Ultrathin, Flexible Organic–Inorganic Hybrid Solar Cells Based on Silicon Nanowires and PEDOT:PSS

Recently, free-standing, ultrathin, single-crystal silicon (c-Si) membranes have attracted considerable attention as a suitable material for low-cost, mechanically flexible electronics. In this paper, we report a promising ultrathin, flexible, hybrid solar cell based on silicon nanowire (SiNW) arrays and poly­(3,4-ethylenedioxythiophene):poly­(styrenesulfonate) (PEDOT:PSS). The free-standing, ultrathin c-Si membranes of different thicknesses were produced by KOH etching of double-side-polished silicon wafers for various etching times. The processed free-standing silicon membranes were observed to be mechanically flexible, and in spite of their relatively small thickness, the samples tolerated the different steps of solar cell fabrication, including surface nanotexturization, spin-casting, dielectric film deposition, and metallization. However, in terms of the optical performance, ultrathin c-Si membranes suffer from noticeable transmission losses, especially in the long-wavelength region. We describe the experimental performance of a promising light-trapping scheme in the aforementioned ultrathin c-Si membranes of thicknesses as small as 5.7 μm employing front-surface random SiNW texturization in combination with a back-surface distribution of silver (Ag) nanoparticles (NPs). We report the enhancement of both the short-circuit current density (<i>J</i>_SC) and the open-circuit voltage (<i>V</i>_OC) that has been achieved in the described devices. Such enhancement is attributable to the plasmonic backscattering effect of the back-surface Ag NPs, which led to an overall 10% increase in the power conversion efficiency (PCE) of the devices compared to similar structures without Ag NPs. A PCE in excess of 6.62% has been achieved in the described devices having a c-Si membrane of thickness 8.6 μm. The described device technology could prove crucial in achieving an efficient, low-cost, mechanically flexible photovoltaic device in the near future

Plasmonic Effects of Au/Ag Bimetallic Multispiked Nanoparticles for Photovoltaic Applications

In recent years, there has been considerable interest in the use of plasmons, that is, free electron oscillations in conductors, to boost the performance of both organic and inorganic thin film solar cells. This has been driven by the possibility of employing thin active layers in solar cells in order to reduce materials costs, and is enabled by significant advances in fabrication technology. The ability of surface plasmons in metallic nanostructures to guide and confine light in the nanometer scale has opened up new design possibilities for solar cell devices. Here, we report the synthesis and characterization of highly monodisperse, reasonably stable, multipode Au/Ag bimetallic nanostructures using an inorganic additive as a ligand for photovoltaic applications. A promising surface enhanced Raman scattering (SERS) effect has been observed for the synthesized bimetallic Au/Ag multispiked nanoparticles, which compare favorably well with their Au and Ag spherical nanoparticle counterparts. The synthesized plasmonic nanostructures were incorporated on the rear surface of an ultrathin planar c-silicon/organic polymer hybrid solar cell, and the overall effect on photovoltaic performance was investigated. A promising enhancement in solar cell performance parameters, including both the open circuit voltage (<i>V</i>_OC) and short circuit current density (<i>J</i>_SC), has been observed by employing the aforementioned bimetallic multispiked nanoparticles on the rear surface of solar cell devices. A power conversion efficiency (PCE) value as high as 7.70% has been measured in a hybrid device with Au/Ag multispiked nanoparticles on the rear surface of an ultrathin, crystalline silicon (c-Si) membrane (∼12 μm). This value compares well to the measured PCE value of 6.72% for a similar device without nanoparticles. The experimental observations support the hope for a sizable PCE increase, due to plasmon effects, in thin-film, c-Si solar cells in the near future

Gold–Copper Nano-Alloy, “<i>Tumbaga</i>”, in the Era of Nano: Phase Diagram and Segregation

Gold–copper (Au–Cu) phases were employed already by pre-Columbian civilizations, essentially in decorative arts, whereas nowadays, they emerge in nanotechnology as an important catalyst. The knowledge of the phase diagram is critical to understanding the performance of a material. However, experimental determination of nanophase diagrams is rare because calorimetry remains quite challenging at the nanoscale; theoretical investigations, therefore, are welcomed. Using nanothermodynamics, this paper presents the phase diagrams of various polyhedral nanoparticles (tetrahedron, cube, octahedron, decahedron, dodecahedron, rhombic dodecahedron, truncated octahedron, cuboctahedron, and icosahedron) at sizes 4 and 10 nm. One finds, for all the shapes investigated, that the congruent melting point of these nanoparticles is shifted with respect to both size and composition (copper enrichment). Segregation reveals a gold enrichment at the surface, leading to a kind of core–shell structure, reminiscent of the historical artifacts. Finally, the most stable structures were determined to be the dodecahedron, truncated octahedron, and icosahedron with a Cu-rich core/Au-rich surface. The results of the thermodynamic approach are compared and supported by molecular-dynamics simulations and by electron-microscopy (EDX) observations

