Raman study of Si–Ge intermixing in Ge quantum rings and dots

The Ge/Si (1 0 0) nanostructures have been studied by atomic force microscopy (AFM) and Micro Raman optical spectroscopy. Two layers of Ge of total thickness 0.75 nm and Si cap with thickness 2.5 nm were deposited by the method of molecular beam epitaxy at the temperature range 640–700 °C. AFM shows both quantum dots and ring-shape Ge nanostructures. From the analysis of the intensity and energy shift of the Raman signal we have found that the average concentration of Ge decreases considerably from 44% to 27%, when the growth temperature increases, whereas the degree of strain relaxation remains roughly the same. This allows us to conclude that intermixing is a dominating mechanism for strain relaxation in processes of transformation of Ge quantum dots to quantum rings.     

Femtosecond pulsed laser deposition of Ge quantum dot growth on Si(1 0 0)-(2 × 1)

Ge quantum dots were grown on Si(1 0 0)-(2 × 1) by femtosecond pulsed laser deposition at various substrate temperatures using a femtosecond Ti:sapphire laser. In situ reflection high-energy electron diffraction and ex situ atomic force microscopy were used to analyze the film structure and morphology. The morphology of germanium islands on silicon was studied at different coverages. The results show that femtosecond pulsed laser deposition reduces the minimum temperature for epitaxial growth of Ge quantum dots to ∼280 °C, which is 120 °C lower than previously observed in nanosecond pulsed laser deposition and more than 200 °C lower than that reported for molecular beam epitaxy and chemical vapor deposition.     

Growth and optical properties of Ge/Si quantum dots formed on patterned SiO2/Si(0 0 1) substrates

Single and stacked layers of Ge/Si quantum dots were grown in SiO₂ windows patterned by electron-beam lithography on oxidized Si (0 0 1) substrates. The growth of a silicon buffer layer prior to Ge deposition is found to be an additional parameter for adjusting the Ge-dot nucleation process. We show that the silicon buffer layer evolves towards [1 1 3]-faceted pyramids, which reduces the area of the topmost (0 0 1) surface available for Ge nucleation. By controlling the top facet area of the Si buffer layers, only one dot per circular window and a high cooperative arrangement of dots on a striped window can be achieved. In stacked layers, the dot homogeneity can be improved through the adjustment of the Ge deposited amount in the upper layers. The optical properties of these structures measured by photoluminescence spectroscopy are also reported. In comparison with self-assembled quantum dots, we observed, both in single and stacked layers, the absence of the wetting-layer component and an energy blue shift, confirming therefore the dot formation by selective growth.     

Resonant Raman scattering by strained and relaxed germanium quantum dots

This paper reports on the results of resonant Raman scattering investigations of the fundamental vibrations in Ge/Si structures with strained and relaxed germanium quantum dots. Self-assembled strained Ge/Si quantum dots are grown by molecular-beam epitaxy on Si(001) substrates. An ultrathin SiO₂ layer is grown prior to the deposition of a germanium layer with the aim of forming relaxed germanium quantum dots. The use of resonant Raman scattering (selective with respect to quantum dot size) made it possible to assign unambiguously the line observed in the vicinity of 300 cm^?1 to optical phonons confined in relaxed germanium quantum dots. The influence of confinement effects and mechanical stresses on the vibrational spectra of the structures with germanium quantum dots is analyzed.     

Resonant Raman scattering of discrete hole states in self-assembled Si/Ge quantum dots

We report the first resonant electronic Raman spectroscopy study of discrete electronic transitions within small p-doped self-assembled Si/Ge quantum dots (QDs). A heavy hole (hh) to light hole (lh) Raman transition with a dispersionless energy of 105 meV and a resonance energy of the hh states to virtually localised electrons at the direct band gap of 2.5 eV are observed. The hh–lh transition energy shifts to lower values with increasing annealing temperature due to significant intermixing of Si and Ge in the QDs. Structural parameters of the small Si/Ge dots have been determined and introduced into 6-band k·p valence band structure calculations. Both the value of the electronic Raman transition of localised holes as well as the resonance energy at the E₀ gap are in excellent agreement with the calculations.     

