六方Fe2Ge合金块体及其(001)表面电子结构和磁性的第一性原理

采用基于密度泛函理论第一性原理的赝势平面波方法,计算了块体Fe₂Ge及其(001)表面的电子结构和磁性。考虑了两种类型的终端(001)表面:Ge(Ⅰ)-(001)表面和Ge(Ⅱ)-(001)表面。电子结构方面,不同类型的Fe₂Ge(001)表面都表现出金属特性,这与块体的金属性保持一致。通过计算它们的自旋极化率,得出Ge(Ⅰ)-(001)表面的自旋极化程度最高。磁性方面,在块体和Ge(Ⅱ)-(001)表面的Ge原子是铁磁自旋有序的,而在Ge(Ⅰ)-(001)表面第一层的Ge原子是亚铁磁自旋有序的。此外,Ge(Ⅱ)-(001)表面Ge原子的自旋磁矩优于块体中和Ge(Ⅰ)-(001)表面Ge原子的自旋磁矩。这些结果与Fe的d态和Ge的p态电子的杂化有关,本文中通过分析它们的态密度进行了讨论。     

The effect of the translational symmetry of crystalline silicon on the structure of amorphous germanium in the interfacial region

The structure of an amorphous Ge layer near an interface with a Si(111) crystal was studied by quantitative high-resolution electron microscopy. It was found that the translational symmetry of a Si crystal leads to the crystal-like order in the positions of Ge atoms in the interfacial region, the width of which is about 1.4 nm. In this region, the average orientation of interatomic bonds tilted with respect to the interface compensates for the difference in the bond lengths in crystalline Si and amorphous Ge and is responsible for the tetragonal distortion of the most likely atomic positions.     

Spectroscopic and electrical detection of intermediate phases and chemical bonding self-organizations in (i) dielectric films for semiconductor devices,and (ii) chalcogenide alloys for optical memory devices

This paper presents a discussion of intermediate phases in thin film materials that have been incorporated into liquid crystal displays, LCDs, and optical memory thin film devices. The formation of intermediate phases in the a-Si₃N₄:H (a-Si:N:H) alloys used for gate dielectrics in thin film transistors, TFTs, of LCDs, and the a-Ge–Sb–Te (GST) alloys used for read-write optical writing and storage in optical memory discs are qualitatively different than those first addressed by the Boolchand group in Ge–Se bulk glass alloys. In the a-Si:N:H and a-GST thin films, the chemical self-organizations that suppress percolation of strain, involve chemically-ordered bonding arrangements that break bond bending constraints at the four-fold coordinated Si and Ge atoms in a-Si:N:H and a-GST, respectively. In the GST alloys, this results in over-coordinated and under-coordinated atomic constituents, or valence alternation pairs, VAPs, of charged defects. Finally, other technologically important systems in which broken constraints, and/or VAP defects are important in intermediate phase formation include group IVB (Ti, Zr and Hf) Si oxynitride alloys, and hydrogenated amorphous Si (a-Si:H).     

Solutocapillary convection in germanium‐silicon melts

Surface tension gradients in free crystal growth melts give rise to convective flow. If these gradients are due to thermal gradients, the well known thermocapillary (Marangoni) convection ensues. Concentration gradients due to segregation at the interface during growth can lead to additional solutocapillary convection. A system with large solutocapillary convection is Ge‐Si due to the pronounced segregation and the strong difference in surface tension; solutal buoyancy convection is also present due to the large density difference between Ge and Si. Solutocapillary convection will oppose thermocapillary convection in the Ge‐Si system since Si, having the higher surface tension, is preferentially incorporated into the crystal. A set of experiments directly proving and partially quantifying the effect has been conducted under microgravity during a parabolic flight campaign by recrystallizing Ge‐Si mixtures of different compositions, between 3% and 9% Si, in a crucible with tracers to visualize the movement. Solutocapillary flow with initial flow rates in excess of 5.5 cm/s at the onset of crystallization was measured. A slight dependence of the flow velocity on the initial Si content has been found. Experiments on the ground showed the same effect but with overall smaller speeds; this difference can be explained by the additional action of solutal buoyancy convection. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

MOVPE growth of GaAs on Ge substrates by inserting a thin low temperature buffer layer

