing, and catalysis. Gold-germanium clusters are of particular interest due to their potential for enhanced stability and tailored electronic properties. This study investigates the structures, bonding, and electronic properties of Au2Ge9ˉ and Au2Ge10ˉ clusters using anion photoelectron spectroscopy and theoretical calculations. The clusters were generated using laser vaporization and studied using anion photoelectron spectroscopy. Theoretical calculations employed density functional theory and coupled-cluster methods. Au2Ge9ˉ and Au2Ge10ˉ clusters exhibit weak aurophilic interactions between the two gold atoms. The gold atoms mimic the electronic and structural properties of germanium atoms, acting as surrogates within the cluster framework. Understanding the role of gold in these germanium clusters provides insights for designing novel materials with tailored properties for applications in catalysis, electronics, and other fields.

Applicability of the Zintl Concept to Understanding the Crystal Chemistry of Lithium-Rich Germanides and Stannides.

With this contribution, we take a new, critical look at the structures of the binary phases Li5Ge2 and Li5Sn2. Both are isostructural (centrosymmetric space group R3̅m, no. 166), and in their structures, all germanium (tin) atoms are dimerized. Application of the valence rules will require the allocation of six additional valence electrons per [Ge2] or [Sn2] unit considering single covalent bonds, akin to those in the dihalogen molecules. Alternatively, four additional valence electrons per [Ge2] or [Sn2] anion will be needed if homoatomic double bonds exist, in an analogy with dioxygen. Therefore, five lithium atoms in one formula unit cannot provide the exact number of electrons, leaving open questions as to what is the nature of the chemical bonding within these moieties. Additionally, by means of single-crystal X-ray diffraction, synchrotron powder X-ray diffraction, and neutron powder diffraction, we established that the Li and Sn atoms in Li5Sn2 are partially disordered, i.e., the actual chemical formula of this compound is Li5-xSn2+x (0 < x < 0.1). The convoluted atomic bonding in the case where tin atoms partially displace lithium atoms results in the formation of larger covalently bonded fragments. Our first-principle calculations suggest that such disorder leads to electron doping. Contrary to that, both experimental and computational findings indicate that in the Li5Ge2 structure, the [Ge2] dimers are slightly oxidized, i.e., hole-doped, as a result of approximately 30% vacancies on a Li site, i.e., the actual chemical formula of this compound is Li5-xGe2 (x ≈ 0.3).

Synthesis and Characterization of an All-Germanium Analogue of Cyclobutane-1,3-diyl.

A tetragermacyclobutane-1,3-diyl was prepared and structurally characterized via the reduction of chlorogermylene-coordinated germylgermylene with potassium graphite, which represents the first all-germanium analogue of cyclobutane-1,3-diyl. Single-crystal X-ray analysis of the tetragermacyclobutane-1,3-diyl disclosed that it adopts a planar-cis structure, which is different from those reported all-silicon cyclobutane-1,3-diyls. DFT calculations revealed that both the bulky substituents on the germanium atoms and the tethering of the amido groups are important for the planar cis-configuration of 5.

Reactivity of a Linear 2-Germapropadiene with Acids, Ketones, and Amines.

The reactivity of an isolable 2-germapropadiene with acids, ketones, and amines was investigated. The reactions of 2-germapropagiene 1 with hydrogen chloride and acetic acid afforded the corresponding dichlorogermane (2) and diacetoxygermane (3), respectively, indicating that the central germanium atom of 1 is electrophilic. The reaction of 1 with benzaldehyde proceeds via a formal [2+2] cycloaddition to afford the corresponding spiro compound (4). Moreover, 1 reacts smoothly with acetone to furnish germane 5, which contains a six-membered ring involving two acetone molecules. Furthermore, 1 undergoes N-H bond insertion with methylamine or aniline to afford diamino germanes 7 and 8, respectively. The reaction of 1 with urea selectively afforded the corresponding N-H-insertion product (8).

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile.