Structure and photoluminescence study of type-II GaAs quantum wires and dots grown on nano-faceted (3 1 1)A surface

(3 1 1)A GaAs/AlAs corrugated superlattices (CSLs) and satellite (3 1 1)B and (1 0 0) SLs were studied using Raman spectroscopy, high-resolution transmittance electron microscopy (HRTEM) and photoluminescence (PL). The thickness of GaAs layers was varied from 1 monolayer (ML) to 10 ML, the thickness of AlAs barriers was 10 ML in (3 1 1) direction. The strongest modification of the Raman spectra is found for the case of partial (<1 nm) GaAs filling of the AlAs surface. The calculated and experimental Raman spectra demonstrated a good agreement for both complete (1 nm) and partial (<1 nm) GaAs filling of the AlAs surface. According to Raman and HRTEM data, in the case of partial filling of (3 1 1)A AlAs surface, GaAs forms quantum well wires of finite length (quantum dots). A drastic difference of PL from grown side-by-side (3 1 1)A and (3 1 1)B SLs was observed. A strong room temperature PL in the green–yellow spectral region was observed in GaAs/AlAs (3 1 1)A CSLs containing GaAs type-II quantum dots.     

Optical phonons in Ge quantum dots obtained on Si(111)

The Raman light scattering from optical phonons of Ge quantum dots grown by molecular beam epitaxy on a Si(111) surface is studied. A series of Raman lines related to the quantization of phonon spectrum is observed. It is shown that phonon frequencies are adequately described in terms of the elastic properties and the dispersion of the optical phonons of bulk Ge. The strain experienced by the Ge quantum dots is estimated.     

Ge quantum dots growth on nanopatterned Si(0 0 1) surface: Morphology and stress relaxation study

The self-organized growth of germanium quantum dots on square nanopatterned Si(0 0 1) substrates is investigated by scanning tunnelling microscopy (STM) and grazing incidence X-ray diffraction (GIXRD) techniques. A regular surface patterning in the 10-100 nm period range is obtained by etching an interface dislocation network obtained by the controlled molecular bonding of Si substrates. The depth of the silicon surface profile is increased by a double etching process. Growth experiments are performed by solid source molecular beam epitaxy (MBE), and for deep trenches, germanium growth conditions are optimized to obtain one Ge dot per Si mesa. It is shown that the trench depth and the mesa profile strongly affect the dot size and its coincidence with the initial regular surface network. Anomalous GIXRD measurements are performed to highlight the Ge elastic relaxation and intermixing during heteroepitaxial growth. We report a significant modification in the stress state of Ge dots as a function of thermal annealing after growth.     

Optical properties of arrays of Si nanopillars on the (1 0 0) surface of crystalline Si

We studied Si nanopillars arrays interesting for potential applications in both photonics and electronics. Two types of the Si nanopillars arrays were investigated. The first type is a regular array (square lattice with the spacing of 270 nm) made up of nanopillars with diameters of 60–70 nm (non-quantum nanopillars). Polarized reflection spectra displaying photonic band gap features and the corresponding photonic band structures were studied. The second type is a non-regular array made up of nanopillars with diameters of 10–20 nm (quantum nanopillars). Enhancement of the optical phonon Raman band, change of selection rules and a low-frequency shift of 0.5 cm⁻¹ of the band corresponding to the quantum size effect in Si cylinders with average diameter 15 nm were observed for the quantum nanopillars.     

Optical properties of Stranski–Krastanov grown three-dimensional Si/Si1−xGex nanostructures

Detailed Raman and photoluminescence (PL) measurements are reported for Si/Si_1−xGe_x nanostructures grown by molecular beam epitaxy under near Stranski–Krastanov (S–K) growth mode conditions. In samples with x ranging from 0.096 to 0.53, we observe that an increase in the Raman signal related to Ge–Ge vibrations correlates with (i) a red shift in the PL peak position, (ii) an increase in the activation energy of PL thermal quenching, and (iii) an increase in the PL quantum efficiency. The results indicate that for x>0.5 Ge atoms form nanometer size clusters with a nearly pure Ge core surrounded by a SiGe shell. Time-resolved PL measurements reveal a stretched-exponential long-lived PL component that is associated with compositional and dimensional fluctuations in the SiGe dots.     

