Tapering-free monocrystalline Ge nanowires synthesized via plasma-assisted VLS using In and Sn catalysts.

In and Sn are the type of catalysts which do not introduce deep level electrical defects within the bandgap of germanium (Ge). However, Ge nanowires produced using these catalysts usually have a large diameter, a tapered morphology, and mixed crystalline and amorphous phases. In this study, we show that plasma-assisted vapor-liquid-solid (PA-VLS) method can be used to synthesize Ge nanowires. Moreover, at certain parameter domains, the sidewall deposition issues of this synthesis method can be avoided and long, thin tapering-free monocrystalline Ge nanowires can be obtained with In and Sn catalysts. We find two quite different parameter domains where Ge nanowire growth can occur via PA-VLS using In and Sn catalysts: (i) a low temperature-low pressure domain, below âˆ¼235 °C at a GeH4partial pressure of âˆ¼6 mTorr, where supersaturation in the catalyst occurs thanks to the low solubility of Ge in the catalysts, and (ii) a high temperature-high pressure domain, at ∼400 °C and a GeH4partial pressure above âˆ¼20 mTorr, where supersaturation occurs thanks to the high GeH4concentration. While growth at 235 °C results in tapered short wires, operating at 400 °C enables cylindrical nanowire growth. With the increase of growth temperature, the crystalline structure of the nanowires changes from multi-crystalline to mono-crystalline and their growth rate increases from ∼0.3 nm s-1to 5 nm s-1. The cylindrical Ge nanowires grown at 400°C usually have a length of few microns and a radius of around 10 nm, which is well below the Bohr exciton radius in bulk Ge (24.3 nm). To explain the growth mechanism, a detailed growth model based on the key chemical reactions is provided.

Low-cost high-efficiency system for solar-driven conversion of CO2 to hydrocarbons.

Conversion of carbon dioxide into hydrocarbons using solar energy is an attractive strategy for storing such a renewable source of energy into the form of chemical energy (a fuel). This can be achieved in a system coupling a photovoltaic (PV) cell to an electrochemical cell (EC) for CO2 reduction. To be beneficial and applicable, such a system should use low-cost and easily processable photovoltaic cells and display minimal energy losses associated with the catalysts at the anode and cathode and with the electrolyzer device. In this work, we have considered all of these parameters altogether to set up a reference PV-EC system for CO2 reduction to hydrocarbons. By using the same original and efficient Cu-based catalysts at both electrodes of the electrolyzer, and by minimizing all possible energy losses associated with the electrolyzer device, we have achieved CO2 reduction to ethylene and ethane with a 21% energy efficiency. Coupled with a state-of-the-art, low-cost perovskite photovoltaic minimodule, this system reaches a 2.3% solar-to-hydrocarbon efficiency, setting a benchmark for an inexpensive all-earth-abundant PV-EC system.

Improvement of carrier collection in Si/a-Si:H nanowire solar cells by using hybrid ITO/silver nanowires contacts.

Optoelectronic devices based on high aspect ratio nanowires bring new challenges for transparent electrodes, which can be well addressed by using hybrid structures. Here we demonstrate that a composite contact to radial junction nanowire solar cells made of a thin indium-tin oxide (ITO) layer and silver nanowires greatly improves the collection of charge carriers as compared to a single thick ITO layer by reducing the series resistance losses while improving the transparency. The optimization is performed on p-i-n solar cells comprising of dense non-vertical nanowires with a p-doped c-Si core and an ultra-thin a-Si:H absorption layer grown by plasma-enhanced chemical vapor deposition on glass substrates. The optimal hybrid contact developed in this work is demonstrated to increase the solar cell conversion efficiency from 4.3% to 6.6%.

Tin dioxide nanoparticles as catalyst precursors for plasma-assisted vapor-liquid-solid growth of silicon nanowires with well-controlled density.

The fabrication of arrays of silicon nanowires (Si NWs) with well-defined surface coverage using the vapor-liquid-solid process requires a good control of the density and size distribution for the metal catalyst. We report on a cost-effective bottom-up approach to produce Si NWs by a low-temperature deposition technology using plasma-enhanced chemical vapor deposition and tin dioxide (SnO2) nanoparticles as the source of tin catalyst. This strategy offers a straightforward method to select specific particle sizes by conventional colloidal techniques, and to tune the surface coverage using a polyelectrolyte layer to efficiently immobilize the particles on the substrate by electrostatic grafting. After a further step of reduction into tin metal droplets using hydrogen plasma treatment, the catalyst particles are used for the growth of Si NWs. This approach allows the prodcution of controlled Si NWs arrays which can be used as a template for radial junction thin film solar cells.

