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.     

Low temperature formation of multi-layered structures of ferromagnetic silicide Fe3Si and Ge

Low-temperature (<300 °C) molecular beam epitaxy of Fe₃Si/Ge was investigated. By optimizing growth conditions, Fe₃Si layers with a flat interface and good crystallinity were epitaxially grown on Ge(1 1 1) substrates. In addition, double heteroepitaxial growth of Fe₃Si/Ge on high quality Fe₃Si/Ge substrates was investigated. Reflective high-energy electron diffraction measurements suggested Fe₃Si and Ge layers were epitaxially grown on Fe₃Si/Ge substrates. However, transmission electron microscopy measurements indicated stacking faults formed in the intermediate Ge and top Fe₃Si layers. Improved crystallinity of the intermediate Ge layer is essential to realize high quality [Fe₃Si/Ge]₂ multi-layered structures.     

Evolution of Si0.8Ge0.2 quantum dots during Si encapsulation

Surface structure, determined by scanning tunneling microscopy (STM), surface morphology, determined by atomic force microscopy (AFM), and surface composition, determined by X-ray photoelectron spectroscopy (XPS) of 20.0 nm Si_0.8Ge_0.2 quantum dots formed at 800 °C and encapsulated with 0-10 nm of Si at 500 °C and 800 °C are presented. It is observed that the quantum dot surface morphology changes during the Si encapsulation at 800 °C by the smoothing of the quantum dots. The height of the quantum dots decreases faster than can be accounted for from the amount of Si deposited, indicating that there is movement of material out of the quantum dots during the encapsulation process. Encapsulation at 500 °C results in a retention of the quantum dot surface morphology with increased Ge segregation compared to Si encapsulation at 800 °C. We conclude that the changing surface morphology at 800 °C is not the result of Ge segregation but due to intermixing resulting from the tensile strain of Si depositing on SiGe.     

Surface and interfacial structural characterization of MBE grown Si/Ge multilayers

Si/Ge multilayer structures have been grown by solid source molecular beam epitaxy (MBE) on Si (1 1 1) and (1 0 0) substrates and were characterized by high-resolution X-ray diffraction (XRD), atomic force microscopy (AFM), high-depth-resolution secondary ion mass spectroscopy (SIMS) and cross-section high-resolution transmission electron microscopy (HRTEM). A reasonably good agreement has been obtained for layer thickness, interfacial structure and diffusion between SIMS and HRTEM measurements. Epitaxial growth and crystalline nature of the individual layer have been probed using cross-sectional HRTEM and XRD measurements. Surface and interface morphological studies by AFM and HRTEM show island-like growth of both Si and Ge nanostructures.     

Ordering of Ge nanocrystals using FIB nanolithography

Formation and ordering of Ge nanocrystals (NC) are studied on Si(0 0 1) and SiO₂/Si(0 0 1) substrates patterned by focused ion beam (FIB). In both cases we use a three step process consisting of FIB milling of hole patterns with various periodicities, ex-situ substrate cleaning to remove Ga contamination and Ge NC growth by molecular beam epitaxy (MBE). We show that Ge NC can be ordered between or inside the holes on patterned Si(0 0 1) substrates and inside the holes on patterned SiO₂/Si(0 0 1) substrates.     

L10 FePt thin films with [0 0 1] crystalline growth fabricated by SiO2 addition—rapid thermal annealing and dot patterning of the films

FePt films that have a high degree of order S in their L1₀ structure (S>0.90) and well-defined [0 0 1] crystalline growth perpendicular to the film plane were fabricated on thermally oxidized Si substrates by the addition of an oxide and successive rapid thermal annealing (RTA). The mechanism of L1₀ ordering and [0 0 1] crystalline growth perpendicular to the film plane arising through the oxide addition and RTA process is also discussed. The L1₀ ordering (S>0.90) and the [0 0 1] crystalline growth were achieved by (1) lowering the activation energy due to in-plane tensile stress and the initiation of L1₀ ordering at a low temperature, (2) [0 0 1] crystalline growth through in-plane tensile stress, and (3) enhancement of atomic diffusion via the addition of an oxide and the resultant lowering of the ordering temperature. Effect (1) was observed in the case of SiO₂ addition, effect (2) was generally observed in the case of oxide addition and the RTA process, and effect (3) was prominent in the case of ZnO addition. With the addition of ZnO, the L1₀ ordering started at below 400 °C and was completed at 500 °C. Finally, dot patterns were successfully fabricated down to a diameter of 15 nm using electron beam lithography, and the magnetic state of the dot pattern was observed by magnetic force microscopy.     

Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

XPS study of annealing induced effects on surface and interface electronic properties of Si/Ge nanostructures

The present study is focused on the influence of vacuum thermal treatment on surface/interface electronic properties of Si/Ge multilayer structures (MLS) characterized using X-ray photoelectron spectroscopy (XPS) technique. Desired [Si(5 nm)/Ge(5 nm)]_×10 MLS were prepared using electron beam evaporation technique under ultra high vacuum (UHV) conditions. The core-level XPS spectra of as-deposited as well as multilayer samples annealed at different temperatures such as 100 °C, 150 °C and 200 °C for 1 h show substantial reduction in Ge 2p peak integrated intensity, whereas peak intensity of Si 2p remains almost constant. The complete interdiffusion took place after annealing the sample at 200 °C for 5 h as confirmed from depth profiling of annealed MLS. The asymmetric behaviour in intensity patterns of Si and Ge with annealing was attributed to faster interdiffusion of Si into Ge layer. However, another set of experiments on these MLS annealed at 500 °C suggests that interdiffusion can also be studied by annealing the system at higher temperature for relatively shorter time duration.     

Enhanced formation of periodic arrays of low-resistivity NiSi nanocontacts on (0 0 1)Si0.7Ge0.3 by nanosphere lithography with a thin interposing Si layer

In this study, we demonstrated significant enhancement of the formation of low-resistivity NiSi nanocontacts with controlled size on (0 0 1)Si_0.7Ge_0.3 substrates by combining the nanosphere lithography with the use of a new Ni/a-Si bilayer nanodot structure. Low-resistivity NiSi with an average size of 78 nm was observed to be the only silicide phase formed in samples annealed at 350-800 °C. The presence of the interposing Si layer with appropriate thickness was found to effectively prevent Ge segregation and maintain the interface stability in forming NiSi nanocontacts on (0 0 1)Si_0.7Ge_0.3. As the annealing temperature was increased to 900 °C, amorphous SiO_x nanowires were observed to grow from silicide nanocontact regions. The NSL technique in conjunction with a sacrificial Si interlayer process promises to be applicable in fabricating periodic arrays of other low-resistivity silicide nanocontacts on Si_1−xGe_x substrates without complex lithography.     

In situ monitoring of nucleation and evolution of Ge nanodots on faintly oxidized Si(1 1 1) surfaces

We have investigated the nucleation and evolution of germanium (Ge) nanodot (ND)s taking place while depositing Ge onto the silicon (Si) (1 1 1) surfaces with ultra-thin Si oxide films by using ultra-high vacuum in situ high-resolution transmission electron microscopy in the profile-imaging geometry. Various types of growth phenomena such as nucleation, growth and coalescence of Ge NDs have successfully been observed. The results show that the growth phenomena of the Ge NDs are dramatically rapid after their size reaches the size of the critical nucleus. The critical nucleus size estimated from a model using the cohesive energy of the Ge NDs has been consistent with observed one.     

Nanoimprint lithography using IR laser irradiation

A new technique called “infrared laser-assisted nanoimprint lithography” was utilised to soften the thermoplastic polymer material mR-I 8020 during nanoimprint lithography. A laser setup and a sample holder with pressure and temperature control were designed for the imprint experiments. The polymer was spin coated onto crystalline Si <1 1 1> substrates. A prepatterned Si <1 1 1> substrate, which is transparent for the CO₂ laser irradiation, was used as an imprint stamp as well. It was shown, that the thermoplastic resist mR-I 8020 could be successfully imprinted using the infrared CW CO₂ laser irradiation (λ = 10.6 μm). The etching rate of the CO₂ laser beam irradiated mR-I 8020 resist film under O₂ RF (13.56 MHz) plasma treatment and during O₂ reactive ion beam etching was investigated as well.     

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.     

Crystal chemistry of layered carbide, Ti3(Si0.43Ge0.57)C2

 The crystal structure of a layered ternary carbide, Ti₃(Si_0.43Ge_0.57)C₂, was studied with single-crystal X-ray diffraction. The compound has a hexagonal symmetry with space group P6₃/mmc and unit-cell parameters a=3.0823(1) Å, c=17.7702(6) Å, and V=146.21(1) Å³. The Si and Ge atoms in the structure occupy the same crystallographic site surrounded by six Ti atoms at an average distance of 2.7219 Å, and the C atoms are octahedrally coordinated by two types of symmetrically distinct Ti atoms, with an average C-Ti distance of 2.1429 Å. The atomic displacement parameters for C and Ti are relatively isotropic, whereas those for A (=0.43Si+0.57Ge) are appreciably anisotropic, with U₁₁ (=U₂₂) being about three times greater than U₃₃. Compared to Ti₃SiC₂, the substitution of Ge for Si results in an increase in both A-Ti and C-Ti bond distances. An electron density analysis based on the refined structure shows that each A atom is bonded to 6Ti atoms as well as to its 6 nearest neighbor A site atoms, whether the site is occupied by Si or Ge, suggesting that these bond paths may be significantly involved with electron transport properties.     

