Evolution of Cu-In Catalyst Nanoparticles under Hydrogen Plasma Treatment and Silicon Nanowire Growth Conditions.

We report silicon nanowire (SiNW) growth with a novel Cu-In bimetallic catalyst using a plasma-enhanced chemical vapor deposition (PECVD) method. We study the structure of the catalyst nanoparticles (NPs) throughout a two-step process that includes a hydrogen plasma pre-treatment at 200 °C and the SiNW growth itself in a hydrogen-silane plasma at 420 °C. We show that the H2-plasma induces a coalescence of the Cu-rich cores of as-deposited thermally evaporated NPs that does not occur when the same annealing is applied without plasma. The SiNW growth process at 420 °C induces a phase transformation of the catalyst cores to Cu7In3; while a hydrogen plasma treatment at 420 °C without silane can lead to the formation of the Cu11In9 phase. In situ transmission electron microscopy experiments show that the SiNWs synthesis with Cu-In bimetallic catalyst NPs follows an essentially vapor-solid-solid process. By adjusting the catalyst composition, we manage to obtain small-diameter SiNWs-below 10 nm-among which we observe the metastable hexagonal diamond phase of Si, which is predicted to have a direct bandgap.

Large Area Radial Junction Silicon Nanowire Solar Mini-Modules.

In this work, we introduce the demonstration of 5 × 5 cm2 mini-modules based on radial junction silicon nanowire (RJ SiNW) devices grown by plasma-assisted vapor-liquid-solid (VLS) technique. The mini-modules are obtained thanks to an industrial laser scribing technique. The electrical parameters have been highlighted to address the performance of these devices and perspectives towards competitive RJ SiNW solar modules. Moreover, electroluminescence (EL) measurements were also conducted to assess the uniformity of the fabricated mini-modules. In addition, the structural characterization of solar cells and laser scribed lines has been assessed by scanning electron microscopy (SEM). The challenges and perspectives are also discussed.

Plasma nanotexturing of silicon surfaces for photovoltaics applications: influence of initial surface finish on the evolution of topographical and optical properties.

Using a plasma to generate a surface texture with feature sizes on the order of tens to hundreds of nanometers ("nanotexturing") is a promising technique being considered to improve efficiency in thin, high-efficiency crystalline silicon solar cells. This study investigates the evolution of the optical properties of silicon samples with various initial surface finishes (from mirror polish to various states of micron-scale roughness) during a plasma nanotexturing process. It is shown that during said process, the appearance and growth of nanocone-like structures are essentially independent of the initial surface finish, as quantified by the auto-correlation function of the surface morphology. During the first stage of the process (2 min to 15 min etching), the reflectance and light-trapping abilities of the nanotextured surfaces are strongly influenced by the initial surface roughness; however, the differences tend to diminish as the nanostructures become larger. For the longest etching times (15 min or more), the effective reflectance is less than 5% and a strong anisotropic scattering behavior is also observed for all samples, leading to very elevated levels of light-trapping.

Unravelling a simple method for the low temperature synthesis of silicon nanocrystals and monolithic nanocrystalline thin films.

In this work, we present new results on the plasma processing and structure of hydrogenated polymorphous silicon (pm-Si:H) thin films. pm-Si:H thin films consist of a low volume fraction of silicon nanocrystals embedded in a silicon matrix with medium range order, and they possess this morphology as a significant contribution to their growth comes from the impact on the substrate of silicon clusters and nanocrystals synthesized in the plasma. Quadrupole mass spectrometry, ion flux measurements, and material characterization by transmission electron microscopy (TEM) and atomic force microscopy all provide insight on the contribution to the growth by silicon nanocrystals during PECVD deposition. In particular, cross-section TEM measurements show for the first time that the silicon nanocrystals are uniformly distributed across the thickness of the pm-Si:H film. Moreover, parametric studies indicate that the best pm-Si:H material is obtained at the conditions after the transition between a pristine plasma and one containing nanocrystals, namely a total gas pressure around 2 Torr and a silane to hydrogen ratio between 0.05 to 0.1. From a practical point of view these conditions also correspond to the highest deposition rate achievable for a given RF power and silane flow rate.

Plasma-Assisted Growth of Silicon Nanowires by Sn Catalyst: Step-by-Step Observation.

A comprehensive study of the silicon nanowire growth process has been carried out. Silicon nanowires were grown by plasma-assisted-vapor-solid method using tin as a catalyst. We have focused on the evolution of the silicon nanowire density, morphology, and crystallinity. For the first time, the initial growth stage, which determines the nanowire (NW) density and growth direction, has been observed step by step. We provide direct evidence of the merging of Sn catalyst droplets and the formation of Si nanowires during the first 10 s of growth. We found that the density of Sn droplets decreases from ~9000 Sn droplets/µm2 to 2000 droplets/µm2 after just 10 s of growth. Moreover, the long and straight nanowire density decreases from 170/µm2 after 2 min of growth to less than 10/µm2 after 90 min. This strong reduction in nanowire density is accompanied by an evolution of their morphology from cylindrical to conical, then to bend conical, and finally, to a bend inverted conical shape. Moreover, the changes in the crystalline structure of nanowires are from (i) monocrystalline to (ii) monocrystalline core/defective crystalline shell and then to (iii) monocrystalline core/defective crystalline shell/amorphous shell. The evolutions of NW properties have been explained in detail.

Strong ionization asymmetry in a geometrically symmetric radio frequency capacitively coupled plasma induced by sawtooth voltage waveforms.

The ionization dynamics in geometrically symmetric parallel plate capacitively coupled plasmas driven by radio frequency tailored voltage waveforms is investigated using phase resolved optical emission spectroscopy (PROES) and particle-in-cell (PIC) simulations. Temporally asymmetric waveforms induce spatial asymmetries and offer control of the spatiotemporal dynamics of electron heating and associated ionization structures. Sawtooth waveforms with different rise and fall rates are employed using truncated Fourier series approximations of an ideal sawtooth. Experimental PROES results obtained in argon plasmas are compared with PIC simulations, showing excellent agreement. With waveforms comprising a fast voltage drop followed by a slower rise, the faster sheath expansion in front of the powered electrode causes strongly enhanced ionization in this region. The complementary waveform causes an analogous effect in front of the grounded electrode.

Understanding the amorphous-to-microcrystalline silicon transition in SiF4/H2/Ar gas mixtures.

We report on the growth of microcrystalline silicon films from the dissociation of SiF4/H2/Ar gas mixtures. For this growth chemistry, the formation of HF molecules provides a clear signature of the amorphous to microcrystalline growth transition. Depositing films from silicon tetrafluoride requires the removal of F produced by SiF4 dissociation, and this removal is promoted by the addition of H2 which strongly reacts with F to form HF molecules. At low H2 flow rates, the films grow amorphous as all the available hydrogen is consumed to form HF. Above a critical flow rate, corresponding to the full removal of F, microcrystalline films are produced as there is an excess of atomic hydrogen in the plasma. A simple yet accurate phenomenological model is proposed to explain the SiF4/H2 plasma chemistry in accordance with experimental data. This model provides some rules of thumb to achieve high deposition rates for microcrystalline silicon, namely, that increased RF power must be balanced by an increased H2 flow rate.