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.

Single-Crystal Nanowire Cesium Tin Triiodide Perovskite Solar Cell.

This work reports for the first time a highly efficient single-crystal cesium tin triiodide (CsSnI3 ) perovskite nanowire solar cell. With a perfect lattice structure, low carrier trap density (≈5 × 1010 cm-3 ), long carrier lifetime (46.7 ns), and excellent carrier mobility (>600 cm2 V-1 s-1 ), single-crystal CsSnI3 perovskite nanowires enable a very attractive feature for flexible perovskite photovoltaics to power active micro-scale electronic devices. Using CsSnI3 single-crystal nanowire in conjunction with highly conductive wide bandgap semiconductors as front-surface-field layers, an unprecedented efficiency of 11.7% under AM 1.5G illumination is achieved. This work demonstrates the feasibility of all-inorganic tin-based perovskite solar cells via crystallinity and device-structure improvement for the high-performance, and thus paves the way for the energy supply to flexible wearable devices in the future.

Influence of the Electron Beam and the Choice of Heating Membrane on the Evolution of Si Nanowires' Morphology in In Situ TEM.

We used in situ transmission electron microscopy (TEM) to observe the dynamic changes of Si nanowires under electron beam irradiation. We found evidence of structural evolutions under TEM observation due to a combination of electron beam and thermal effects. Two types of heating holders were used: a carbon membrane, and a silicon nitride membrane. Different evolution of Si nanowires on these membranes was observed. Regarding the heating of Si nanowires on a C membrane at 800 °C and above, a serious degradation dependent on the diameter of the Si nanowire was observed under the electron beam, with the formation of Si carbide. When the membrane was changed to Si nitride, a reversible sectioning and welding of the Si nanowire was observed.

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.

Coupled Investigation of Contact Potential and Microstructure Evolution of Ultra-Thin AlOx for Crystalline Si Passivation.

In this work, we report the same trends for the contact potential difference measured by Kelvin probe force microscopy and the effective carrier lifetime on crystalline silicon (c-Si) wafers passivated by AlOx layers of different thicknesses and submitted to annealing under various conditions. The changes in contact potential difference values and in the effective carrier lifetimes of the wafers are discussed in view of structural changes of the c-Si/SiO2/AlOx interface thanks to high resolution transmission electron microscopy. Indeed, we observed the presence of a crystalline silicon oxide interfacial layer in as-deposited (200 °C) AlOx, and a phase transformation from crystalline to amorphous silicon oxide when they were annealed in vacuum at 300 °C.

Controlling solid-liquid-solid GeSn nanowire growth modes by changing deposition sequences of a-Ge:H layer and SnO2nanoparticles.

Alloying Ge with Sn is one of the promising ways for achieving Si compatible optoelectronics. Here, GeSn nanowires (NWs) are realized via nano-crystallization of a hydrogenated amorphous Ge (a-Ge:H) layer with the help of metal Sn droplets. The full process consists of three steps: (1) SnO2nanoparticle (NP) reduction in a hydrogen plasma to produce Sn catalyst; (2) a-Ge:H deposition at 120 °C and (3) annealing. GeSn alloys with rich morphologies such as discrete nanocrystals (NCs), random, and straight NWs were successfully synthesized by changing process conditions. We show that annealing under Ar plasma favors the elaboration of straight GeSn NWs in contrast to the conventional random GeSn NWs obtained when annealing is performed under a H2atmosphere. Interestingly, GeSn in the form of discrete NCs can be fabricated during the deposition of a-Ge:H at 180 °C. Even more, the synthesis of out-of-plane GeSn NWs has been demonstrated by reversing the deposition sequence of SnO2NPs and a-Ge:H layer.

Germanium quantum dot infrared photodetectors addressed by self-aligned silicon nanowire electrodes.

Germanium quantum dots (GeQDs), addressed by self-aligned and epitaxial silicon nanowires (SiNWs) as electrodes, represent the most fundamental and the smallest units that can be integrated into Si optoelectronics for 1550 nm wavelength detection. In this work, individual GeQD photodetectors have been fabricated based on a low temperature self-condensation of uniform amorphous Si (a-Si)/a-Ge bilayers at 300 °C, led by rolling indium (In) droplets. Remarkably, the diameter of the GeQD nodes can be independently controlled to achieve wider GeQDs for maximizing infrared absorption with narrower SiNW electrodes to ensure a high quality Ge/Si hetero-epitaxial connection. Importantly, these hetero GeQD/SiNW photodetectors can be deployed into predesigned locations for scalable device fabrication. The photodetectors demonstrate a responsivity of 1.5 mA W-1 and a photoconductive gain exceeding 102 to the communication wavelength signals, which are related to the beneficial type-II Ge/Si alignment, gradient Ge/Si epitaxial transition and a larger QD/NW diameter ratio. These results indicate a new approach to batch-fabricate and integrate GeQDs for ultra-compact Si-compatible photodetection and imaging applications.

Annealing of Boron-Doped Hydrogenated Crystalline Silicon Grown at Low Temperature by PECVD.

