In-Situ Transmission Electron Microscopy Observation of Germanium Growth on Freestanding Graphene: Unfolding Mechanism of 3D Crystal Growth During Van der Waals Epitaxy.

Breakthroughs in cutting-edge research fields such as hetero-integration of materials and the development of quantum devices are heavily bound to the control of misfit strain during heteroepitaxy. While remote epitaxy offers one of the most intriguing avenues, demonstrations of functional hybrid heterostructures are hardly possible without a deep understanding of the nucleation and growth kinetics of 3D crystals on graphene and their mutual interactions. Here, the kinetics of such processes from real-time observations of germanium (Ge) growth on freestanding single layer graphene (SLG) using in-situ transmission electron microscopy are unraveled. This powerful technique provides a unique opportunity to observe new and yet unexplored phenomena, which are not accessible to the standard ex situ characterizations. Through direct observations, remote interactions are elucidated between Ge crystals through the graphene layer in double heterostructures of Ge/graphene/Ge. Notably, the data show real-time evidence of vertical Ge atoms diffusion through the graphene layer. This phenomenon is attributed to the remote interactions of Ge atoms through the graphene lattice, due to its interatomic interaction transparency. Additionally, key mechanisms governing nucleation and initial growth in graphene were systematically determined. These findings enlighten the growth mechanism of graphene and provide a new pathway for disruptive hybrid semiconductor-graphene devices.

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.

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.

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.