Phosphagermylenylidenes (R-P═Ge), as heavier analogs of isonitriles, whether in their free state or as complexes with a Lewis base, have not been previously identified as isolable entities. In this study, we report the synthesis of a stable monomeric phosphagermylenylidene within the coordination sphere of a Lewis base under ambient conditions. This species was synthesized by Lewis base-induced dedimerization of a cyclic phosphagermylenylidene dimer or via Me3SiCl elimination from a phosphinochlorogermylene framework. The deliberate integration of a bulky, electropositive N-heterocyclic boryl group at the phosphorus site, combined with coordination stabilization by a cyclic (alkyl)(amino)carbene at the low-valent germanium site, effectively mitigated its natural tendency toward oligomerization. Structural analyses and theoretical calculations have demonstrated that this unprecedented species features a P═Ge double bond, characterized by conventional electron-sharing π and σ bonds, complemented by lone pairs at both the phosphorus and germanium atoms. Preliminary reactivity studies show that this base-stabilized phosphagermylenylidene demonstrates facile release of ligands at the Ge atom, coordination to silver through the lone pair on P, and versatile reactivity including both (cyclo)addition and cleavage of the P═Ge double bond.

Silicon with Binary Compounds GexSi1-x

This paper presents the results of studies of the electrophysical, photoelectric, and magnetic properties of silicon samples doped by diffusion of germanium impurity atoms. It has been shown that impurity germanium atoms form in silicon binary compounds of the GexSi1-x type, the concentration of which varies with the depth of the original silicon. The developed diffusion technology of silicon doping with impurity germanium atoms made it possible to obtain a material with different concentrations of impurity germanium atoms, resistivity, and the type of conductivity. The optimal electrophysical parameters of the obtained samples for studying the electrophysical parameters and the magnetic properties were determined, which made it possible to show the possibilities of creating new types of sensors and devices for semiconductor electronics. The presented studies make it possible to develop respective directions in the field of materials science with magnetic properties and the creation of efficient photovoltaic cells for photoenergetics.

Consideration of electronic mean heat transport via a low dimension system

The object of research is the complex realm of energy localization and coherent ballistic electronic transport within low-dimensional silicon quantum wires, specifically those doped with germanium atoms. Unlike their three-dimensional counterparts, low-dimensional systems exhibit unique electronic transport behaviors, necessitating novel analytical approaches for a comprehensive understanding. The core of this investigation leverages the Phase Field Matching Theory (PMFT) and the tight-binding (TB) approximation, sophisticated methodologies that enable a deep dive into the quantum mechanical nuances of these systems. Through this lens, we examine the intricate dynamics of dispersion relationships, phase factors, group velocities, and notably, the impact of defects introduced by the germanium doping. This research meticulously analyzes how these defects affect electronic and thermal conductivities, along with densities of states, offering new insights into the role of Fano resonances in the fluctuation of transmission and reflection spectra. These resonances, we find, are crucially dependent on the nature of the defects, their configuration, and the electronic parameters in their vicinity, underscoring the nuanced interplay between material composition and electronic properties in low-dimensional systems. The implications of our findings extend far beyond the theoretical. They pave the way for significant advancements in nanotechnology and the design of electronic devices, highlighting the potential for creating more efficient, high-performance components. Furthermore, this work proposes a framework for developing non-destructive testing methodologies that could revolutionize material science by enabling the precise analysis of defects in low-dimensional systems without causing damage. This is particularly critical for the ongoing development of materials with optimized properties for various applications, from electronics to energy storage. In essence, this research not only enriches our understanding of the physics governing low-dimensional systems but also offers practical insights into leveraging these properties for technological innovation. By bridging the gap between theoretical physics and material science, our study sets the stage for the next generation of electronic components and non-destructive evaluation techniques, marking a significant step forward in the application of quantum mechanics to real-world challenges.

