In-plane and out-of-plane shape transitions of heteroepitaxially self-assembled nanostructures

In this work, shapes and shape transitions of several types of self-assembled heteroepitaxial nanostructures, as observed in in situ scanning tunneling microscopy experiments during growth, are examined in the framework of several equilibrium and kinetic models. In particular, heteroepitaxial TiSi₂ and CoSi₂ islands on Si(1 1 1) are shown to behave in accordance with generalized Wulff-Kaishew theorem of equilibrium strained and supported crystal shapes. More specifically, these silicide nanocrystals exhibit out-of-plane thickening shape transition by increasing their vertical aspect ratio with growth, as long as they are strained, and inverse (flattening) transition upon relaxation by misfit dislocations. On the other hand, heteroepitaxial Ge and CoSi₂ islands on Si(0 0 1) are well-known for their in-plane anisotropic elongation. Plausible energetic and kinetic reasons for such elongation, based on the unique nucleation features of Ge-hut/Si(0 0 1) and non-planar CoSi₂-hut/Si(0 0 1) interface, are discussed.     

Scanning tunneling microscopy observation of ultrathin epitaxial CoSi<Subscript>2</Subscript>(111) films grown at a high temperature

Scanning tunneling microscopy (STM) is used to study the basic laws of growth of ultrathin epitaxial CoSi₂(111) films with Co coverages up to 4 ML formed upon sequential deposition of Co and Si atoms taken in a stoichiometric ratio onto the Co–Si(111) surface at room temperature and subsequent annealing at 600–700°C. When the coverage of Co atoms is lower than ~2.7 ML, flat CoSi₂ islands up to ~3 nm high with surface structure 2 × 2 or 1 × 1 grow. It is shown that continuous epitaxial CoSi₂ films containing 3–4 triple Si–Co–Si layers grow provided precise control of deposition. CoSi₂ films can contain inclusions of the local regions with (2 × 1)Si reconstruction. At a temperature above 700°C, a multilevel CoSi₂ film with pinholes grows because of vertical growth caused by the difference between the free energies of the CoSi₂(111) and Si(111) surfaces. According to theoretical calculations, structures of A or B type with a coordination number of 8 of Co atoms are most favorable for the CoSi₂(111)2 × 2 interface.     

Thermal stability of nanoscale silver metallization in Ag/W/Co/Si(1 0 0) multilayer

In this work, we have studied thermal stability of nanoscale Ag metallization and its contact with CoSi₂ in heat-treated Ag(50 nm)/W(10 nm)/Co(10 nm)/Si(1 0 0) multilayer fabricated by sputtering method. To evaluate thermal stability of the systems, heat-treatment was performed from 300 to 900 °C in an N₂ ambient for 30 min. All the samples were analyzed by four-point-probe sheet resistance measurement (R_s), Rutherford backscattering spectrometry (RBS), X-ray diffractometry (XRD), and atomic force microscopy (AFM). Based on our data analysis, no interdiffiusion, phase formation, and R_s variation was observed up to 500 °C in which the Ag layer showed a (1 1 1) preferred crystallographic orientation with a smooth surface and R_s of about 1 Ω/□. At 600 °C, a sharp increase of R_s value was occurred due to initiation of surface agglomeration, WSi₂ formation, and interdiffusion between the layers. Using XRD spectra, CoSi₂ formed at the Co/Si interface preventing W silicide formation at 750 and 800 °C. Meantime, RBS analysis showed that in this temperature range, the W acts as a cap layer, so that we have obtained a W encapsulated Ag/CoSi₂ contact with a smooth surface. At 900 °C, the CoSi₂ layer decomposed and the layers totally mixed. Therefore, we have shown that in Ag/W/Co/Si(1 0 0) multilayer, the Ag nano-layer is thermally stable up to 500 °C, and formation of W-capped Ag/CoSi₂ contact with R_s of 2 Ω/□ has been occurred at 750-800 °C.     

