The precise knowledge of the atomic order in monocrystalline alloys is fundamental to understand and predict their physical properties. With this perspective, we utilized laser-assisted atom probe tomography to investigate the three-dimensional distribution of atoms in non-equilibrium epitaxial Sn-rich group IV SiGeSn ternary semiconductors. Different atom probe statistical analysis tools including frequency distribution analysis, partial radial distribution functions, and nearest neighbor analysis were employed in order to evaluate and compare the behavior of the three elements to their spatial distributions in an ideal solid solution. This atomistic-level analysis provided clear evidence of an unexpected repulsive interaction between Sn and Si leading to the deviation of Si atoms from the theoretical random distribution. This departure from an ideal solid solution is supported by first principal calculations and attributed to the tendency of the system to reduce its mixing enthalpy throughout the layer-by-layer growth process.
Hall-effect and magnetoresistivity of holes in silicon and germanium are considered with due regard for mutual drag of light and heavy band carriers. Search of contribution of this drag shows that this interaction has a sufficient and non-trivial influence on both effects.
Compared with direct-gap semiconductors, the valley degeneracy of silicon and germanium opens up new channels for spin relaxation that counteract the spin degeneracy of the inversion-symmetric system. Here the symmetries of the electron-phonon interaction for silicon and germanium are identified and the resulting spin lifetimes are calculated. Room-temperature spin lifetimes of electrons in silicon are found to be comparable to those in gallium arsenide, however, the spin lifetimes in silicon or germanium can be tuned by reducing the valley degeneracy through strain or quantum confinement. The…
Germanium-Tin is emerging as a material exhibiting excellent photonic properties. Here we demonstrate optical initialization and readout of spins in this intriguing group IV semiconductor alloy and report on spin quantum beats between Zeeman-split levels under an external magnetic field. Our optical experiments reveal robust spin orientation in a wide temperature range and a persistent spin lifetime that approaches the ns regime at room temperature. Besides important insights into nonradiative recombination pathways, our findings disclose a rich spin physics in novel epitaxial structures direc…
We report the fabrication and electrical characterization of a single electron transistor in a modulation doped silicon/silicon-germanium heterostructure. The quantum dot is fabricated by electron beam lithography and subsequent reactive ion etching. The dot potential and electron density are modified by laterally defined side gates in the plane of the dot. Low temperature measurements show Coulomb blockade with a single electron charging energy of 3.2 meV.
We have investigated the structural sequence of the high-pressure phases of silicon and germanium. We have focussed on the cd->beta-tin->Imma->sh phase transitions. We have used the plane-wave pseudopotential approach to the density-functional theory implemented within the Vienna ab-initio simulation package (VASP). We have determined the equilibrium properties of each structure and the values of the critical parameters including a hysteresis effect at the phase transitions. The order of the phase transitions has been obtained alternatively from the pressure dependence of the enthalpy and of t…
The universal building block which is an essential part of all atomic structures on (1 1 0) silicon and germanium surfaces and their vicinals is proposed from first-principles calculations and a comparison of results with available experimental data. The atomic models for the (1 1 0)-(16x2), (1 1 0)-c(8x10), (1 1 0)-(5x8) and (17 15 1)-(2x1) surface reconstructions are developed on the basis of the building block structure. The models exhibit very low surface energies and excellent agreements with bias-dependent scanning tunneling microscopy (STM) images. It is shown experimentally using STM t…
Core-shell nanowires made of Si and Ge can be grown experimentally with excellent control for different sizes of both core and shell. We have studied the structural properties of Si/Ge and Ge/Si core-shell nanowires aligned along the $[110]$ direction, with diameters up to 10.2~nm and varying core to shell ratios, using linear scaling Density Functional Theory (DFT). We show that Vegard's law, which is often used to predict the axial lattice constant, can lead to an error of up to 1\%, underlining the need for a detailed \emph{ab initio} atomistic treatment of the nanowire structure. We analys…
We present ab initio calculations of the electronic and optical properties of hexagonal SiGe alloys in the lonsdaleite structure. Lattice constants and electronic band structures in excellent agreement with experiment are obtained using density-functional theory. Hexagonal Si has an indirect band gap, while hexagonal Ge has a pseudo-direct gap, i.e. the optical transitions at the minimum direct band gap are very weak. The pseudo-direct character of pure hexagonal Ge is efficiently lifted by alloying. Already for a small admixture of Si, symmetry reduction enhances the oscillator strength of th…
This article continues our recent publication [I.A. Baburin and D.M. Proserpio and V.A. Saleev and A.V. Shipilova, Phys. Chem. Chem. Phys.17, 1332 (2015)] where we have presented a comprehensive computational study of sp3 carbon allotropes based on the topologies proposed for zeolites. Here we predict six new silicon and six new germanium allotropes which have the same space group symmetries and topologies as those predicted earlier for the carbon allotropes, and study their structural, elastic, vibrational, electronic and optical properties.
