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.     

The effects of incorporating fluorine in amorphous germanium-silicon alloy films

The structural, electrical and optical properties of rf sputtered fluorinated amorphous GeSi alloy films have been studied as a function of the amount of fluorine incorporated in the films. The results indicate an increased coordination in the binary semiconductor alloys with the increasing fluorine content. Fluorine attaches with extreme preference to silicon over germanium in the alloys. Due to this high preferential ratio, the increase in coordination on fluorination is much less than that observed in fluorinated amorphous silicon. The thermal stability of fluorinated alloys is found to be higher than similarly prepared hydrogenated samples.     

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.     

Radial distribution studies of glassy tellurium-silicon alloys

X-ray investigations of glassy tellurium-silicon alloys (Si content 10–40 at%) are described. Alloys with 13 to 27 at% Si were obtained in bulk form, non-crystalline samples with 10, 30, 33, 36 and 40 at% Si were obtained by rapid quenching from the melt by the splat-cooling technique. The interference functions and the radial distribution functions of all alloys show a great similarity. However, the positions of the maxima of the pair distribution function decrease continuously with growing Si content and lead to values which are similar to atomic distances in crystalline Te and Si₂Te₃. The areas of the first two peaks of the RDF, F₁ (rougnly 2) and F₂ (roughly 12), are compared with calculated areas derived from different structural models which are based on the short-range order in crystalline Te with a chain structure and in Si₂Te₃ with a tetrahedron configuration. An interstitial model with Si atoms in holes of Te chains and a random substitution model, where the Te atoms and the Si atoms have the same short-range order, both show a concentration dependence of the areas F₁ contrary to the experimental values. A structural model which assumes the tetrahedron configuration of Si₂Te₃ for Si atoms (coordination number N_Si = 4) and a coordination number N_Te = 2 for Te atoms can describe the short-range order of glassy TeSi alloys in the whole investigated concentration range with 10–40 at% Si.     

EXAFS studies of arsenic in amorphous silicon

Extended X-ray absorption fine structure measurements were used to determine nearest neighbor coordination numbers and distances for As in amorphous Si prepared by 100 keV As ion-implantation of single crystal Si. In the limit of low As concentration, the average As---Si coordination number was 3.2±0.1 and the As-to-Si distance was 2.37±0.02 Å, compared with 4 and 2.41±0.02 Å, respectively, for As in crystalline Si. It is concluded that 20% of the As atoms are fourfold coordinated and 80% are threefold coordinated in the amorphous Si, and that the lack of electrical doping by the fourfold coordinated As results from electron trapping by dangling bonds or other structural defects.     

Correlations between electronic structure of transition metal atoms and performance of high-k gate dielectrics in advanced Si devices

This paper develops a classification scheme for non-crystalline dielectrics that separates them into three groups with different amorphous morphologies, and identifies a linear scaling relationship between average bond ionicity and oxygen atom coordination. The classification scheme is applied to transition metal silicate and aluminate alloys and provides a structural model for molecular orbital, MO, calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. The MO calculations show that conduction band offset energies with respect to Si scale inversely with the energy difference between transition metal atomic n+1 s- and n d-states providing an important insight into the choice of alternative gate dielectrics for advanced Si devices.     

Impact of amorphous Ge thin layer at the amorphous Si/Al interface on Al-induced crystallization

We investigated the impact of an amorphous Ge (a-Ge) thin layer inserted at the amorphous Si (a-Si)/Al interface on Al-induced crystallization. In situ observation of the growth process clarified that the nucleation rate is drastically reduced by insertion of a-Ge, which led to increase in the average size of crystal grains. This was interpreted as resulting from decrease in the driving force of crystallization, mainly due to the larger solubility of Ge in Al than that of Si in Al. The obtained films were SiGe alloys with lateral distribution of Ge content, and its origin is discussed based on the two-step nucleation process.     

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.     