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.

Ultrathin Epitaxial Silicon Solar Cells with Inverted Nanopyramid Arrays for Efficient Light Trapping.

Ultrathin c-Si solar cells have the potential to drastically reduce costs by saving raw material while maintaining good efficiencies thanks to the excellent quality of monocrystalline silicon. However, efficient light trapping strategies must be implemented to achieve high short-circuit currents. We report on the fabrication of both planar and patterned ultrathin c-Si solar cells on glass using low temperature (T < 275 °C), low-cost, and scalable techniques. Epitaxial c-Si layers are grown by PECVD at 160 °C and transferred on a glass substrate by anodic bonding and mechanical cleavage. A silver back mirror is combined with a front texturation based on an inverted nanopyramid array fabricated by nanoimprint lithography and wet etching. We demonstrate a short-circuit current density of 25.3 mA/cm(2) for an equivalent thickness of only 2.75 µm. External quantum efficiency (EQE) measurements are in very good agreement with FDTD simulations. We infer an optical path enhancement of 10 in the long wavelength range. A simple propagation model reveals that the low photon escape probability of 25% is the key factor in the light trapping mechanism. The main limitations of our current technology and the potential efficiencies achievable with contact optimization are discussed.

Application of the arbitrary decomposition to finite spot size Mueller matrix measurements.

Finite spot size Mueller matrix polarimetric measurements whereby the light spot impinges on two different areas of the sample, e.g., a grating and a substrate, are relatively frequently met in practice. It has been shown that if the Mueller matrix of one of the areas (the substrate) is known from an additional measurement then the Mueller matrix of the remaining medium (the grating) can be obtained from the (substrate-grating) overall response by the polarimetric subtraction method. We show that, provided a specific condition is fulfilled, the individual polarimetric responses of the two areas can be retrieved from the finite spot size measurement by using a special form of the arbitrary decomposition even if none of the individual responses is known a priori. The decomposition method is illustrated on a microelectronics grating structure and its accuracy, as well as limits of applicability, is discussed.

Assessing individual radial junction solar cells over millions on VLS-grown silicon nanowires.

Silicon nanowires (SiNWs) grown on low-cost substrates provide an ideal framework for the monolithic fabrication of radial junction photovoltaics. However, the quality of junction formation over a random matrix of SiNWs, fabricated via a vapor-liquid-solid (VLS) mechanism, has never been assessed in a realistic context. To address this, we probe the current response of individual radial junction solar cells under electron-beam and optical-beam excitations. Excellent current generation from the radial junction units, compared to their planar counterparts, has been recorded, indicating a high junction quality and effective doping in the ultra-thin SiNWs with diameters thinner than 20 nm. Interestingly, we found that the formation of radial junctions by plasma deposition can be quite robust against geometrical disorder and even the crossings of neighboring cell units. These results provide a strong support to the feasibility of building high-quality radial junction solar cells over high-throughput VLS-grown SiNWs on low-cost substrates.

Bismuth-catalyzed and doped silicon nanowires for one-pump-down fabrication of radial junction solar cells.

Silicon nanowires (SiNWs) are becoming a popular choice to develop a new generation of radial junction solar cells. We here explore a bismuth- (Bi-) catalyzed growth and doping of SiNWs, via vapor-liquid-solid (VLS) mode, to fabricate amorphous Si radial n-i-p junction solar cells in a one-pump-down and low-temperature process in a single chamber plasma deposition system. We provide the first evidence that catalyst doping in the SiNW cores, caused by incorporating Bi catalyst atoms as n-type dopant, can be utilized to fabricate radial junction solar cells, with a record open circuit voltage of V(oc) = 0.76 V and an enhanced light trapping effect that boosts the short circuit current to J(sc) = 11.23 mA/cm(2). More importantly, this bi-catalyzed SiNW growth and doping strategy exempts the use of extremely toxic phosphine gas, leading to significant procedure simplification and cost reduction for building radial junction thin film solar cells.

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.

Radial junction amorphous silicon solar cells on PECVD-grown silicon nanowires.