Conductivity of p-Si and p-Ge is considered for two band model with due regard for mutual drag of light and heavy holes. It is shown that for small and moderate temperatures this drag significantly diminishes drift velocity of light holes and, as result, the total conductivity of crystal. Considered here drag-effect appears as well in the form of nonmonotonous dependences of conductivity on temperature and carrier density.
Based on first-principles calculations of structure optimization, phonon modes and finite temperature molecular dynamics, we predict that silicon and germanium have stable, two-dimensional, low-buckled, honeycomb structures. Similar to graphene, they are ambipolar and their charge carriers can behave like a massless Dirac fermions due to their pi- and pi*-bands which are crossed linearly at the Fermi level. In addition to these fundamental properties, bare and hydrogen passivated nanoribbons of Si and Ge show remarkable electronic and magnetic properties, which are size and orientation depende…
A theoretical modeling of the oxygen diffusivity in silicon and germanium crystals both at normal and high hydrostatic pressure has been carried out using molecular mechanics, semiempirical and ab initio methods. It was established that the diffusion process of an interstitial oxygen atom (Oi) is controlled by the optimum configuration of three silicon (germanium) atoms nearest to Oi. The calculated values of the activation energy Ea(Si)= 2.59 eV, Ea(Ge)= 2.05 eV and pre-exponential factor Do (Si) = 0.28 sm2 s-1, Do (Ge) = 0.39 sm2 s-1 are in a good agreement with experimental ones and for the…
Germanium and silicon-germanium alloys have found entry into Si technology thanks to their compatibility with Si processing and their ability to tailor electronic properties by strain and band-gap engineering. Germanium's potential to extend Si functionalities, as exemplified by lasing action of strained-Ge on Si substrates, has brought the material back to attention. Yet despite these advances, non-radiative transitions, induced by crystal defects originating from the Ge/Si interface, continue to be a serious bottleneck. Here we demonstrate the drastic emission enhancement achieved via contro…
Temperature effects on the energetics of the 90-degree partial dislocation in silicon and germanium are investigated, using non-equilibrium methods to estimate free energies, coupled with Monte Carlo simulations. Atomic interactions are described by Tersoff and EDIP interatomic potentials. Our results indicate that the vibrational entropy has the effect of increasing the difference in free energy between the two possible reconstructions of the 90-degree partial, namely, the single-period and the double-period geometries. This effect further increases the energetic stability of the double-perio…
We discuss a model for the on-site matrix elements of the sp3d5s* tight-binding hamiltonian of a strained diamond or zinc-blende crystal or nanostructure. This model features on-site, off-diagonal couplings between the s, p and d orbitals, and is able to reproduce the effects of arbitrary strains on the band energies and effective masses in the full Brillouin zone. It introduces only a few additional parameters and is free from any ambiguities that might arise from the definition of the macroscopic strains as a function of the atomic positions. We apply this model to silicon, germanium and the…
We present a comprehensive theory of the circularly polarized luminescence and its dependence on strain in spin-polarized Si and Ge. Symmetries of wavefunctions and interactions are used to derive concise ratios between intensities of the right and left circularly polarized luminescence for each of the dominant phonon-assisted optical transitions. These ratios are then used to explain the circular polarization degrees of the luminescence peaks in the spectra of biaxially-strained Si and Ge, and of relaxed ${\rm{Si}}_{1-x}{\rm{Ge}}_{x}$ alloys. The spectra are numerically calculated by a combin…
The dynamics of the luminescence decay from germanium nanocrystals embedded in crystalline silicon has been studied for temperatures varied between 16 K and room temperature. At room temperature the characteristic decay time is of the order of 50 nanoseconds while it extends into the microsecond range at low temperatures. The decay is dominated by non-radiative processes, which show a typical thermal activation energy of a few meV.