High quality GaAs layers have been grown by low pressure MOVPE on Ge(001) and Ge(001) 9° off oriented in [110] direction by using a thin low temperature (LT) GaAs layer. Investigations of the initial growth step were performed at different V/III ratios and temperatures. To show the good buffer layer quality solar cell structures were grown on off oriented n‐Ge(001) and n‐GaAs(001) substrates. The surface morphology was studied by atomic force microscopy which showed the step‐flow growth mode on 1.2 µm thick GaAs/Ge structures. The crystalline qualities of this structures and the smooth surface morphology were investigated by double crystal X‐ray diffraction (XRD) and atomic force microscopy (AFM). (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructural analysis of atomistic models of Si-rich amorphous silicon-germanium alloys

A detailed microstructural analysis of amorphous silicon-germanium alloys with Ge fraction ranging from 0.1 to 0.5 is performed by means of a numerical modeling technique. By substituting Ge atoms for Si atoms in the nanoporous paracrystalline network of amorphous silicon, several amorphous silicon-germanium structures have been generated. Our main aim in the present work is to study the effect of compositional heterogeneities on the structural properties of amorphous silicon-germanium alloys in comparison with the standard case, that of a homogeneous random distribution of the atoms. We have limited ourselves here to the borderline case, that of segregation of Ge atoms at the nanoscale. The microstructure of our structural models is analyzed by examining the macroscopic mass density, the intensity of X-ray diffraction, the pair distribution functions, the bond lengths and the coordination numbers within the first coordination shell of Si and Ge atoms. Our structural models account for the experimentally derived mass densities regardless of the Ge distribution pattern. They also account for the intense small-angle X-ray scattering observed for some amorphous silicon-germanium samples. The short-range compositional disorder, reflected in the bond lengths and the coordination numbers within the first coordination shell of Ge atoms, is found to be very sensitive to how these atoms are arranged in the alloys.     

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

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

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

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

Si–Ge–Sn alloys: From growth to applications

In this review article, we address key material parameters as well as the fabrication and application of crystalline GeSn binary and SiGeSn ternary alloys. Here, the transition from an indirect to a fundamental direct bandgap material will be discussed. The main emphasis, however, is put on the Si–Ge–Sn epitaxy. The low solid solubility of α-Sn in Ge and Si of below 1 at.% along with the large lattice mismatch between α-Sn (6.489 Å) and Ge (5.646 Å) or Si (5.431 Å) of about 15% and 20%, respectively, requires non-equilibrium growth processes. The most commonly used approaches, i.e. molecular beam epitaxy (MBE) and chemical vapor deposition (CVD), will be reviewed in terms of crucial process parameters, structural as well as optical quality and employed precursor combinations including Germanium hydrides, Silicon hydrides and a variety of Sn compounds like SnD₄, SnCl₄ or C₆H₅SnD₃. Special attention is devoted to the growth temperature window and growth rates being the most important growth parameters concerning the substitutional incorporation of Sn atoms into the Ge diamond lattice. Furthermore, the mainly CVD-driven epitaxy of high quality SiGeSn ternary alloys, allowing the decoupling of band engineering and lattice constant, is presented. Since achieving fundamental direct bandgap Sn-based materials strongly depends on the applied strain within the epilayers, ways to control and modify the strain are shown, especially the plastic strain relaxation of (Si)GeSn layers grown on Ge.Based on recently achieved improvements of the crystalline quality, novel low power and high mobility GeSn electronic and photonic devices have been developed and are reviewed in this paper. The use of GeSn as optically active gain or channel material with its lower and potentially direct bandgap compared to fundamentally indirect Ge (0.66 eV) and Si (1.12 eV) provides a viable solution to overcome the obstacles in both fields photonics and electronics. Moreover, the epitaxial growth of Sn-based semiconductors using CMOS compatible substrates on the road toward a monolithically integrated and efficient group IV light emitter is presented.     

Formation of Ge-diffusion-suppressed GaAs layers and InAs quantum dots on Ge/Si substrates

Crystal growth of GaAs layers and InAs quantum dots (QDs) on the GaAs layers was investigated on Ge/Si substrates using ultrahigh vacuum chemical vapor deposition. Ga-rich GaAs with anti-site Ga atoms grown at a low V/III ratio was found to suppress the diffusion of Ge into GaAs. S-K mode QD formation was observed on GaAs layers grown on Ge/Si substrates with Ga-rich GaAs initial layers, and improved photoluminescence from 1.3 μm-emitting InAs QDs was demonstrated.     

