The formation mechanisms of epitaxial GaN nanowires grown within a self-induced approach by molecular-beam epitaxy have been investigated at the onset of the nucleation process by combining in situ reflection high-energy electron-diffraction measurements and ex situ high-resolution transmission electron microscopy imaging. It is shown that the self-induced growth of GaN nanowires on the AlN buffer layer is initially governed by the nucleation of dislocation-free coherent islands. These coherent islands develop through a series of shape transitions from spherical caps through truncated to full pyramids in order to elastically relieve the lattice-mismatch-induced strain. A strong correlation between the subsequent process of plastic relaxation and the final shape transition from full pyramids toward the very first nanowires is found. The experimental critical radius at which the misfit dislocation nucleates is in very good agreement with the theoretical critical radius for the formation of the misfit dislocation in full pyramids, showing that the plastic relaxation process does take place within full pyramids: this critical size corresponds to the initial radius of the very first nanowires. We associate the plastic relaxation of the lattice-mismatch-induced strain occurring within full pyramids with a drastic change in their total free energy: this gives rise to a driving force for the shape transition toward the very first nanowires, which is mainly due to the anisotropy of surface energy.
2 March 2016 in The Journal of Physical Chemistry C
The polar nature of the wurtzite crystalline structure of GaN and ZnO results in the existence of a spontaneous electric polarization within these materials and their associated alloys (Ga,Al,In)N and (Zn,Mg,Cd)O. The polarity has also important consequences on the stability of the different crystallographic surfaces, and this becomes especially important when considering epitaxial growth. Furthermore, the internal polarization fields may adversely affect the properties of optoelectronic devices but is also used as a potential advantage for advanced electronic devices. In this article, polarity-related issues in GaN and ZnO are reviewed, going from theoretical considerations to electronic and optoelectronic devices, through thin film, and nanostructure growth. The necessary theoretical background is first introduced and the stability of the cation and anion polarity surfaces is discussed. For assessing the polarity, one has to make use of specific characterization methods, which are described in detail. Subsequently, the nucleation and growth mechanisms of thin films and nanostructures, including nanowires, are presented, reviewing the specific growth conditions that allow controlling the polarity of such objects. Eventually, the demonstrated and/or expected effects of polarity on the properties and performances of optoelectronic and electronic devices are reported. The present review is intended to yield an in-depth view of some of the hot topics related to polarity in GaN and ZnO, a fast growing subject over the last decade.
As an abundant and non-toxic wide band gap semiconductor with a high electron mobility, ZnO in the form of nanowires (NWs) has emerged as an important electron transporting material in a vast number of nanostructured solar cells. ZnO NWs are grown by low-cost chemical deposition techniques and their integration into solar cells presents, in principle, significant advantages including efficient optical absorption through light trapping phenomena and enhanced charge carrier separation and collection. However, they also raise some significant issues related to the control of the interface properties and to the technological integration. The present review is intended to report a detailed analysis of the state-of-the-art of all types of nanostructured solar cells integrating ZnO NWs, including extremely thin absorber solar cells, quantum dot solar cells, dye-sensitized solar cells, organic and hybrid solar cells, as well as halide perovskite-based solar cells.
The formation mechanisms of GaN nanowires grown on a SiN amorphous interlayer within a self-induced approach by molecular beam epitaxy have been investigated by combining in situ reflection high-energy electron-diffraction measurements with ex situ high-resolution transmission electron microscopy imaging. It is found that GaN initially nucleates as spherical cap-shaped islands with a wetting angle of . Subsequently, these islands coarsen and undergo a shape transition toward the nanowire morphology at an experimental critical radius of 5 nm. As the epitaxial constraint is very weak on an amorphous interlayer, the equivalent Laplace pressure due to the effects of surface stress has been taken into account. Analytical and finite-element method calculations show that the Laplace pressure results at the nanoscale dimensions in significant volume elastic strain in both spherical caps and nanowires. From thermodynamic considerations, it is revealed that the related strain energy density is slightly in favor of the shape transition toward the nanowire geometry owing to its higher ability to relieve the strain. Nevertheless, the anisotropy of surface energy is an even stronger driving force, since the nanowires are composed of - and -planes with very low surface energies. It is deduced that an energy barrier does exit for the shape transition and may be related to edge effects, resulting in a growth condition-dependent critical radius.