For Si and Ge nanocrystals (NCs) embedded in wide band-gap matrices, Auger recombination (AR) and carrier multiplication (CM) lifetimes are computed exactly in a three-dimensional real space grid using empirical pseudopotential wave functions. Our results in support of recent experimental data offer new predictions. We extract simple Auger constants valid for NCs. We show that both Si and Ge NCs can benefit from photovoltaic efficiency improvement via CM due to the fact that under an optical excitation exceeding twice the band gap energy, the electrons gain lion's share from the total excess e…
Special point defects in semiconductors have been envisioned as suitable components for quantum-information technology. The identification of new deep centers in silicon that can be easily activated and controlled is a main target of the research in the field. Vacancy-related complexes are suitable to provide deep electronic levels but they are hard to control spatially. With the spirit of investigating solid state devices with intentional vacancy-related defects at controlled position, here we report on the functionalization of silicon vacancies by implanting Ge atoms through single-ion impla…
The thermal coefficient of resistance (TCR) for epitaxial silicon-germanium (SiGe) layers has been analyzed by experiment and simulation. Predictive simulation using drift-diffusion formalism and self-consistent quantum-mechanical solutions yielded similar results, TCR around 2%/K at 300 K. This modeling approach can be used for different, graded and constant, SiGe profiles,. It is also capable of predicting the influence of background auto-doping on the TCR of the detectors
The lifting of the two-fold degeneracy of the conduction valleys in a strained silicon quantum well is critical for spin quantum computing. Here, we obtain an accurate measurement of the splitting of the valley states in the low-field region of interest, using the microwave spectroscopy technique of electron valley resonance (EVR). We compare our results with conventional methods, observing a linear magnetic field dependence of the valley splitting, and a strong low-field suppression, consistent with recent theory. The resonance linewidth shows a marked enhancement above $T\simeq 300$ mK.
We calculate the thermoelectric figure of merit, zT=S^2GT/(κ_l+κ_e), for p-type Si nanowires with axial Ge heterostructures using a combination of first-principles density-functional theory, interatomic potentials, and Landauer-Buttiker transport theory. We consider nanowires with up to 8400 atoms and twelve Ge axial heterostructures along their length. We find that introducing heterostructures always reduces S^2G, and that our calculated increases in zT are predominantly driven by associated decreases in κ_l. Of the systems considered, <111> nanowires with a regular distribution of Ge heteros…
In this work we report new silicon and germanium tubular nanostructures with no corresponding stable carbon analogues. The electronic and mechanical properties of these new tubes were investigated through ab initio methods. Our results show that the structures have lower energy than their corresponding nanoribbon structures and are stable up to high temperatures (500 and 1000 K, for silicon and germanium tubes, respectively). Both tubes are semiconducting with small indirect band gaps, which can be significantly altered by both compressive and tensile strains. Large bandgap variations of almos…
The theoretical analysis of the process of diffusion of interstitial oxygen atoms and hydrogen molecules in silicon and germanium crystals has been performed. The calculated values of the activation energy and pre-exponential factor for an interstitial oxygen atom Ea(Si) = 2.59 eV, Ea(Ge) = 2.05 eV, D(Si)= 0.28 cm2s-1, D(Ge)= 0.39 cm2s-1 and interstitial hydrogen molecule Ea(Si) = 0.79-0.83 eV, Ea(Ge) = 0.58-0.62 eV, D(Si)= 7.4 10(-4) cm2s-1, D(Ge)= 6.5 10(-4) cm2s-1 are in an excellent agreement with experimental ones and for the first time describe perfectly an experimental temperature depen…
We present a first-principles study of bare and hydrogen passivated armchair nanoribbons of the puckered single layer honeycomb structures of silicon and germanium. Our study includes optimization of atomic structure, stability analysis based on the calculation of phonon dispersions, electronic structure and the variation of band gap with the width of the ribbon. The band gaps of silicon and germanium nanoribbons exhibit family behavior similar to those of graphene nanoribbons. The edges of bare nanoribbons are sharply reconstructed, which can be eliminated by the hydrogen termination of dangl…