Effect of Ni interlayer on stress level of CoSi2 films in Co/Ni/Si(1 0 0) bi-layered system

The effect of Ni interlayer on stress level of cobalt silicides was investigated. The X-ray diffraction patterns (XRD) show that low temperature formation of Co_1−xNi_xSi₂ solid solution was obtained while Ni interlayer was present in Co/Si system, which was confirmed by Auger electron spectrum (AES) and sheet resistance measurement. XRD was also used to measure the internal stress in CoSi₂ films by a 2θ_ψ − sin²ψ method. The result shows that the tensile stress in CoSi₂ films evidently decreased in Co/Ni/Si(1 0 0) system. The reduction of lattice mismatch, due to the presence of Ni in Co_xNi_1−xSi₂ solid solution, is proposed to explain this phenomenon.     

Photoelectron Si 2<Emphasis Type="Italic">p</Emphasis> spectra of ultrathin CoSi<Subscript>2</Subscript> layers formed on Si(100)2×1

Solid-phase formation of ultrathin CoSi₂ layers on Si(100)2×1 was studied using high-resolution (～140 meV) photoelectron spectroscopy with synchrotron radiation (hν=130 eV). The evolution of Si 2p spectra was recorded both under deposition of cobalt on the surface of samples maintained at room temperature and in the course of their subsequent annealing. It was shown that Co adsorption on Si(100)2×1 is accompanied by a loss of reconstruction of the original silicon surface while not bringing about the formation of a stable CoSi₂-like phase. As the amount of deposited cobalt continues to increase (up to six monolayers), a discontinuous film of the Co-Si solid solution begins to grow on the silicon surface coated by chemisorbed cobalt. The solid-phase reaction of CoSi₂ formation starts at a temperature close to 250°C and ends after the samples have been annealed to ～350°C.     

Structure transition of single-texture CoSi2 nanolayer grown by refractory-interlayer-mediated epitaxy method

In this investigation, the crystalline structure of a nanometric CoSi₂ layer, formed in heat treated Co/W_xTa_(1−x)/Si(1 0 0) systems, has been studied by XRD analysis. Careful measurements of the diffraction intensities revealed that temporary formation of a metastable diamond cubic structure of CoSi₂ phase, rather than its usual CaF₂ structure, was occurred. It has been shown that formation of this metastable structure depends on the kind of the applied interlayer in addition to the annealing temperature. Among the studied systems with x = 0, 0.25, 0.5, 0.75 and 1, the second and the last systems resulted in growing a (1 0 0) single-texture CoSi₂ layer with the preferred usual CaF₂ structure, a strained lattice parameter, and the best thermal stability (900-1000 °C).     

Co-silicide layers studied by Mössbauer spectroscopy and Rutherford backscattering spectroscopy

Co-silicides were prepared with several techniques, such as annealing of evaporated Co-layers on a Si-substrate (silicide surface layers) and annealing of Co-implanted Si (buried silicide layers). By adding some⁵⁷Co to the stable⁵⁹Co, the formation of the various Co-silicides could clearly be followed as a function of annealing temperature by means of Mössbauer spectroscopy. In the case of surface silicide layers, Co₂Si, CoSi and CoSi₂ were formed subsequently. In the case of buried layers however, CoSi₂ was the only crystalline phase that could be observed. In both cases, the CoSi₂ spectra showed an anomalous side resonance. Moreover, it was found that when⁵⁷Fe was implanted (instead of⁵⁷Co), a drastic increase in the intensity of this side resonance could be detected by CEMS.     

Growth of high quality CoSi2/Si - superstructures on Si (111)

Using a newly developed solid phase epitaxy technique (SPE) it is shown that ultrathin essentially pinhole-free CoSi₂ layers can be grown epitaxially on Si (111). These form the basis of a number of short period metal/semiconductor superlattices that have been grown by combining SPE-grown CoSi₂ with MBE-grown Si. Substrate temperatures for Si-MBE have to be chosen very low (≈ 350 °C) in order to avoid a roughening of the layers.     