High Efficiency Hybrid Silicon Nanopillar–Polymer Solar Cells

Recently, inorganic/organic hybrid solar cells have been considered as a viable alternative for low-cost photovoltaic devices because the Schottky junction between inorganic and organic materials can be formed employing low temperature processing methods. We present an efficient hybrid solar cell based on highly ordered silicon nanopillars (SiNPs) and poly­(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS). The proposed device is formed by spin coating the organic polymer PEDOT:PSS on a SiNP array fabricated using metal assisted electroless chemical etching process. The characteristics of the hybrid solar cells are investigated as a function of SiNP height. A maximum power conversion efficiency (PCE) of 9.65% has been achieved for an optimized SiNP array hybrid solar cell with nanopillar height of 400 nm, despite the absence of a back surface field enhancement. The effect of an ultrathin atomic layer deposition (ALD), grown aluminum oxide (Al₂O₃), as a passivation layer (recombination barrier) has also been studied for the enhanced electrical performance of the device. With the inclusion of the ultrathin ALD deposited Al₂O₃ between the SiNP array textured surface and the PEDOT:PSS layer, the PCE of the fabricated device was observed to increase to 10.56%, which is ∼10% greater than the corresponding device without the Al₂O₃ layer. The device described herein is considered to be promising toward the realization of a low-cost, high-efficiency inorganic/organic hybrid solar cell

Gold–Copper Nano-Alloy, “<i>Tumbaga</i>”, in the Era of Nano: Phase Diagram and Segregation

Gold–copper (Au–Cu) phases were employed already by pre-Columbian civilizations, essentially in decorative arts, whereas nowadays, they emerge in nanotechnology as an important catalyst. The knowledge of the phase diagram is critical to understanding the performance of a material. However, experimental determination of nanophase diagrams is rare because calorimetry remains quite challenging at the nanoscale; theoretical investigations, therefore, are welcomed. Using nanothermodynamics, this paper presents the phase diagrams of various polyhedral nanoparticles (tetrahedron, cube, octahedron, decahedron, dodecahedron, rhombic dodecahedron, truncated octahedron, cuboctahedron, and icosahedron) at sizes 4 and 10 nm. One finds, for all the shapes investigated, that the congruent melting point of these nanoparticles is shifted with respect to both size and composition (copper enrichment). Segregation reveals a gold enrichment at the surface, leading to a kind of core–shell structure, reminiscent of the historical artifacts. Finally, the most stable structures were determined to be the dodecahedron, truncated octahedron, and icosahedron with a Cu-rich core/Au-rich surface. The results of the thermodynamic approach are compared and supported by molecular-dynamics simulations and by electron-microscopy (EDX) observations

Atomically Resolved Anisotropic Electrochemical Shaping of Nano-electrocatalyst

Catalytic properties of advanced functional materials are determined by their surface and near-surface atomic structure, composition, morphology, defects, compressive and tensile stresses, etc; also known as a structure–activity relationship. The catalysts structural properties are dynamically changing as they perform via complex phenomenon dependent on the reaction conditions. In turn, not just the structural features but even more importantly, catalytic characteristics of nanoparticles get altered. Definitive conclusions about these phenomena are not possible with imaging of random nanoparticles with unknown atomic structure history. Using a contemporary PtCu-alloy electrocatalyst as a model system, a unique approach allowing unprecedented insight into the morphological dynamics on the atomic-scale caused by the process of dealloying is presented. Observing the detailed structure and morphology of the same nanoparticle at different stages of electrochemical treatment reveals new insights into atomic-scale processes such as size, faceting, strain and porosity development. Furthermore, based on precise atomically resolved microscopy data, Kinetic Monte Carlo (KMC) simulations provide further feedback into the physical parameters governing electrochemically induced structural dynamics. This work introduces a unique approach toward observation and understanding of nanoparticles dynamic changes on the atomic level and paves the way for an understanding of the structure–stability relationship

Corrosion Protection of Platinum-Based Electrocatalyst by Ruthenium Surface Decoration

