Growth of GaAs nanowires on Si (111) for photovoltaic applications

The goal of this thesis is to master the synthesis of GaAs nanowires ensembles on Si for their application in solar cells. Semiconductor nanowires present promising characteristics for photovoltaic applications: they benefit from their longitudinal high aspect ratio geometry to enhance light absorption, minimize material consumption and efficiently collect the carriers. To fully unleash their potential, the following properties have to be controlled: number density, diameter and orientation. The latter is of utmost importance to have uniform junctions and to avoid leakages/shortcuts, whereas number density and diameter allow to tune light absorption and minimize material utilization. Our nanowires have been grown by molecular beam epitaxy (MBE), a well-known technique for the high crystalline quality and atomically sharp interfaces in thin film applications. Moreover, to develop a scalable technique and to avoid any possible contamination we used a self-assembly and self-catalyzed approach, which involves only Ga and As, without any patterning of the surface. In a first place we studied the occurrence of GaAs nanowires growth for different types of silicon oxides, such as thermal oxide, native oxide and hydrogen silsesquioxane (HSQ). We determined the critical thicknesses to achieve nanowire growth and investigated the influence of surface roughness. This comparison study lead us to choose native oxide as oxide of choice for GaAs nanowires growth on Si. With this type of oxide, reproducibility and uniformity of results outpaced the others. Successively we developed a simple technique to control native oxide thickness and characterized the chemical composition and wetting. Once the behavior of the oxide properties as a function of oxide thickness was clarified we studied their influence over nanowire growth. We found that impacted the overall possibility of nanowires growth and to control their orientation with respect to the substrate. The root cause of the change in growth morphology was identified to be in the different thermal stability of the oxides with different compositions, and the wetting properties. The understanding of the influence of the surface properties over nanowires nucleation was of paramount importance to achieve reproducible, uniform and scalable growth of vertical nanowires. Once full control over the substrate was achieved, we investigated the tailoring of diameter and density by growth conditions using the self-assembly of Ga droplets. We demonstrated an approach to tailor diameter-density distribution that minimize nanowires-array reflectivity. These results give a clear pathway on how to obtain fully controlled nanowires growth in terms of diameter, density and orientation, paving the way to the development of GaAs nanowires based solar cells on Si

Molecular beam epitaxy of InAs nanowires in SiO2 nanotube templates: challenges and prospects for integration of III-Vs on Si

Guided growth of semiconductor nanowires in nanotube templates has been considered as a potential platform for reproducible integration of III-Vs on silicon or other mismatched substrates. Herein, we report on the challenges and prospects of molecular beam epitaxy of InAs nanowires on SiO2/Si nanotube templates. We show how and under which conditions the nanowire growth is initiated by In-assisted vapor-liquid-solid growth enabled by the local conditions inside the nanotube template. The conditions for high yield of vertical nanowires are investigated in terms of the nanotube depth, diameter and V/III flux ratios. We present a model that further substantiates our findings. This work opens new perspectives for monolithic integration of III-Vs on the silicon platform enabling new applications in the electronics, optoelectronics and energy harvesting arena

Wetting of Ga on SiOx and Its Impact on GaAs Nanowire Growth

Ga-assisted growth of GaAs nanowires on silicon provides a path for integrating high-purity III-Vs on silicon. The nature of the oxide on the silicon surface has been shown to impact the overall possibility of nanowire growth and their orientation with the substrate. In this work, we show that not only the exact thickness, but also the nature of the native oxide determines the feasibility of nanowire growth. During the course of formation of the native oxide, the surface energy varies and results in a different contact angle of Ga droplets. We find that, only for a contact angle around 90 degrees (i.e., oxide thickness similar to 0.9 nm), nanowires grow perpendicularly to the silicon substrate. This native oxide engineering is the first step toward controlling the self-assembly process, determining mainly the nanowire density and orientation

Ga-assisted growth of GaAs nanowires on silicon, comparison of surface SiOx of different nature

Physical properties of surfaces are extremely important for initiation and nucleation of crystal growth, including nanowires. In recent years, fluctuations in surface characteristics have often been related to unreproducible growth of GaAs nanowires on Si by the Ga-assisted method. We report on a systematic study of the occurrence of GaAs nanowire growth on silicon by the Ga-assisted method for different kinds of silicon oxides: native, thermal and hydrogen silsesquioxane (HSQ). We find that success in achieving nanowires and the growth conditions such as gallium rate and substrate temperature depend mainly on the physical properties of the surface: oxide stoichiometry, oxide thickness and surface roughness. These results constitute a step further towards the integration of GaAs technology on the Si platform. (C) 2014 Elsevier B.V. All rights reserved