Low temperature ion beam mixing of Co/Si systems

Co/Si systems were ion beam mixed at 77 K using a 100 keV Ar beam. The formation of different phases as a function of irradiation dose has been studied, using Mössbauer spectroscopy (MS) and Rutherford backscattering spectroscopy (RBS). It was found that Co₂Si, CoSi and CoSi₂ are formed subsequently in parallel layers. After high dose irradiation, a phase with stoichiometry Co∶Si equal to 1∶3 was observed, suggesting CoSi₃ has been formed. However, MS gave clear evidence that this phase consists of precipitates of CoSi₂ and Si. Finally, we found that the amount of mixing scales linearly with the square root of the fluence, with a mixing rate of 1.0×10⁴Å⁴.     

Estimation of changes in parameters of a crystal lattice and energy bands upon variation in the size of nanocrystals and nanofilms of silicides prepared by ion implantation

Changes in the parameters of the crystal lattice and energy bands of CoSi₂ nanofilms and nanocrystals formed in the surface Si layers by ion implantation combined with annealing are studied. It is shown that the band gap E _g of CoSi₂/Si(100) nanofilms with the thickness θ ≤ 40–50 Å is higher by ～0.1 eV than for “thick” films; in the case of nanocrystals, E _g is 0.3–0.4 eV higher than for macrocrystals.     

Surfactant-mediated growth of CoSi2 on Si(100)

Thin co-deposited CoSi₂ films grown at 500–600°C on Si(100) are studied by scanning tunneling microscopy (STM). With a Si rich deposition we observe initially the formation of elongated three-dimensional CoSi₂ islands. The use of one preadsorbed atomic layer of As as a surfactant results in a drastic increase of the island density. This effect appears to be a consequence of a decreased rate of surface diffusion of Co and Si. At higher coverages the roughness of the CoSi₂ film is reduced considerably by the surfactant. The results are discussed with regard to the method of allotaxy which allows the fabrication of buried silicide layers. Here, the requirements for small precipitates and high growth temperature can possibly be met more efficiently using As as a surfactant.     

First-principles study of cobalt silicide nanosheet and nanotubes: Stability and electronic properties

We perform first-principle calculations to study the geometric and electronic structures of cobalt silicide (CoSi₂) nanosheet and nanotubes. The structure of layered CoSi₂ is characterized by a CoSi₂ nanosheet, analogous to the (1 1 1) surface of CoSi₂ crystal. The strain energy involved in rolling up a CoSi₂ nanosheet to CoSi₂ nanotubes is very low. Both the CoSi₂ nanosheet and nanotubes are energetically stable. CoSi₂ nanotubes prefer to form bundles to further release strain energy. All CoSi₂ nanotubes exhibit uniformly metallicity and steady work functions, independent of tube chirality.     

Formations and morphological stabilities of ultrathin CoSi2 films

In this paper we investigate the formations and morphological stabilities of Co-silicide fihns using 1-8-nm thick Co layers sputter-deposited on silicon （100） substrates. These ultrathin Co-silicide films are formed via solid-state reaction of the deposited Co films with Si substrate at annealing temperatures from 450 ℃ to 850 ℃. For a Co layer with a thickness no larger than i nm, epitaxially aligned CoSi2 films readily grow on silicon （100） substrate and exhibit good morphological stabilities up to 600 ℃. For a Co layer thicker than 1 nm, polycrystalline CoSi and CoSi2 films are observed. The critical thickness below which epitaxially aligned CoSi2 film prevails is smaller than the reported critical thickness of the Ni layer for epitaxial alignment of NiSi2 on silicon （100） substrate. The larger lattice mismatch between the CoSi2 film and the silicon substrate is the root cause for the smaller critical thickness of the Co layer.     

Reactive epitaxy of cobalt disilicide on Si(100)

The growth of cobalt disilicide on the Si(100) surface by reactive epitaxy at T=350°C was studied within the 10–40 ML cobalt coverage range. A new method of mapping the atomic structure of the surface layer by inelastically scattered medium-energy electrons was employed. The films thus formed were shown to consist of CoSi₂(221) grains of four azimuthal orientations turned by 90° with respect to one another. This domain structure originates from substrate surface faceting by (111) planes, a process occurring during silicide formation. B-oriented CoSi₂(111) layers grow epitaxially on (111) facets.     