Constructing radial junction hydrogenated amorphous silicon (a-Si:H) solar cells on top of silicon nanowires (SiNWs) represents a promising approach towards high performance and cost-effective thin film photovoltaics. We here develop an all-in situ strategy to grow SiNWs, via a vapour-liquid-solid (VLS) mechanism on top of ZnO-coated glass substrate, in a plasma-enhanced chemical vapour deposition (PECVD) reactor. Controlling the distribution of indium catalyst drops allows us to tailor the as-grown SiNW arrays into suitable size and density, which in turn results in both a sufficient light trapping effect and a suitable arrangement allowing for conformal coverage of SiNWs by subsequent a-Si:H layers. We then demonstrate the fabrication of radial junction solar cells and carry on a parametric study designed to shed light on the absorption and quantum efficiency response, as functions of the intrinsic a-Si:H layer thickness and the density of SiNWs. These results lay a solid foundation for future structural optimization and performance ramp-up of the radial junction thin film a-Si:H photovoltaics.

Detection of second malignancies during long-term follow-up of testicular cancer survivors.

BACKGROUND: Second cancers are an important cause of mortality and morbidity in long-term survivors of testicular germ cell tumors (TGCTs). Studies on the impact of follow-up for the first tumor on the outcome of second malignancies are lacking. The aim of this study was to study the details of diagnosis of second cancers and the role of focused oncology follow-up. METHODS: Medical records and the electronic database of a tertiary referral center for germ cell neoplasms were searched for second cancers diagnosed in TGCT survivors. In a database of 1057 patients, 63 cases of metachronous second malignancies (26 contralateral testicular cancers and 37 nontesticular cancers) were found in 57 patients. Long-term oncology follow-up consisted of yearly history, physical examination, germ cell tumor markers, and imaging including abdominal computed tomography (CT) scans and chest x-ray. RESULTS: The second malignancies occurred after a medium follow-up of 9.9 years (range, 1.1-33 years) after the diagnosis of the first tumor. Only 17 (27%) of the 63 second tumors were detected by oncology follow-up investigations, and a further 12 (29%) were detected by nononcology physicians during a preplanned clinical visit. In 34 (54%) cases, patients themselves or their relatives initiated a clinical appointment because of symptoms. Follow-up investigations all had low yields for the detection of second malignancies, although CT imaging did detect several cases of cancer at an early stage. CONCLUSIONS: In this retrospective study, most second cancers occurring in long-term TGCT survivors were missed by regular oncology follow-up that included yearly physical examination, tumor marker, and imaging.

Real-time in situ Mueller matrix ellipsometry of GaSb nanopillars: observation of anisotropic local alignment.

The formation of GaSb nanopillars by low energy ion sputtering is studied in real-time by spectroscopic Mueller matrix ellipsometry, from the initial formation in the smooth substrate until nanopillars with a height of 200-300 nm are formed. As the nanopillar height increased above 100 nm, coupling between orthogonal polarization modes was observed. Ex situ angle resolved Mueller polarimetry measurements revealed a 180° azimuth rotation symmetry in the off-diagonal Mueller elements, which can be explained by a biaxial material with different dielectric functions εx and εy in a plane parallel to the substrate. This polarization coupling can be caused by a tendency for local direction dependent alignment of the pillars, and such a tendency is confirmed by scanning electron microscopy. Such observations have not been made for GaSb nanopillars shorter than 100 nm, which have optical properties that can be modeled as a uniaxial effective medium.

High Density of Quantum-Sized Silicon Nanowires with Different Polytypes Grown with Bimetallic Catalysts.

When Si nanowires (NWs) have diameters below about 10 nm, their band gap increases as their diameter decreases; moreover, it can be direct if the material adopts the metastable diamond hexagonal structure. To prepare such wires, we have developed an original variant of the vapor-liquid-solid process based on the use of a bimetallic Cu-Sn catalyst in a plasma-enhanced chemical vapor deposition reactor, which allows us to prevent droplets from coalescing and favors the growth of a high density of NWs with a narrow diameter distribution. Controlling the deposited thickness of the catalyst materials at the sub-nanometer level allows us to get dense arrays (up to 6 × 1010 cm-2) of very-small-diameter NWs of 6 nm on average (standard deviation of 1.6 nm) with crystalline cores of about 4 nm. The transmission electron microscopy analysis shows that both 3C and 2H polytypes are present, with the 2H hexagonal diamond structure appearing in 5-13% of the analyzed NWs per sample.