An anomalous X-ray structural study of an amorphous La55Al25Ni20 alloy with a wide supercooled liquid region

The atomic structures of amorphous La₅₅Al₂₅Ni₂₀ alloys which have a wide supercooled liquid region and a high reduced glass transition temperature have been studied using anomalous X-ray scattering (AXS) at the Ni K-absorption edge as well as the ordinary X-ray diffraction with Mo K radiation. The interference functions and the radial distribution functions were determined for the amorphous alloys as-quenched and after annealing at various temperatures and also for a fully crystallized sample. These systematic structural studies revealed a drastic change in Ni environment upon crystallization. The need for such atomic rearrangements around the Ni atoms during crystallization may be the reason why the amorphous phase is thermally stable.     

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.     

离子束溅射制备Si/Ge多层膜的结晶研究

采用离子束溅射制备Si/Ge多层膜,通过X射线小角衍射计算其周期厚度及各子层的厚度,用Raman光谱对Si/Ge多层膜的微观结构及Si子层的结构进行表征.结果表明,所制备的Si/Ge多层膜中,当Ge子层的厚度为6.2nm时,Si子层的结晶质量较好,表明适量的Ge含量有诱导Si结晶的作用.     

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).     

Structural investigation of amorphous and liquid Ge0.175Te0.825 by neutron scattering

The angular distribution of intensities of 1.003 Å neutrons scattered by an alloy of Ge_0.175Te_0.825 both in the amorphous and in the liquid state have been measured. The bulk amorphous sample, prepared by water quenching of the melt, has been examined at room temperature and just above the crystallization temperature T_x. The liquid sample has been examined at 400, 600 and 800°C. The analysis of the structure factors obtained from the corrected and scaled intensities indicates that the structural features of the amorphous sample are similar to those which would be expected if it were possible to cool the alloy to room temperature, while maintaining it in the liquid state. The analysis of the radical distribution functions, from Fourier inversion of the structure factors, indicates that a change of the coordination number n₁ from 2.43 to 3.25 occurs in passing from the amorphous to the liquid state at 400°C. This result has been interpreted in terms of coordination models. In the liquid state, it has been found that a model with fourfold coordinated Ge and threefold coordinated Te is consistent with n₁=3.25. The internal consistency of this model for the liquid state allows us to make a reasonable choice between the possibility of a 3 or 4 fold coordination for Ge in the glass. We conclude that a model based on four-fold coordinated Ge and twofold coordinated Te seems an appropriate representation for the coordination of the amorphous material.     

EXAFS study on poly-Si1−XGeX films prepared by reactive thermal CVD method

Extended X-ray absorption fine structure analyses were carried out on Si_1−XGe_X films of different thicknesses, prepared by the reactive thermal chemical vapor deposition (CVD) method. From a Rutherford backscattering measurement, the Ge fraction was found to be high near the substrate interface. The Ge coordination ratio, Ge–Ge bond length and Ge–Si bond length decreased with increasing film thickness. The Ge fraction dependences of these parameters were found to be different from the results of previous studies on Si_1−XGe_X films prepared by molecular beam epitaxy. Our results are considered to be caused by the local structure formation around the Ge atoms during the reactive thermal CVD process.     

Theoretical calculation of dense random packings of equal and non-equal sized hard spheres applications to amorphous metallic alloys

A model describing the structure of amorphous metallic alloys is proposed using a packing of non-equal-sized hard spheres. Models containing up to 1000 spheres were generated by computation. Hypotheses guiding the calculation are chosen in order to obtain a model as compact as possible and to take into account affinity between metal and metalloids: therefore two small spheres are not allowed to be in hard contact. This method of calculation is first tested by building up heaps of equal-sized spheres. Both the radial distribution function and the interference function are calculated for each model and the variations of these curves with the number of spheres are studied. In the case of two sizes of spheres heaps calculations are devoted to the study of the so-called ‘shoulder interference function’ which characterizes many amorphous alloys such as NiP, PdSi, etc. It is shown that the existence of such a shoulder depends on two parameters: the ratio of sphere diameters and the relative concentration of small and large spheres. These results are in good agreement with some recent experimental observations. This shoulder is well-marked when the diameter ratio reaches 10% and when the concentration in small spheres lies in the range 10–15%. In such a structure (e.g. amorphous NiP and PdSi alloys) it is observed that small spheres are always surrounded by nine large spheres such as P or Si atoms in crystalline Ni₃P or Pd₃Si. Large spheres, i.e. metallic atoms, form distorted icosahedra, the distortion of which varies from one to the other. The short-range order has a five-fold symmetry which is not compatible with any long-range order.     