We investigate low-temperature (<200 °C) plasma-enhanced chemical vapor deposition (PECVD) for the formation of p-n junctions. Compared to the standard diffusion or implantation processes, silicon growth at low temperature by PECVD ensures a lower thermal budget and a better control of the doping profile. We previously demonstrated the successful growth of boron-doped epitaxial silicon layers (p+ epi-Si) at 180 °C. In this paper, we study the activation of boron during annealing via dark conductivity measurements of p+ epi-Si layers grown on silicon-on-insulator (SOI) substrates. Secondary Ion Mass Spectroscopy (SIMS) profiles of the samples, carried out to analyze the elemental composition of the p+ epi-Si layers, showed a high concentration of impurities. Finally, we have characterized the p+ epi-Si layers by low-temperature photoluminescence (PL). Results revealed the presence of a broad defect band around 0.9 eV. In addition, we observed an evolution of the PL spectrum of the sample annealed at 200 °C, suggesting that additional defects might appear upon annealing.

Advanced radial junction thin film photovoltaics and detectors built on standing silicon nanowires.

Three-dimensional (3D) construction of radial junction hydrogenated amorphous silicon (a-Si:H) thin film solar cells on standing silicon nanowires (SiNWs) is a promising strategy to maximize the light harvesting performance and improve the photocarrier collection in an optimized junction configuration. The unique light in-coupling and absorption behaviour in the antenna-like 3D photonic structures also necessitates a set of new theoretical models and simulation tools to design, predict and optimize the photovoltaic performance of radial junction solar cells, which can be rather different from planar junction solar cells. Recently, the performance of radial junction a-Si:H thin film solar cells has progressed steadily to a level comparable or even superior to that of their planar counterparts, with plenty of room for further improvement. This review will first address the growth strategy and critical parameter control of SiNWs produced via a plasma-assisted low-temperature vapour-liquid-solid procedure using low-melting-point metals as the catalyst. Then, the construction of high-performance radial junction thin film solar cells over the standing SiNW matrix, as well as their optimal structural designs, will be introduced. At the end, the new applications of 3D radial junction units will be summarized, which include, for example, the construction of very flexible, low-cost and efficient a-Si:H solar cells with the highest power-to-weight ratio, the demonstration of highly sensitive solar-blind photodetectors operating at the ultraviolet wavelength spectrum and the development of novel biomimetic radial tandem junction photodetectors with an intrinsic red-green-blue (RGB) colour distinguishing capability.

Rational design of nanowire solar cells: from single nanowire to nanowire arrays.

In this review, we report several rational designs of nanowire-based solar cells from single nanowire to nanowire arrays. Two methods of nanowires fabrication: via 'top-down' and 'bottom-up', and two types of configurations including axial and radial junction are presented for nanowire-based solar cells. To enhance absorption, several photon management schemes are shown in detail, including anti-reflection coating, diffractive grating, and plasmonics. Considering the rational design of nanowire arrays, we summarize a total of seven solar cell structures including axial junctions, radial junctions, substrate interfacial junctions, planar junctions, conductors, junctionless and tandem. Each type is supported by examples which are presented and discussed. Finally, a general comparison between bulk and nanowire solar cell efficiencies is given.

Local VOC Measurements by Kelvin Probe Force Microscopy Applied on P-I-N Radial Junction Si Nanowires.

This work focuses on the extraction of the open circuit voltage (VOC) on photovoltaic nanowires by surface photovoltage (SPV) based on Kelvin probe force microscopy (KPFM) measurements. In a first approach, P-I-N radial junction (RJ) silicon nanowire (SiNW) devices were investigated under illumination by KPFM and current-voltage (I-V) analysis. Within 5%, the extracted SPV correlates well with the VOC. In a second approach, local SPV measurements were applied on single isolated radial junction SiNWs pointing out shadowing effects from the AFM tip that can strongly impact the SPV assessment. Several strategies in terms of AFM tip shape and illumination orientation have been put in place to minimize this effect. Local SPV measurements on isolated radial junction SiNWs increase logarithmically with the illumination power and demonstrate a linear behavior with the VOC. The results show notably that contactless measurements of the VOC become feasible at the scale of single photovoltaic SiNW devices.

Nanodroplet Hydrodynamic Transformation of Uniform Amorphous Bilayer into Highly Modulated Ge/Si Island-Chains.

Geometric and compositional modulations are the principal parameters of control to tailor the band profile in germanium/silicon (Ge/Si) heteronanowires (NWs). This has been achieved mainly by alternating the feeding precursors during a uniaxial growth of Ge/Si NWs. In this work, a self-automated growth of Ge/Si hetero island-chain nanowires (hiNWs), consisting of wider c-Ge islands connected by thinner c-Si chains, has been accomplished via an indium (In) droplet-mediated transformation of uniform amorphous a-Si/a-Ge bilayer thin films. The surface-running In droplet enforces a circulative hydrodynamics in the nanoscale droplet, which can modulate the absorption depth into the amorphous bilayer and enable a single-run growth of a superlattice-like hiNWs without the need for any external manipulation. Meanwhile, the separation and accumulation of electrons and holes in the phase-modulated Ge/Si superlattice leads to a modulated surface potential profile that can be directly resolved by Kelvin probe force microscopy. This simple self-assembly growth and modulation dynamics can help to establish a powerful new concept or strategy to tailor and program the geometric and compositional profiles of more complex hetero nanowire structures, as promising building blocks to develop advanced nanoelectronics or optoelectronics.