A comprehensive insight into the electrochemical performance of PtCu₃ electrocatalyst nanoparticles with and without Ru decoration is provided. The online dissolution investigation using the highly sensitive online analytical methodology of electrochemical flow cell coupled to inductively coupled plasma mass spectrometry reveals that the addition of Ru nanoparticles inhibits Pt dissolution presumably because of three effects: (i) suppression of Pt oxide formation, (ii) sacrificial corrosion of Ru, and (iii) lowering of local surface pH. The Ru nanoparticles, however, also lead to a decrease of the amount of crystal structure ordering, which in turn is one of the reasons for the increase of the corrosion of Cu. By measuring the potential of total zero charge it is shown that Ru decoration does not alter the electrochemical properties of the native Pt surface. Finally, Ru decoration of the Pt-based electrocatalyst is shown to present a viable approach to enhance the platinum corrosion resistance, which is confirmed by thin-film rotating disc electrode accelerated degradation tests

Adjusting the Operational Potential Window as a Tool for Prolonging the Durability of Carbon-Supported Pt-Alloy Nanoparticles as Oxygen Reduction Reaction Electrocatalysts

A current trend in the investigation of state-of-the-art Pt-alloys as proton exchange membrane fuel cell (PEMFC) electrocatalysts is to study their long-term stability as a bottleneck for their full commercialization. Although many parameters have been appropriately addressed, there are still certain issues that must be considered. Here, the stability of an experimental Pt-Co/C electrocatalyst is investigated by high-temperature accelerated degradation tests (HT-ADTs) in a high-temperature disk electrode (HT-DE) setup, allowing the imitation of close-to-real operational conditions in terms of temperature (60 °C). Although the US Department of Energy (DoE) protocol has been chosen as the basis of the study (30,000 trapezoidal wave cycling steps between 0.6 and 0.95 VRHE with a 3 s hold time at both the lower potential limit (LPL) and the upper potential limit (UPL)), this works demonstrates that limiting both the LPL and UPL (from 0.6–0.95 to 0.7–0.85 VRHE) can dramatically reduce the degradation rate of state-of-the-art Pt-alloy electrocatalysts. This has been additionally confirmed with the use of an electrochemical flow cell coupled to inductively coupled plasma mass spectrometry (EFC-ICP-MS), which enables real-time monitoring of the dissolution mechanisms of Pt and Co. In line with the HT-DE methodology observations, a dramatic decrease in the total dissolution of Pt and Co has once again been observed upon narrowing the potential window to 0.7–0.85 VRHE rather than 0.6–0.95 VRHE. Additionally, the effect of the potential hold time at both LPL and UPL on metal dissolution has also been investigated. The findings demonstrate that the dissolution rate of both metals is proportional to the hold time at UPL regardless of the applied potential window, whereas the hold time at the LPL does not appear to be as detrimental to the stability of metals

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X‑ray Absorption Spectroscopy Study

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO₂ particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir­(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer

Metal–Support Interaction between Titanium Oxynitride and Pt Nanoparticles Enables Efficient Low-Pt-Loaded High-Performance Electrodes at Relevant Oxygen Reduction Reaction Current Densities

In the present work, we report on a synergistic relationship between platinum nanoparticles and a titanium oxynitride support (TiOxNy/C) in the context of oxygen reduction reaction (ORR) catalysis. As demonstrated herein, this composite configuration results in significantly improved electrocatalytic activity toward the ORR relative to platinum dispersed on carbon support (Pt/C) at high overpotentials. Specifically, the ORR performance was assessed under an elevated mass transport regime using the modified floating electrode configuration, which enabled us to pursue the reaction closer to PEMFC-relevant current densities. A comprehensive investigation attributes the ORR performance increase to a strong interaction between platinum and the TiOxNy/C support. In particular, according to the generated strain maps obtained via scanning transmission electron microscopy (STEM), the Pt-TiOxNy/C analogue exhibits a more localized strain in Pt nanoparticles in comparison to that in the Pt/C sample. The altered Pt structure could explain the measured ORR activity trend via the d-band theory, which lowers the platinum surface coverage with ORR intermediates. In terms of the Pt particle size effect, our observation presents an anomaly as the Pt-TiOxNy/C analogue, despite having almost two times smaller nanoparticles (2.9 nm) compared to the Pt/C benchmark (4.8 nm), manifests higher specific activity. This provides a promising strategy to further lower the Pt loading and increase the ECSA without sacrificing the catalytic activity under fuel cell-relevant potentials. Apart from the ORR, the platinum-TiOxNy/C interaction is of a sufficient magnitude not to follow the typical particle size effect also in the context of other reactions such as CO stripping, hydrogen oxidation reaction, and water discharge. The trend for the latter is ascribed to the lower oxophilicity of Pt-based on electrochemical surface coverage analysis. Namely, a lower surface coverage with oxygenated species is found for the Pt-TiOxNy/C analogue. Further insights were provided by performing a detailed STEM characterization via the identical location mode (IL-STEM) in particular, via 4DSTEM acquisition. This disclosed that Pt particles are partially encapsulated within a thin layer of TiOxNy origin