Atypical reversed pressure-induced phase transformation in Ge nanowires.

Phase transformations of Ge under compression/decompression cycle at room temperature were studied in a diamond anvil cell (DAC) using in situ synchrotron x-ray diffraction, Raman spectroscopy and near infrared absorption techniques. Upon compression similar behavior is observed in nanowires and in bulk although a higher stability is observed in nanowires. The cubic-diamond phase (Ge-3C), the most energetically favorable phase, transforms into the ß-tin metallic phase at high pressure and the reverse Ge-ß-tin to Ge-3C transformation is generally inhibited by kinetics when pressure is released. While the transformation in Ge bulk leads mostly to Ge-ST12 phase, the loading/unloading cycle of Ge nanowires in DAC leads back to Ge-3C, exhibiting unprecedented size effects. A comprehensive characterization of the final states is described.

Si and Ge allotrope heterostructured nanowires: experimental evaluation of the thermal conductivity reduction.

We have studied the thermal conductivity of Ge and Si allotrope heterostructured nanowires (NWs) synthesized by phase transformation. The NWs are composed of successive hexagonal 2H and cubic diamond 3C crystal phases along the 〈111〉 axis. Using 3ω-scanning thermal microscopy on NWs embedded in a silica matrix, we present the first experimental evidence of thermal conductivity reduction in such allotrope 2H/3C heterostructured NWs. In Ge heterostructured 2H/3C NWs, similarly to homogeneous 3C NWs, we show a thermal conductivity reduction when the NW diameter decreases. In addition, in Si and Ge NWs, we observe a reduced thermal conductivity due to the heterostructuration 2H/3C. We evidence that the temperature of phase transformation, which influences the size and the number of 2H domains, can constitute an efficient parameter to tune the thermal conductivity.

Crystalline, Phononic, and Electronic Properties of Heterostructured Polytypic Ge Nanowires by Raman Spectroscopy.

Semiconducting nanowires (NWs) offer the unprecedented opportunity to host different crystal phases in a nanostructure, which enables the formation of polytypic heterostructures where the material composition is unchanged. This characteristic boosts the potential of polytypic heterostructured NWs for optoelectronic and phononic applications. In this work, we investigate cubic Ge NWs where small (∼20 nm) hexagonal domains are formed due to a strain-induced phase transformation. By combining a nondestructive optical technique (Raman spectroscopy) with density-functional theory (DFT) calculations, we assess the phonon properties of hexagonal Ge, determine the crystal phase variations along the NW axis, and, quite remarkably, reconstruct the relative orientation of the two polytypes. Moreover, we provide information on the electronic band alignment of the heterostructure at points of the Brillouin zone different from the one (Γ) where the direct band gap recombination in hexagonal Ge takes place. We demonstrate the versatility of Raman spectroscopy and show that it can be used to determine the main crystalline, phononic, and electronic properties of the most challenging type of heterostructure (a polytypic, nanoscale heterostructure with constant material composition). The general procedure that we establish can be applied to several types of heterostructures.

Novel heterostructured Ge nanowires based on polytype transformation.

We report on a strain-induced phase transformation in Ge nanowires under external shear stresses. The resulted polytype heterostructure may have great potential for photonics and thermoelectric applications. ⟨111⟩-oriented Ge nanowires with standard diamond structure (3C) undergo a phase transformation toward the hexagonal diamond phase referred as the 2H-allotrope. The phase transformation occurs heterogeneously on shear bands along the length of the nanowire. The structure meets the common phenomenological criteria of a martensitic phase transformation. This point is discussed to initiate an on going debate on the transformation mechanisms. The process results in unprecedented quasiperiodic heterostructures 3C/2H along the Ge nanowire. The thermal stability of those 2H domains is also studied under annealing up to 650 °C by in situ TEM.

Imaging Thermoelectric Properties at the Nanoscale.

Based on our previous experimental AFM set-up specially designed for thermal conductivity measurements at the nanoscale, we have developed and validated a prototype which offers two major advantages. On the one hand, we can simultaneously detect various voltages, providing, at the same time, both thermal and electrical properties (thermal conductivity, electrical conductivity and Seebeck coefficient). On the other hand, the AFM approach enables sufficient spatial resolution to produce images of nanostructures such as nanowires (NWs). After a software and hardware validation, we show the consistency of the signals measured on a gold layer on a silicon substrate. Finally, we demonstrate that the imaging of Ge NWs can be achieved with the possibility to extract physical properties such as electrical conductivity and Seebeck coefficient, paving the way to a quantitative estimation of the figure of merit of nanostructures.

High current density GaAs/Si rectifying heterojunction by defect free Epitaxial Lateral overgrowth on Tunnel Oxide from nano-seed.

Interest in the heteroepitaxy of GaAs on Si has never failed in the last years due to the potential for monolithic integration of GaAs-based devices with Si integrated circuits. But in spite of this effort, devices fabricated from them still use homo-epitaxy only. Here we present an epitaxial technique based on the epitaxial lateral overgrowth of micrometer scale GaAs crystals on a thin SiO2 layer from nanoscale Si seeds. This method permits the integration of high quality and defect-free crystalline GaAs on Si substrate and provides active GaAs/Si heterojunctions with efficient carrier transport through the thin SiO2 layer. The nucleation from small width openings avoids the emission of misfit dislocations and the formation of antiphase domains. With this method, we have experimentally demonstrated for the first time a monolithically integrated GaAs/Si diode with high current densities of 10 kA.cm(-2) for a forward bias of 3.7 V. This epitaxial technique paves the way to hybrid III-V/Si devices that are free from lattice-matching restrictions, and where silicon not only behaves as a substrate but also as an active medium.