Scattered light measurements on textured crystalline silicon substrates using an angle-resolved Mueller matrix polarimeter.

Dry plasma etching is a promising technique for crystalline silicon surface texturing aimed at improving solar cell efficiencies by reducing incident light reflection and backscattering at the cell front surface. In this work we present a new optical characterization technique for textured surfaces based on a Mueller polarimeter coupled with a high numerical aperture microscope operated either in real or in angular spaces. This tool provides both the specularly reflected and the angle-resolved backscattered intensities in a very efficient manner, due to the absence of moving parts. Three different silicon samples were etched in a standard reactor with SF(6)/O(2) plasmas at various RF powers, resulting in different textures that were characterized by scanning electron microscopy, standard reflectometry, and by our tool. The three techniques yielded consistent results. However, reflectometry could not take into account the backscattered light from highly textured surfaces, leading to significant underestimation of the overall amount of the reflected light. In contrast, our tool has demonstrated the potential to measure both reflected and backscattered light quickly and efficiently for all samples, paving the way for a new characterization technique for textured solar cells both at the development and at the production stage.

ALD of ZnO:Ti: Growth Mechanism and Application as an Efficient Transparent Conductive Oxide in Silicon Nanowire Solar Cells.

In the quest for the replacement of indium tin oxide (ITO), Ti-doped zinc oxide (TZO) films have been synthesized by atomic layer deposition (ALD) and applied as an n-type transparent conductive oxide (TCO). TZO thin films were obtained from titanium (IV) i-propoxide (TTIP), diethyl zinc, and water by introducing TiO2 growth cycle in a ZnO matrix. Process parameters such as the order of precursor introduction, the cycle ratio, and the film thickness were optimized. The as-deposited films were analyzed for their surface morphology, elemental stoichiometry, optoelectronic properties, and crystallinity using a variety of characterization techniques. The growth mechanism was investigated for the first time by in situ quartz crystal microbalance measurements. It evidenced different insertion modes of titanium depending on the precursor introduction, as well as the etching of Zn-Et surface groups by TTIP. Resistivity as low as 1.2 × 10-3 Ω cm and transmittance >80% in the visible range were obtained for 72-nm-thick films. Finally, the first application of ALD-TZO as TCO was reported. TZO films were successfully implemented as top electrodes in silicon nanowire solar cells. The unique properties of TZO combined with conformal coverage realized by the ALD technique make it possible for the cell to show almost flat external quantum efficiency (EQE) response, surpassing the bell-like EQE curve seen in devices with a sputtered ITO top electrode.

Experimental evidence for naturally occurring nondiagonal depolarizers.

We report on two Stokes nondiagonalizable Mueller matrices experimentally observed in a biological and in an organic sample. These matrices are examples of naturally occurring nondiagonal depolarizers whose unique property is to preserve the degree of polarization of all but one totally polarized light state. The description of the experimental matrices within the theory of Bragg scattering on cholesteric liquid crystals, as well as their interpretation in physical and structural terms, are likewise addressed.

Optimization of the optical coupling in nanowire-based integrated photonic platforms by FDTD simulation.

The optimized design of a photonic platform based on a nanowire light emitting diode (LED) and a nanowire photodetector connected with a waveguide is proposed. The light coupling efficiency from the LED to the detector is optimized as a function of the geometrical parameters of the system using the finite difference time domain simulation tool Lumerical. Starting from a design reported in the literature with a coupling efficiency of only 8.7%, we propose an optimized photonic platform with efficiency reaching 65.5%.

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.

Optical Study and Experimental Realization of Nanostructured Back Reflectors with Reduced Parasitic Losses for Silicon Thin Film Solar Cells.

We study light trapping and parasitic losses in hydrogenated amorphous silicon thin film solar cells fabricated by plasma-enhanced chemical vapor deposition on nanostructured back reflectors. The back reflectors are patterned using polystyrene assisted lithography. By using O2 plasma etching of the polystyrene spheres, we managed to fabricate hexagonal nanostructured back reflectors. With the help of rigorous modeling, we study the parasitic losses in different back reflectors, non-active layers, and last but not least the light enhancement effect in the silicon absorber layer. Moreover, simulation results have been checked against experimental data. We have demonstrated hexagonal nanostructured amorphous silicon thin film solar cells with a power conversion efficiency of 7.7% and around 34.7% enhancement of the short-circuit current density, compared with planar amorphous silicon thin film solar cells.