Defects in epitaxial layers of silicon-germanium grown on silicon substrates

Crystal defects of various kinds found in epitaxially grown Si/Ge alloy layers on Si substrate, may be either inherent to the material and originating from atomic radii misfit, or can be traced to the growth process and controlled or eliminated by varying its parameters. A network of slip lines, becoming more pronounced with increased Ge content, indicates plastic deformation resulting from partial relief of stresses during the high temperature growth process. Electron microprobe and X-ray diffraction analysis indicate some Ge segregation in the fault vicinity, and a slight anisotropy in the lattice constant expansion due to the Ge.     

Atomic order in magnetic Mn inclusions in Si crystals: XAS and TEM studies

A Si (1 0 0) crystal implanted with Mn⁺ ions, exhibiting ferromagnetic properties, was studied with XAS and TEM to examine the local atomic order around Mn atoms. The advantage of the XAS technique was its elemental selectivity, which allowed extracting information on the atomic surroundings of Mn atoms even at very low concentrations of this element, incapable of producing a signal in X-ray diffraction. It is very important to find out what is responsible for the ferromagnetism of this new class of materials. The knowledge of the location of Mn atoms in the Si crystal lattice is crucial in developing models of ferromagnetic interactions. The performed studies have proven beyond doubt that Mn atoms are not located randomly in the Si crystalline matrix but form Mn–Si clusters immersed in a strained Si matrix. Assuming the atomic order and dimensions of the cluster found through EXAFS and HRTEM, we have reproduced the electronic structure of Mn atoms by modeling the XANES spectrum in agreement with the experimental one.     

Structural properties of liquid Au–Si and Au–Ge alloys with deep eutectic region

Au–Si and Au–Ge alloys have a deep eutectic region around 19 at.% Si and 28 at.% Ge, respectively. The metallic glass was prepared by quenching around 25 at.% Si near the eutectic composition for the Au–Si alloys [2] which has stimulated many researchers to study on the structural properties of such liquid alloys. However their results were different from each other, which seems due to the experimental difficulties from heavy absorption of both X-ray and neutron beams by Au atom in diffraction experiments. X-ray diffraction measurements have been carried out for liquid Au–Si and Au–Ge alloys around the eutectic region by the transmission method using high-energy X-rays to investigate the atomic arrangements in the liquid state. From the temperature dependence of the observed structure factors, the partial pair correlation and the detailed atomic arrangements will be discussed by Reverse Monte Carlo analysis. The produced atomic arrangements around the eutectic region suggest a substitutional structure and also an increase in liquid density with decreasing temperature.     

Deposition of microcrystalline Ge films using hot-wire technique without toxic gases

To investigate the deposition of Ge films without toxic gas such as germane, we have studied the Ge films prepared by the hot-wire technique, which utilize the reaction between a Ge target and hydrogen atoms generated by the hot-wire decomposition of H₂ gas. The films deposited on Si substrate were microcrystalline Ge films and the mean crystallite size of the films increased from 13.3 to 24.8 nm with increasing the substrate temperature from 300 to 500 °C. Moreover, the deposition rate of Ge films deposited on Si substrate was higher than that of Ge films deposited on Corning 1737 substrate. It was found that the substrate temperature and the kind of substrate are key parameters for the preparation of microcrystalline Ge films by the hot-wire technique.     

Structure evolution of Zn cluster on Si (0 0 1) substrate for ZnO nanostructure growth

In this paper, Monte Carlo simulations are carried out for Zn cluster supported on a static Si (0 0 1) substrate to estimate the morphological evolution of self-catalysis growth of ZnO nanostructures. The tight-binding many-body potential and the Lennard–Jones potential are used to describe Zn–Zn and Zn–Si interactions, respectively. The dynamic processes of Zn cluster in the temperature field decomposing and wetting effects are visualized through the simulation. The Zn atomic aggregates that randomly disperse on the Si (0 0 1) substrate with different shapes, such as a dimer, trimer, multimer and atomic chain, would act as catalytic nucleation sites for the following growth of the ZnO nanostructure. This phenomenon provides a sound explanation for the formation of randomly orientated and diversified ZnO nanostructures on the Si (0 0 1) substrate.     