While several 2D thermometry techniques exist, there is a lack of 3D thermometry techniques that work for wide range of materials and offer good resolution in time, space and temperature. X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) imaging can provide 3D temperature information. However, XRD is typically limited to crystalline materials while NMR is largely limited to liquids where the resonance lines are narrow. We investigate electron paramagnetic resonance (EPR) of n-type silicon and germanium for 3D thermometry. While in germanium the EPR linewidths are too broad, EPR line…
Enhancement of the electronic thermoelectric properties of bulk strained silicon-germanium alloys using the scattering relaxation times from first principles
In a semiconductor heterostructure with type II energy band alignment, the spatial separation between electrons and holes slows down their radiative recombination. With increasing excitation intensity, Auger recombination quickly becomes the dominate recombination channel, and it produces carrier ejection from the quantum well. Here, we show that in Si/SiGe three-dimensional nanostructures, this efficient process facilitates the formation of an electron-hole plasma (EHP) and/or electron-hole droplets (EHDs) in thin Si barriers separating SiGe clusters. In contrast to conventional, strongly tem…
Extending chip performance beyond current limits of miniaturisation requires new materials and functionalities that integrate well with the silicon platform. Germanium fits these requirements and has been proposed as a high-mobility channel material,[1] a light emitting medium in silicon-integrated lasers,[2,3] and a plasmonic conductor for bio-sensing.[4,5] Common to these diverse applications is the need for homogeneous, high electron densities in three-dimensions (3D). Here we use a bottom-up approach to demonstrate the 3D assembly of atomically sharp doping profiles in germanium by a repea…
We present a new interpretation of measured Raman frequencies of a high-pressure structure of Silicon which was assigned previously to the beta-tin phase. Our results show that the beta-tin->Imma->sh phase transitions have been already indicated in this experiment which was performed before the discovery of the Imma phase. We have calculated phonon-dispersion curves for the beta-tin, Imma, and sh phases of silicon using the plane-wave pseudopotential approach to the density-functional theory and the density-functional perturbation theory within the local density approximation. With the new ass…
In this article, the results of investigation of processes occurring during the molecular-beam deposition of germanium layers on Si$_3$N$_4$ dielectric substrates within a wide range of the Ge film growth temperatures (30 to 600°C) are presented. The intensity of the IR absorption bands related to the vibrations of the N$-$H and Si$-$N bonds are established to decrease with the increase of the Ge deposition temperature. It appears that this phenomenon cannot be explained only as a thermally activated process. Simultaneously, the peak corresponding to the Ge$-$N vibration bonds emerges in the X…
Germanium has emerged as an exceptionally promising material for spintronics and quantum information applications, with significant fundamental advantages over silicon. However, efforts to create atomic-scale devices using donor atoms as qubits have largely focussed on phosphorus in silicon. Positioning phosphorus in silicon with atomic-scale precision requires a thermal incorporation anneal, but the low success rate for this step has been shown to be a fundamental limitation prohibiting the scale-up to large-scale devices. Here, we present a comprehensive study of arsine (AsH$_3$) on the germ…
Hexagonal group IV materials like silicon and germanium are expected to display remarkable optoelectronic properties for future development of photonic technologies. However, the fabrication of hexagonal group IV semiconductors within the vapour-liquid-solid method has been obtained using gold as a catalyst thus far. In this letter, we show the synthesis of hexagonal Ge on self-assisted GaAs nanowires using molecular beam epitaxy. With an accurate tuning of the Ga and As molecular beam flux we selected the crystal phase, cubic or hexagonal, of the GaAs NWs during the growth. A 500 nm-long hexa…
The mechanism responsible for the emission of clusters from heavy ion irradiated solids is proposed to be thermal spikes. Collision cascade-based theories describe atomic sputtering but cannot explain the consistently observed experimental evidence for significant cluster emission. Statistical thermodynamic arguments for thermal spikes are employed here for qualitative and quantitative estimation of the thermal spike-induced cluster emission from silicon, germanium and zinc oxide. The evolving cascades and spikes in elemental and molecular semiconducting solids are shown to have fractal charac…