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.

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.

Deterministic Line-Shape Programming of Silicon Nanowires for Extremely Stretchable Springs and Electronics.

Line-shape engineering is a key strategy to endow extra stretchability to 1D silicon nanowires (SiNWs) grown with self-assembly processes. We here demonstrate a deterministic line-shape programming of in-plane SiNWs into extremely stretchable springs or arbitrary 2D patterns with the aid of indium droplets that absorb amorphous Si precursor thin film to produce ultralong c-Si NWs along programmed step edges. A reliable and faithful single run growth of c-SiNWs over turning tracks with different local curvatures has been established, while high resolution transmission electron microscopy analysis reveals a high quality monolike crystallinity in the line-shaped engineered SiNW springs. Excitingly, in situ scanning electron microscopy stretching and current-voltage characterizations also demonstrate a superelastic and robust electric transport carried by the SiNW springs even under large stretching of more than 200%. We suggest that this highly reliable line-shape programming approach holds a strong promise to extend the mature c-Si technology into the development of a new generation of high performance biofriendly and stretchable electronics.

On the Mechanism of In Nanoparticle Formation by Exposing ITO Thin Films to Hydrogen Plasmas.

We present our systematic work on the in situ generation of In nanoparticles (NPs) from the reduction of ITO thin films by hydrogen (H2) plasma exposure. In contrast to NP deposition from the vapor phase (i.e., evaporation), the ITO surface can be considered to be a solid reservoir of In atoms thanks to H2 plasma reduction. On one hand, below the In melting temperature, solid In NP formation is governed by the island-growth mode, which is a self-limiting process because the H2 plasma/ITO interaction will be gradually eliminated by the growing In NPs that cover the ITO surface. On the other hand, we show that above the melting temperature In droplets prefer to grow along the grain boundaries on the ITO surface and dramatic coalescence occurs when the growing NPs connect with each other. This growth-connection-coalescence behavior is even strengthened on In/ITO bilayers, where In particles larger than 10 µm can be formed, which are made of evaporated In atoms and in situ released ones. Thanks to this understanding, we manage to disperse dense evaporated In NPs under H2 plasma exposure when inserting an ITO layer between them and substrate like c-Si wafer or glass by modifying the substrate surface chemistry. Further studies are needed for more precise control of this self-assembling method. We expect that our findings are not limited to ITO thin films but could be applicable to various metal NPs generation from the corresponding metal oxide thin films.

High performance transparent in-plane silicon nanowire Fin-TFTs via a robust nano-droplet-scanning crystallization dynamics.

High mobility, scalable and even transparent thin-film transistors (TFTs) are always being pursued in the field of large area electronics. While excimer laser-beam-scanning can crystallize amorphous Si (a-Si) into high mobility poly-Si, it is limited to small areas. We here demonstrate a robust nano-droplet-scanning strategy that converts an a-Si:H thin film directly into periodic poly-Si nano-channels, with the aid of well-coordinated indium droplets. This enables the robust batch-fabrication of high performance Fin-TFTs with a high hole mobility of >100 cm2 V-1 s-1 and an excellent subthreshold swing of only 163 mV dec-1, via a low temperature <350 °C thin film process. More importantly, precise integration of tiny poly-Si channels, measuring only 60 nm in diameter and 2 µm apart on glass substrates, provides an unprecedented transparent Si-based TFT technology to visible light, which is widely sought for the next generation of high aperture displays and fully transparent electronics. The successful implementation of such a reliable nano-droplet-scanning strategy, rooted in the strength of nanoscale growth dynamics, will enable eventually the batch-manufacturing and upgrade of high performance large area electronics in general, and high definition and scalable flat-panel displays in particular.

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.

Heteroepitaxial Writing of Silicon-on-Sapphire Nanowires.

The heteroepitaxial growth of crystal silicon thin films on sapphire, usually referred to as SoS, has been a key technology for high-speed mixed-signal integrated circuits and processors. Here, we report a novel nanoscale SoS heteroepitaxial growth that resembles the in-plane writing of self-aligned silicon nanowires (SiNWs) on R-plane sapphire. During a low-temperature growth at <350 °C, compared to that required for conventional SoS fabrication at >900 °C, the bottom heterointerface cultivates crystalline Si pyramid seeds within the catalyst droplet, while the vertical SiNW/catalyst interface subsequently threads the seeds into continuous nanowires, producing self-oriented in-plane SiNWs that follow a set of crystallographic directions of the sapphire substrate. Despite the low-temperature fabrication process, the field effect transistors built on the SoS-SiNWs demonstrate a high on/off ratio of >5 × 104 and a peak hole mobility of >50 cm2/V·s. These results indicate the novel potential of deploying in-plane SoS nanowire channels in places that require high-performance nanoelectronics and optoelectronics with a drastically reduced thermal budget and a simplified manufacturing procedure.

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.