A C21Ge two-dimensional material with high sensitivity and strong adsorption capacity for CO

Density functional theory (DFT) calculations were employed to investigate the adsorption of a single CO molecule on C21Ge (named due to the presence of 21 carbon atoms and 1 germanium atom in its structure). The study involved the determination of the most stable geometric structures, adsorption energies, adsorption heights, and density of states for the system, exploring the interactions between the adsorbed CO molecule and the substrate. The results revealed a high degree of CO adsorption on C21Ge, with adsorption energies of −1.34 eV and −1.33 eV for C atoms near the adsorption site and O atoms near the adsorption site, respectively. The adsorption distances were determined to be 2.89 Å and 3.04 Å, with the most stable adsorption sites identified as H3 and B3. The adsorption strength was slightly higher when C atoms were in proximity compared to O atoms. The high degree of hybridization between the density of states orbitals indicated strong interactions between the CO molecule and C21Ge, emphasizing the pronounced adsorption capability of C21Ge for CO.

Small-Molecule Activation by Low-Coordinated Germanium Compounds

AbstractWe have been interested in the differences between the properties of low-coordinated carbon compounds and their heavier homologues based on elements of group 14, e.g., Si and Ge. Fundamental research on the synthesis and characterization of divalent and multiply bonded compounds of heavier group 14 elements has led to a variety of isolated low-coordinated species of heavier group 14 elements that can replace transition metals in small-molecule transformations. We have focused on low-coordinated germanium compounds with double or triple bonds between germanium atoms, as well as germanium-containing aromatic compounds. Once isolated, the reactivity of these low-coordinated germanium compounds was examined with regard to small-molecule activation. In this account, the reactivity patterns of these compounds will be described.1 Introduction2 1,2-Dibromodigermenes and Bromogermylenes3 Digermynes4 1,2-Digermacyclobutene5 1,3-Digerma-2-silaallene6 Digerma-Aromatic Compounds7 Germanium-Catalyzed Cyclotrimerization of Alkynes8 Summary

The germanides ScTGe2 (T = Fe, Co, Ru, Rh) – crystal chemistry, 45Sc solid-state NMR and 57Fe Mössbauer spectroscopy

Abstract The TiMnSi2-type (space group Pbam) germanides ScTGe2 (T = Fe, Co, Ru, Rh) were synthesized from the elements by arc-melting. Single crystals were grown by annealing sequences of the arc-melted buttons in an induction furnace. The structures of ScFeGe2, ScRuGe2 and ScRhGe2 were refined from single-crystal X-ray diffraction data. In ScRuGe2, the ruthenium atoms have distorted octahedral germanium coordination (242–268 pm Ru–Ge). Three trans-face-sharing octahedra form a sub-unit which is condensed via common edges in c direction and connected via common corners with four adjacent blocks, forming a three-dimensional [RuGe2 type] substructure. The two crystallographically independent scandium sites have coordination numbers 15 (Sc1@Ge8Ru4Sc3) and 17 (Sc2@Ge7Ru6Sc4). Electronic band structure calculations for ScCoGe2 and ScRuGe2 show a net charge transfer from the scandium to the transition metal and germanium atoms, leading to a description with polyanionic networks Sc δ+[TGe2]δ−. The two crystallographically independent Sc sites are easily distinguishable by 45Sc magic-angle spinning (MAS)-NMR spectroscopy. Isotropic chemical shift values and nuclear electric quadrupolar interaction parameters were deduced from an analysis of the triple-quantum (TQ)-MAS NMR spectra. The electric field gradient parameters deduced from these experiments are in good agreement with quantum-chemical calculations using the Wien2k code. Likewise, the two crystallographically independent iron sites in ScFeGe2 could be discriminated in the 57Fe Mößbauer spectra through their isomer shifts and quadrupole splitting parameters: δ = 0.369(1) mm s−1 and ∆E Q = 0.232(2) mm s−1 for Fe1 and δ = 0.375(2) mm s−1 and ∆E Q = 0.435(4) mm s−1 for Fe2 (data at T = 78 K).

Synthesis of 1‐Adamantylaminogermylene and Its Chalcogenation Reactions

AbstractThe synthesis, isolation, and characterization of 1‐adamantylaminogermylene 1 have been achieved utilizing kinetic stabilization with a bulky aryl group on the germanium atom. Aminogermylene 1 was found to be stable in toluene solution at 110 °C for 3 days without decomposition. The chalcogenation reaction of 1 aiming to synthesize heavy amides gave the head‐to‐tail type dimers of the corresponding heavy amides.