The amorphous structure of immiscible Fe---Cu---Ag alloys

By means of facing target dc sputtering, an amorphous phase has been produced for immiscible Fe---Cu---Ag alloys at around the central concentration of the ternary phase diagram. The radial distribution function estimated from X-ray diffraction measurements indicates that a tetrahedron is the dominant structure unit and that the average coordination number is about 11. In the extended X-ray absorption fine structure radial structure function, a clear peak is detected at the nearest neighbor distance, but the peak intensity is weaker than those for binary crystalline Fe---Cu and Fe---Ag alloys and no clear peak is detectable at larger distances. A hard or soft sphere dense random packing model is appropriate for the amorphous structure in these immiscible alloys.     

Differential anomalous X-ray scattering studies of amorphous Cd59As41 and Cd26As74

The local structure of amorphous cadmium arsenide semiconducting films has been studied by differential anomalous X-ray scattering. Intensity measurements were carried out on two samples, containing 41 and 74 at.% As, in the vicinity of the absorption K edges of both constituents using synchrotron radiation. The computational procedure, similar to that proposed by Warren for an amorphous sample with more than one kind of atom, was applied to obtain the structural parameters from the experimental data. It has been found that atoms in the amorphous CdAs films remain almost tetrahedrally coordinated and that the investigated films are chemically ordered. The structural changes going from cadmium- to arsenic-rich composition have been revealed. The differential anomalous X-ray scattering technique proved to be effective, providing the evidence for the CdCd and AsAs near neighbour correlations in Cd₅₉As₄₁ and Cd₂₆As₇₄, respectively. The simulations of the differential radial distribution functions have shown that for the amorphous film containing 41 at.% As the distorted tetrahedral structure, intermediate between the CdAs and Si III type structures, is adequate to account for the experimental data. At 74 at.% As, the atomic arrangement can be described satisfactorily by the structural model based on the tetragonal CdAs₂ structure. The structural parameters obtained from the present study and those previously derived using the extended X-ray absorption fine structure and conventional large angle X-ray scattering techniques are compared.     

Small-angle X-ray scattering studies of a-Si1−xGex: H alloys

Small-angle X-ray scattering (SAXS) is used to study a-Si:H, a-Ge:H, and a-Si_1−xGe_x: H alloys prepared by plasma-enhanced CVD methods. These amorphous semiconductors show various types of scattering characteristics related to their composition, deposition method, and deposition conditions. For poor quality alloys at low scattering vectors, h, the scattering curve shows an I(h)h⁻² dependence, because of the fractal nature of the inhomogeneities present. Also, a-Ge:H shows these features. Therefore, it is concluded that the inhomogeneities arise principally from clustering of Ge atoms.     

On the structure of amorphous germanium and silicon

The simple microcrystallite model is used to calculate the diffraction and radial distribution functions for a variety of tetrahedrally coordinated crystal structures: diamond, wurtzite, Ge III and Si III — two high-pressure polytypes of Ge and Si — and two clathrate structures based on pentagonal dodecahedral units. Comparison with data for sputtered amorphous Ge suggests that the simple microcrystallite model is inadequate to fit diffraction data. A statistical or combination microcrystallite model may be more promising. Recent electron microscopic investigations of Rudee and Howie are also discussed.     

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.