Study of growth and doping of semiconductor films by the method of computer simulation

The possibility of Computer Simulation Monte-Carlo Method for the study of growth and doping regularities of semiconductor films with diamond type lattice and for control of their parameters is considered. The events probabilities of isolation attachment and diffusion displacements of atoms on the growing surface of the basic material and doping impurities are compared. The periodic regional conditions on the boundary of the considered area are presented. It is shown the limitations of the computer simulation methods because of growth processes knowing level and computer possibility. The modeling calculations are made for growth and doping of one-component material films and for growth of two-component compounds. It can be noticed the connection between supersaturation, deposition temperature, time growth rate, surface film roughness (impurity atoms), capture coefficient, doping level, critical thickness of continuous films, defects density. Computer experimental results are compared with experimental data on growth and doping of Si, Ge, GaAs film with the various orientations from vapour or molecular beams in vacuum. The ways of further development of computer simulation method are discussed.     

Strain dependent growth of silicon on Ge/Si–C heterostructures

We report on structural investigations of strain dependent growth of Si on Ge/Si–C heterostructures. Very small islands of Ge were obtained by using a little C precoverage before the Ge deposition. These islands are visualized by scanning tunneling microscopy (STM) and the subsequent Si epitaxy is pursued. STM pictures taken upon some monolayers of Si epitaxy reveal an inhomogeneous growth mode, which leads to ditch like rings formed around the islands. Pictures of the following Si deposition suggest a strain dependent surface diffusion of Si until sufficient material has been deposited which then flattens the surface resulting in perfect epitaxial structures.     

Microstructural analysis of nanostructured amorphous silicon-germanium alloys: Numerical modeling

A detailed microstructural analysis of amorphous silicon-germanium alloys with germanium fraction ranging from 0.1 to 0.5 is performed by means of a numerical modeling technique. By substituting Ge atoms for Si atoms in nanoporous paracrystalline network of amorphous silicon, several amorphous silicon-germanium structures have been generated then relaxed. The main aim of our work is to study the effect of compositional heterogeneities on the structural properties of amorphous silicon-germanium alloys in comparison with the standard case, that of a homogeneous random distribution of the atoms. In the present work we envisage the two-phase amorphous silicon-germanium model proposed by Goerigk and Williamson to interpret their anomalous small-angle X-ray scattering measurements; it consists on a mixture of Ge-rich and Ge-poor domains at the nanoscale. The microstructure of our structural models is analyzed by examining the macroscopic mass density, the X-ray diffraction intensity, the radial distribution functions, the bond lengths and the coordination numbers within the first coordination shell of Si and Ge atoms.     

Characterization of thin‐film a‐Si:H/µc‐Si:H tandem solar cells on glass substrates

Techniques, such as photoluminescence (PL) and electron‐beam‐induced current (EBIC), have already proven their effectiveness and applicability for solar materials. Although, the methods are standard techniques for multicrystalline Si PV, their application to thin films is challenging and requires special adjustment and a careful selection of the measuring parameters. Here we report on the investigation of thin‐film tandem solar cells consisting of hydrogenated amorphous (a‐Si:H) and microcrystalline silicon (µc‐Si:H) on glass substrates. We observe a homogeneous spatial distribution of the PL signals caused by the dominance of the surface recombination. A typical PL spectrum exhibits sub‐band gap features of a‐Si:H. We relate the sub‐band‐gap spectral features mainly to transitions of carriers trapped in deep states. Observations on partially processed stacks support this supposition. PL is only detectable on the a‐Si:H layer, while EBIC signal is generated mainly in the µc‐Si:H layer. It is found out that the luminescence features of the thin a‐Si:H layer resemble those on bulk a‐Si:H.     

Analysis of ambient gas influence on silicon layers crystallized by means of LPE

Epitaxial growth of thin layers from the liquid phase can occur with the use of solutions saturated under different ambient gases. Most often this process takes place in a vacuum or gaseous atmosphere of hydrogen or argon. As the experimental data show, the morphology of crystallized layers is determined by the ambient type in which the process occurs.The cohesion energy responsible for epitaxial lateral deposition processes on the substrate surface depends on the surface free energy which is a measure of attraction of the solution atoms by substrate atoms. In the case of crystallization of an epitaxial lateral layer of Si on a substrate partially masked with dielectric, the chemical potentials of atoms in the neighboring phases (determining the interface evolution) are not without influence on the relaxation velocity of the saturated liquid phase, and on the horizontal and vertical growth rate.The aim of the investigation was to analyze experimentally the influence of the ambient gases used during the LPE growth on the cohesion of the Sn–Si solution with substrates applied for the lateral epitaxial growth of Si layers. This work presents comparative temperature analysis of the wetting angle of such surfaces as Si, SiO₂ and SiN_x by the Sn–Si solution.