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%.     

Modified growth of Ge quantum dots using C2H4 mediation by ultra-high vacuum chemical vapor deposition

C₂H₄ mediations were used to modify the Stranski-Krastanow growth mode of Ge dots on Si(0 0 1) at 550 °C by ultra-high vacuum chemical vapor deposition. With appropriate C₂H₄-mediation to modify the Si surface, the elongated Ge hut clusters can be transformed to highly uniform Ge domes with a high Ge composition at the core. These C₂H₄-mediated Ge dots, almost bounded by {1 1 3} facets, have an average diameter and height of 55 and 9 nm, respectively. We propose two major mechanisms to depict the formation of these C₂H₄-mediated Ge dots: (i) an almost hydrogen-passivated Si surface to limit the nucleation sites for dot formation, and (ii) the incorporation of Ge atoms, repelled by the C-rich areas, into the existing Ge dots. This work provides a useful scheme to tune the topography of Ge dots in an UHV/CVD condition for possible optoelectronic applications.     

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%.     

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.     

X-ray triple-axis diffractometry investigation of Si/SiGe/Si on silicon-on-insulator subjected to in situ low-temperature annealing

X-ray triple-axis diffractometry (XRTD) was used to characterize heterostructure Si/SiGe/Si on silicon-on-insulator (SOI) subjected to in situ low-temperature annealing. Crystallographic tilt, lattice constant and relaxation percentage were examined, respectively. Two peaks have been observed in (0 0 4) reciprocal lattice mappings (RLMs) of Si layers. The (0 0 4) RLMs indicate that Si cladding is in tensile strain. We have also found two peaks with different k_∥ and k_⊥ in (1 1 3) asymmetric RLMs of Si layers. It is deduced from comprehensive analyses on (0 0 4) and (1 1 3) RLMs that Ge diffusion and in-plane tensile strain lead to 2θ shift of the Si layers underneath SiGe layer in (0 0 4) RLMs. And the diffusion concentration of Ge accurately determined by XRTD is mole fraction 0.84%.     

Photoinduced effect in Ga-Ge-S based thin films

Glassy films of Ga₁₀Ge₂₅S₆₅ with 4 μm thickness were deposited on quartz substrates by electron beam evaporation. Photoexpansion (PE) (photoinduced increase in volume) and photobleaching (PB) (blue shift of the bandgap) effects have been examined. The exposed areas have been analyzed using perfilometer and an expansion of 1.7 μm (ΔV/V ≈ 30%) is observed for composition Ga₁₀Ge₂₅S₆₅ exposed during 180 min and 3 mW/cm² power density. The optical absorption edge measured for the film Ge₂₅Ga₁₀S₆₅ above and below the bandgap show that the blue shift of the gap by below bandgap photon illumination is considerable higher (ΔE_g = 440 meV) than ΔE_g induced by above bandgap illumination (ΔE_g = 190 meV). The distribution of the refraction index profile showed a negative change of the refraction index in the irradiated samples (Δn = −0.6). The morphology was examined using a scanning electron microscopy (SEM). The chemical compositions measured using an energy dispersive analyzer (EDX) indicate an increase of the oxygen atoms into the irradiated area. Using a Lloyd's mirror setup for continuous wave holography it was possible to record holographic gratings using the photoinduced effects that occur in them. Diffraction efficiency up to 25% was achieved for the recorded gratings and atomic force microscopy images are presented.     

Investigating the lateral motion of SiGe islands by selective chemical etching

SiGe islands grown by deposition of 10 monolayers of Ge on Si(0 0 1) at 740 °C were investigated by using a combination of selective wet chemical etching and atomic force microscopy. The used etchant, a solution consisting of ammonium hydroxide and hydrogen peroxide, shows a high selectivity of Ge over Si_xGe_1−x and is characterized by relatively slow etching rates for Si-rich alloys. By performing successive etching experiments on the same sample area, we are able to gain a deeper insight into the lateral displacement the islands undergo during post growth annealing.