Composition and properties of nanoscale Si structures formed on the CoSi<Subscript>2</Subscript>/Si(111) surface by Ar<Superscript>+</Superscript> ion bombardment

The variations in the composition and structure of CoSi₂/Si(111) surface layers under Ar⁺ ion bombardment with subsequent annealing has been studied. It has been demonstrated that nanocluster phases enriched with Si atoms form on the CoSi₂ surface at low doses D ≤ 10¹⁵ cm^–2, and a pure Si nanofilm forms at high doses.     

Reactive epitaxy of cobalt disilicide on Si(111)

A study of the mechanism governing the initial stages in silicide formation under deposition of 1–10 monolayers of cobalt on a heated Si(111) 7×7 crystal is reported. The structural data were obtained by an original method of diffraction of inelastically scattered medium-energy electrons, which maps the atomic structure of surface layers in real space. The elemental composition of the near-surface region to be analyzed was investigated by Auger electron spectroscopy. Reactive epitaxy is shown to stimulate epitaxial growth of a B-oriented CoSi₂(111) film on Si(111). In the initial stages of cobalt deposition (1–3 monolayers), the growth proceeds through island formation. The near-surface layer of a CoSi₂(111) film about 30 Å thick does not differ in elemental composition from the bulk cobalt disilicide, and the film terminates in a Si-Co-Si monolayer triad.     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>x</Subscript>/Si(001) relaxed buffer layers grown by chemical vapor deposition at atmospheric pressure

Relaxed step-graded buffer layers of Si_1?xGe_x/Si(001) heterostructures with a low density of threading dislocations are grown through chemical vapor deposition at atmospheric pressure. The surface of the Si_1?xGe_x/Si(001) (x ～ 25%) buffer layers is subjected to chemical mechanical polishing. As a result, the surface roughness of the layers is decreased to values comparable to the surface roughness of the Si(001) initial substrates. It is demonstrated that Si_1?xGe_x/Si(001) buffer layers with a low density of threading dislocations and a small surface roughness can be used as artificial substrates for growing SiGe/Si heterostructures of different types through molecular-beam epitaxy.     

Chemical composition of matrix-embedded ternary II–VI nanocrystals derived from first- and second-order Raman spectra

A one- and multiphonon Raman scattering study is performed for an extensive set of CdS_1–xSe_x, Cd_1–yZn_yS, Cd_1–yZn_ySe, and CdSe_1–xTe_x nanocrystals to investigate the applicability of first- and second-order Raman spectra for the determination of the matrix-embedded ternary nanocrystal composition. For one-mode ternary systems both the LO and 2LO phonon frequencies in the Raman spectra are shown to be a good measure of the nanocrystal composition. For two-mode systems, the approaches based on the difference of the LO phonon frequencies (first-order Raman spectra) or double LO overtone and combination tone frequencies (second-order Raman spectra) as well as on the LO phonon band intensity ratios are analysed. The weak electron–phonon coupling in the II–VI nanocrystals and the polaron constant values for the nanocrystal sublattices are discussed.     

First-principles study of cobalt silicide nanosheet and nanotubes: Stability and electronic properties

We perform first-principle calculations to study the geometric and electronic structures of cobalt silicide (CoSi₂) nanosheet and nanotubes. The structure of layered CoSi₂ is characterized by a CoSi₂ nanosheet, analogous to the (1 1 1) surface of CoSi₂ crystal. The strain energy involved in rolling up a CoSi₂ nanosheet to CoSi₂ nanotubes is very low. Both the CoSi₂ nanosheet and nanotubes are energetically stable. CoSi₂ nanotubes prefer to form bundles to further release strain energy. All CoSi₂ nanotubes exhibit uniformly metallicity and steady work functions, independent of tube chirality.