It was previously believed that the Bloch electronic states of non-magnetic materials with inversion symmetry cannot have finite spin polarizations. However, since the seminal work by Zhang et al. [Nat. Phys. 10, 387-393 (2014)] on local spin polarizations of Bloch states in non-magnetic, centrosymmetric materials, the scope of spintronics has been significantly broadened. Here, we show, using a framework that is universally applicable independent of whether hidden spin polarizations are small (e.g., diamond, Si, Ge, and GaAs) or large (e.g., MoS2 and WSe2), that the corresponding quantity ari…
Searches for low-energy tetrahedral polymorphs of carbon and silicon have been performed using density functional theory computations and the ab initio random structure searching (AIRSS) ap- proach. Several of the hypothetical phases obtained in our searches have enthalpies that are lower or comparable to those of other polymorphs of group 14 elements that have either been experimentally synthesized or recently proposed as the structure of unknown phases obtained in experiments, and should thus be considered as particularly interesting candidates. A structure of P bam symmetry with 24 atoms in…
Ge-on-Si structures in-situ doped with phosphorus or arsenic via metal organic chemical vapor deposition (MOCVD) were investigated. Surface roughness, strain, threading dislocation desnity, Si-Ge interdiffusion, dopant diffusion, and photoluminescence were characterized to study the impacts of defect annealing and Si substrate offcut effects on the Ge film quality and most importantly, the light emission properties. All samples have a smooth surface (roughness < 1.5 nm), and the Ge films have a small tensile strain of 0.2%. As-grown P and As-doped Ge films have threading dislocaiton densities …
Implicit summation is a technique for the conversion of sums over intermediate states in multiphoton absorption and the high-order susceptibility in hydrogen into simple integrals. Here, we derive the equivalent technique for hydrogenic impurities in multi-valley semiconductors. While the absorption has useful applications, it is primarily a loss process; conversely, the non-linear susceptibility is a crucial parameter for active photonic devices. For Si:P, we predict the hyperpolarizability ranges from $χ^{(3)}/n_{\text{3D}}=2.9 $ to $580 \times 10^{-38}$ $\text{m}^5/\text{V}^2$ depending on …
Monochalcogenides of germanium (or tin) are considered as stable isoelectronic and isostructural analogue of black phosphorous. Their two-dimensional (2D) forms have been just predicted to shown strong thickness-dependent physical properties, and even indirect to direct band gap crossover at the monolayer limit. Here, we demonstrate the synthesis of atomically thin GeSe by direct sonication-assisted exfoliation of bulk microcrystalline powders in solvents. The exfoliated few-layer GeSe sheets characterize high crystallinity with lateral sizes over 100 nm and, importantly, strong resistance aga…
We used molecular dynamics (MD) simulations to investigate the mechanical properties of cubic zinc blende (ZB) Si0.5Ge0.5 alloy nanowire (NW). Tersoff potential is employed to elucidate the effect of nanowire size, crystal orientations, and temperature on the material properties. We found that the reduction in the cross-sectional area results in lower ultimate tensile strength and Youngs modulus of this alloy which can be attributed to the increased surface to volume ratio. The [111] oriented Si0.5Ge0.5 NW exhibits the highest fracture strength compared to other crystal orientations but [110] …
Two-dimensional electron and hole gas systems, enabled through band structure design and epitaxial growth on planar substrates, have served as key platforms for fundamental condensed matter research and high performance devices. The analogous development of one-dimensional (1D) electron or hole gas systems through controlled growth on 1D nanostructure substrates, which could open up opportunities beyond existing carbon nanotube and nanowire systems, has not been realized. Here we report the synthesis and transport studies of a 1D hole gas system based on a free-standing germanium/silicon (Ge/S…
Embedded Si and Ge nanocrystals (NCs) in wide band-gap matrices are studied theoretically using an atomistic pseudopotential approach. From small clusters to large NCs containing on the order of several thousand atoms are considered. Effective band-gap values as a function of NC diameter reproduce very well the available experimental and theoretical data. It is observed that the highest occupied molecular orbital for both Si and Ge NCs and the lowest unoccupied molecular orbital for Si NCs display oscillations with respect to size among the different irreducible representations of the $C_{3v}$…