Tailoring the diameter and density of self-catalyzed GaAs nanowires on silicon

Nanowire diameter has a dramatic effect on the absorption cross-section in the optical domain. The maximum absorption is reached for ideal nanowire morphology within a solar cell device. As a consequence, understanding how to tailor the nanowire diameter and density is extremely important for high-efficient nanowire-based solar cells. In this work, we investigate mastering the diameter and density of self-catalyzed GaAs nanowires on Si(111) substrates by growth conditions using the self-assembly of Ga droplets. We introduce a new paradigm of the characteristic nucleation time controlled by group III flux and temperature that determine diameter and length distributions of GaAs nanowires. This insight into the growth mechanism is then used to grow nanowire forests with a completely tailored diameter-density distribution. We also show how the reflectivity of nanowire arrays can be minimized in this way. In general, this work opens new possibilities for the cost-effective and controlled fabrication of the ensembles of self-catalyzed III-V nanowires for different applications, in particular in next-generation photovoltaic devices

Visual Understanding of Light Absorption and Waveguiding in Standing Nanowires with 3D Fluorescence Confocal Microscopy

Semiconductor nanowires are promising building blocks for next generation photonics. Indirect proofs of large absorption cross sections have been reported in nanostructures with subwavelength diameters, an effect that is even more prominent in vertically standing nanowires. In this work we provide a three-dimensional map of the light around vertical GaAs nanowires standing on a substrate by using fluorescence confocal microscopy, where the strong long-range disruption of the light path along the nanowire is illustrated. We find that the actual long-distance perturbation is much larger in size than calculated extinction cross sections. While the size of the perturbation remains similar, the intensity of the interaction changes dramatically over the visible spectrum. Numerical simulations allow us to distinguish the effects of scattering and absorption in the nanowire leading to these phenomena. This work provides a visual understanding of light absorption in semiconductor nanowire structures, which is of high interest for solar energy conversion applications

Characterization and analysis of InAs/p-Si heterojunction nanowire-based solar cell

The growth of compound semiconductor nanowires on the silicon platform has opened many new perspectives in the area of electronics, optoelectronics and photovoltaics. We have grown a 1 x 1 mm(2) array of InAs nanowires on p-type silicon for the fabrication of a solar cell. Even though the nanowires are spaced by a distance of 800 nm with a 3.3% filling volume, they absorb most of the incoming light resulting in an efficiency of 1.4%. Due to the unfavourable band alignment, carrier separation at the junction is poor. Photocurrent increases sharply at the surrounding edge with the silicon, where the nanowires do not absorb anymore. This is further proof of the enhanced absorption of semiconductors in nanowire form. This work brings further elements in the design of nanowire-based solar cells

Characterization and analysis of InAs/p-Si heterojunction nanowire-based solar cell

The growth of compound semiconductor nanowires on the silicon platform has opened many new perspectives in the area of electronics, optoelectronics and photovoltaics. We have grown a 1 x 1 mm(2) array of InAs nanowires on p-type silicon for the fabrication of a solar cell. Even though the nanowires are spaced by a distance of 800 nm with a 3.3% filling volume, they absorb most of the incoming light resulting in an efficiency of 1.4%. Due to the unfavourable band alignment, carrier separation at the junction is poor. Photocurrent increases sharply at the surrounding edge with the silicon, where the nanowires do not absorb anymore. This is further proof of the enhanced absorption of semiconductors in nanowire form. This work brings further elements in the design of nanowire-based solar cells

Hybrid Semiconductor Nanowire-Metallic Yagi-Uda Antennas

We demonstrate the directional emission of individual GaAs nanowires by coupling this emission to Yagi-Uda optical antennas. In particular, we have replaced the resonant metallic feed element of the nanoantenna by an individual nanowire and measured with the microscope the photoluminescence of the hybrid structure as a function of the emission angle by imaging the back focal plane of the objective. The precise tuning of the dimensions of the metallic elements of the nanoantenna leads to a strong variation of the directionality of the emission, being able to change this emission from backward to forward. We explain the mechanism leading to this directional emission by finite difference time domain simulations of the scattering efficiency of the antenna elements. These results cast the first step toward the realization of electrically driven optical Yagi-Uda antenna emitters based on semiconductors nanowires

High Yield of GaAs Nanowire Arrays on Si Mediated by the Pinning and Contact Angle of Ga

GaAs nanowire arrays on Silicon offer great perspectives in the :optoeleetronics and solar cell industry. To fulfill this potential, gold-free growth in predetermined positions should be achieved. Ga-assisted growth of GaAs nano-wires in the form of array has been shown to be challenging and difficult to reproduce. In this work, we provide some of the key elements for obtaining a high yield of GaAs nanowires on patterned Si in a reproducible way: contact angle and pinning of the Ga droplet inside the apertures achieved by the modification of the surface properties of the nanoscale areas exposed to growth. As an example, an amorphous silicon layer between the crystalline substrate and the Oxide mask results in a contact angle around 90 degrees, leading to a high yield of vertical nanowires: Another example for tuning the Contact angle is anticipated, native oxide with controlled thickness. This work opens new perspectives for the rational and reproducible growth of GaAs nanowire arrays on silicon