Vibrational density of states of hen egg white lysozyme

The resonant Raman scattering in GeSi/Si structures with GeSi quantum dots has been analyzed. These structures were formed at various temperatures in the process of molecular-beam epitaxy. It has been shown that Raman scattering spectra recorded near resonances with the E₀ and E₁ electronic transitions exhibit the lines of Ge optical phonons whose frequencies differ significantly from the corresponding values in bulk germanium. In the structures grown at low temperatures (300–400°C), the phonon frequency decreases with increasing excitation energy. This behavior is attributed to Raman scattering, which is sensitive to the size of quantum dots, and shows that quantum dots are inhomogeneous in size. In the structures grown at a higher temperature (500°C), the opposite dependence of the frequency of Ge phonons on excitation energy is observed. This behavior is attributed to the competitive effect of internal mechanical stresses in quantum dots, the localization of optical photons, and the mixing of Ge and Si atoms in structures with a bimodal size distribution of quantum dots.     

Mechanism for coarsening of P-mediated Ge quantum dots during in-situ annealing

The coarsening of phosphorus-mediated Ge quantum dots (QDs) on Si(0 0 1) during in-situ annealing at 550 °C is studied. In-situ annealing makes the as-grown sample morphology be remarkably changed: the larger dots are formed and the dot density is greatly reduced. The results of chemical etching and Raman spectra reveal that the incorporation of Ge atoms which originate from the diminishing dots, rather than substrate Si atom incorporation is responsible for the dot coarsening at the incipient stage of in-situ annealing. Besides, Raman spectra suggest that the larger dots formed during in-situ annealing are dislocated, which was confirmed by cross-sectional high-resolution electron microscopy observation. Through the generation of dislocations, the strain in the dots is relaxed by about 50%.     

Simulations of germanium epitaxial growth on the silicon (1 0 0) surface incorporating intermixing

We present kinetic lattice Monte Carlo simulations of Ge deposition onto a reconstructed Si (1 0 0) surface. We account for the exchange of Ge with Si atoms in the substrate, considering two different exchange mechanisms: a dimer exchange mechanism whereby Ge–Ge dimers on the surface become intermixed with substrate Si atoms, and the exchange of Ge atoms below the surface to relieve misfit strain. We examine how Si–Ge exchange affects the interface between the materials when the growth simulations are done at different temperatures.     

SiH4 adsorption on SiGe(0 0 1)

The adsorption process of silane (SiH₄) on a SiGe(0 0 1) surface has been investigated by using infrared absorption spectroscopy in a multiple internal reflection geometry. We have observed that SiH₄ dissociatively adsorbs on a SiGe(0 0 1) surface at room temperature to generate Si and Ge hydrides. The dissociation of Si- and Ge-hydride species is found to strongly depend on the Ge concentration of the SiGe crystal. At a low Ge concentration of 9%, Si monohydride (SiH) and dihydride (SiH₂) are preferentially produced as compared to the higher Si hydride, SiH₃. At higher Ge concentrations of 19%, 36%, on the other hand, monohydrides of SiH and GeH and trihyderide SiH₃ are favorably generated at the initial stage of the adsorption. We interpret that when SiH₄ adsorbs on the SiGe surface, hydrogen atoms released from the SiH₄ molecule stick onto Ge or Si sites to produce Si or Ge monohydrides and the remaining fragments of -SiH₃ adsorb both on Si and Ge sites. The SiH₃ species is readily decomposed to lower hydrides of SiH and SiH₂ by releasing H atoms at low Ge concentrations of 0% and 9%, while the decomposition is suppressed by Ge in cases of 19% and 36%.     

First-principles study of adsorption and diffusion on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces

Using first-principles total-energy calculations, we have investigated the adsorption and diffusion of Si and Ge adatoms on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces. The dimer vacancy lines on Ge/Si(0 0 1)-(2 × 8) and the alternate S_A and rebonded S_B steps on Ge/Si(1 0 5)-(1 × 2) are found to strongly influence the adatom kinetics. On Ge/Si(0 0 1)-(2 × 8) surface, the fast diffusion path is found to be along the dimer vacancy line (DVL), reversing the diffusion anisotropy on Si(0 0 1). Also, there exists a repulsion between the adatom and the DVL, which is expected to increase the adatom density and hence island nucleation rate in between the DVLs. On Ge/Si(1 0 5)-(1 × 2) surface, the overall diffusion barrier of Si(Ge) along direction is relative fast with a barrier of ∼0.83(0.61) eV, despite of the large surface undulation. This indicates that the adatoms can rapidly diffuse up and down the (1 0 5)-faceted Ge hut island. The diffusion is also almost isotropic along [0 1 0] and directions.     