We investigate the pressure-induced metal-insulator transition from diamond to beta-tin in bulk Silicon, using quantum Monte Carlo (QMC) and density functional theory (DFT) approaches. We show that it is possible to efficiently describe many-body effects, using a variational wave function with an optimized Jastrow factor and a Slater determinant. Variational results are obtained with a small computational cost and are further improved by performing diffusion Monte Carlo calculations and an explicit optimization of molecular orbitals in the determinant. Finite temperature corrections and zero p…
Semiconductor superlattices have been extensively investigated for thermoelectric applications, to explore the effects of compositions, interface structures, and lattice strain environments on the reduction of thermal conductivity, and improvement of efficiency. Most studies assumed that their electronic properties remain unaffected compared to their bulk counterparts. However, recent studies demonstrated that electronic properties of silicon (Si)/germanium (Ge) superlattices show significant variations depending on compositions and growth substrates. These studies used a constant relaxation t…
The results of RHEED, FTIR and Raman spectroscopy study of silicon and germanium films with the thickness up to 200 nm grown from molecular beams on dielectric Si$_3$N$_4$/SiO$_2$/Si(001) substrates are presented. Noticeable changes of the intensity of the N$-$H and Si$-$N absorption bands have been observed in the IR absorbance spectra as a result of the deposition of the silicon and germanium films. The thicker was the deposited film, the more considerable were the decrease of N$-$H absorption band intensity and the increase in that of the Si$-$N band. This tendency has been observed during …
Core-shell germanium nanowire (GeNW) is formed with a single-crystalline Ge core and concentric shells of nitride and silicon passivation layer by chemical vapor deposition (CVD), an Al2O3 gate dielectric layer by atomic layer deposition (ALD) and an Al metal surround-gate (SG) shell by isotropic magnetron sputter deposition. Surround gate nanowire field effect transistors (FETs) are then constructed using a novel self-aligned fabrication approach. Individual SG GeNW FETs show improved switching over GeNW FETs with planar gate stacks owing to improved electrostatics. FET devices comprised of m…
Starting from the symmetry aspects and tight-binding method in combination with first-principles calculation, we systematically derive the low-energy effective Hamiltonian involving spin-orbit coupling (SOC) for silicene, which is very general because this Hamiltonian applies to not only the silicene itself but also the low-buckled counterparts of graphene for other group IVA elements Ge and Sn, as well as graphene when the structure returns to the planar geometry. The effective Hamitonian is the analogue to the first graphene quantum spin Hall effect (QSHE) Hamiltonian. Similar to graphene mo…
In spite of remarkable developments in the field of advanced materials, silicon remains one of the foremost semiconductors of the day. Of enduring relevance to science and technology is silicon's nanomechanical behaviour including phase transformation, amorphization and dislocations generation, particularly in the context of molecular dynamics and materials research. So far, comprehensive modelling of the whole cycle of events in silicon during nanoscale deformation has not been possible, however, due to the limitations inherent in the existing interatomic potentials. This paper examines how w…
Depth-Resolved Lattice Distortions in a Silicon-Germanium Qubit Host
Q-NEXT, Argonne National Laboratory（Q-NEXT，阿贡国家实验室）；Materials Science Division, Argonne National Laboratory（材料科学部，阿贡国家实验室）；Pritzker School of Molecular Engineering, University of Chicago（普里茨克分子工程学院，芝加哥大学）；Department of Physics, University of Wisconsin-Madison（物理学系，威斯康星大学麦迪逊分校）；Center for Nanoscale Materials, Argonne National Laboratory（纳米材料中心，阿贡国家实验室）
The electrical manipulation of spins in semiconductors, without magnetic fields or auxiliary ferromagnetic materials, represents the holy grail for spintronics. The use of Rashba effect is very attractive because the k-dependent spin-splitting is originated by an electric field. So far only tiny effects in two-dimensional electron gases (2DEG) have been exploited. Recently, GeTe has been predicted to have bulk bands with giant Rashba-like splitting, originated by the inversion symmetry breaking due to ferroelectric polarization. In this work, we show that GeTe(111) surfaces with inwards or out…