Ge(5 × 5) as a wetting layer on Si(1 1 1)

Ab initio total energy methods are used to investigate the effects on a Ge(1 1 1)-5 × 5 surface of the lateral compressive stress that would be due to a Si substrate, and the effects of intermixing at the interface with the substrate. The effects of stress due to the lattice mismatch between Si and Ge are studied on a Ge slab by changing the lattice constant in the surface plane from that of experimental bulk diamond Ge to that of Si. When this is done the height difference of the Ge adatoms in the faulted half-cell from those in the unfaulted half is accentuated. Effects on the Ge surface due to the presence of the Si-Ge interface were studied using a thin Ge layer on a Si substrate. The presence of the substrate leads to corrugations with significant height differences appearing among the faulted adatoms. The energetics of intermixing were investigated for Si-Ge single atom interchanges. Additional corrugations resulted from the shortened bondlengths due to the Si impurity in the wetting layer.     

Raman scattering of Ge dot superlattices

Self-organised Ge dot superlattices grown by molecular beam epitaxy of Ge and Si layers utilizing Stranski-Krastanov growth mode were investigated by Raman spectroscopy. An average size of Ge quantum dots was obtained from transmission electron microscopy measurements. The strain and interdiffusion of Ge and Si atoms in Ge quantum dots were estimated from the analysis of frequency positions of optical phonons observed in the Raman spectra. Raman scattering by folded longitudinal acoustic phonons in the Ge dot superlattices was observed and explained using of elastic continuum theory. Received 25 January 2000     

Controlling emission wavelength from InAs self-assembled quantum dots on InP (0 0 1) during MOCVD

We studied the growth of InAs quantum dots on InP (0 0 1) substrates in a low-pressure metalorganic chemical vapor deposition by using a so-called InP ‘double-cap’ procedure. With double-capping, a photoluminescence spectrum is modified into a series of multiple peaks, where the emission peaks arise from several quantum dot families with different heights changing in a step of integer number of an InAs monolayer. Cross-sectional transmission electron micrograph observations revealed that the shape of double-capped dots is dramatically changed into a thin plate-like shape with extremely flat upper and lower interfaces, being consistent with our interpretation of the photoluminescence spectrum. We showed that the procedure was extremely useful for controlling the emission wavelength from quantum dots in an InAs/InP (0 0 1) system.     

Phonons in Ge/Si superlattices with Ge quantum dots

Ge/Si superlattices containing Ge quantum dots were prepared by molecular beam epitaxy and studied by resonant Raman scattering. It is shown that these structures possess vibrational properties of both two-and zero-dimensional objects. The folded acoustic phonons observed in the low-frequency region of the spectrum (up to 15th order) are typical for planar superlattices. The acoustic phonon lines overlap with a broad emission continuum that is due to the violation of the wave-vector conservation law by the quantum dots. An analysis of the Ge and Ge-Si optical phonons indicates that the Ge quantum dots are pseudoamorphous and that mixing of the Ge and Si atoms is insignificant. The longitudinal optical phonons undergo a low-frequency shift upon increasing laser excitation energy (2.54–2.71 eV) because of the confinement effect in small-sized quantum dots, which dominate resonant Raman scattering.     

Growth of (√3 × √3)-Ag and (1 1 1) oriented Ag islands on Ge/Si(1 1 1) surfaces

We have studied the growth of Ag on Ge/Si(1 1 1) substrates. The Ge/Si(1 1 1) substrates were prepared by depositing one monolayer (ML) of Ge on Si(1 1 1)-(7 × 7) surfaces. Following Ge deposition the reflection high energy electron diffraction (RHEED) pattern changed to a (1 × 1) pattern. Ge as well as Ag deposition was carried out at 550 °C. Ag deposition on Ge/Si(1 1 1) substrates up to 10 ML has shown a prominent (√3 × √3)-R30° RHEED pattern along with a streak structure from Ag(1 1 1) surface. Scanning electron microscopy (SEM) shows the formation of Ag islands along with a large fraction of open area, which presumably has the Ag-induced (√3 × √3)-R30° structure on the Ge/Si(1 1 1) surface. X-ray diffraction (XRD) experiments show the presence of only (1 1 1) peak of Ag indicating epitaxial growth of Ag on Ge/Si(1 1 1) surfaces. The possibility of growing a strain-tuned (tensile to compressive) Ag(1 1 1) layer on Ge/Si(1 1 1) substrates is discussed.