Hydrothermal Grown Nanoporous Iron Based Titanate, Fe₂TiO₅ for Light Driven Water Splitting

We report the synthesis of iron based titanate (Fe₂TiO₅) thin films using a simple low cost hydrothermal technique. We show that this Fe₂TiO₅ works well as a photoanode for the photoelectrochemical splitting of water due to favorable band energetic. Further characterization of thin films including band positions with respect to water redox levels has been investigated. We conclude that Fe₂TiO₅ is a promising material comparable to hematite for constructing PEC cells

Efficient Polymer Solar Cells Enabled by Low Temperature Processed Ternary Metal Oxide as Electron Transport Interlayer with Large Stoichiometry Window

Highly efficient organic photovoltaic cells are demonstrated by incorporating low temperature solution processed indium zinc oxide (IZO) as cathode interlayers. The IZOs are synthesized using a combustion synthesis method, which enables low temperature processes (150–250 °C). We investigated the IZO films with different electron mobilities (1.4 × 10^–3 to 0.23 cm²/(V·s)), hydroxide–oxide content (38% to 47%), and surface roughness (0.19–5.16 nm) by modulating the ternary metal oxide stoichiometry. The photovoltaic performance was found to be relatively insensitive to the composition ratio of In:Zn over the range of 0.8:0.2 to 0.5:0.5 despite the differences in their electrical and surface properties, achieving high power conversion efficiencies of 6.61%–7.04%. Changes in composition ratio of IZO do not lead to obvious differences in energy levels, diode parameters and morphology of the photoactive layer, as revealed by ultraviolet photoelectron spectroscopy (UPS), dark current analysis and time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements, correlating well with the large IZO stoichiometry window that enables efficient photovoltaic devices. Our results demonstrate the robustness of this ETL system and provide a convenient approach to realize a wide range of multicomponent oxides and compatible with processing on flexible plastic substrates

Ruthenium–Tungsten Composite Catalyst for the Efficient and Contamination-Resistant Electrochemical Evolution of Hydrogen

A new catalyst, prepared by a simple physical mixing of ruthenium (Ru) and tungsten (W) powders, has been discovered to interact synergistically to enhance the electrochemical hydrogen evolution reaction (HER). In an aqueous 0.5 M H₂SO₄ electrolyte, this catalyst, which contained a miniscule loading of 2–5 nm sized Ru nanoparticles (5.6 μg Ru per cm² of geometric surface area of the working electrode), required an overpotential of only 85 mV to drive 10 mA/cm² of H₂ evolution. Interestingly, our catalyst also exhibited good immunity against deactivation during HER from ionic contaminants, such as Cu²⁺ (over 24 h). We unravel the mechanism of synergy between W and Ru for catalyzing H₂ evolution using Cu underpotential deposition, photoelectron spectroscopy, and density functional theory (DFT) calculations. We found a decrease in the d-band and an increase in the electron work function of Ru in the mixed composite, which made it bind to H more weakly (more Pt-like). The H-adsorption energy on Ru deposited on W was found, by DFT, to be very close to that of Pt(111), explaining the improved HER activity

Improving the Efficiency of Hematite Nanorods for Photoelectrochemical Water Splitting by Doping with Manganese

Here, we report a significant improvement of the photoelectrochemical (PEC) properties of hematite (α-Fe₂O₃) to oxidize water by doping with manganese. Hematite nanorods were grown on a fluorine-treated tin oxide (FTO) substrate by a hydrothermal method in the presence on Mn. Systematic physical analyses were performed to investigate the presence of Mn in the samples. Fe₂O₃ nanorods with 5 mol % Mn treatment showed a photocurrent density of 1.6 mA cm^–2 (75% higher than that of pristine Fe₂O₃) at 1.23 V versus RHE and a plateau photocurrent density of 3.2 mA cm^–2 at 1.8 V versus RHE in a 1 M NaOH electrolyte solution (pH 13.6). We attribute the increase in the photocurrent density, and thus in the oxygen evolving capacity, to the increased donor density resulting from Mn doping of the Fe₂O₃ nanorods, as confirmed by Mott–Schottky measurement, as well as the suppression of electron–hole recombination and enhancement in hole transport, as detected by chronoamperometry measurements

Detrimental Effects of Oxygen Vacancies in Electrochromic Molybdenum Oxide

Using the small polaron model, we show clearly that oxygen vacancy defects are detrimental to the electrochromic responses of molybdenum oxide (MoO₃). The observed phenomenon is explained by studying the oxidation states of the molybdenum (Mo) metal, which is central to the site specific small polaron model. First, we used the small polaron pair to explain the red-shift between the absorption peak induced by the vacancy defects and the inserted lithium (Li). Next, we show that any Mo⁵⁺ defects results in either a poor cathodic optical pair, or forms a site that is inactive for Li insertion. The main reason for the latter is due to the inability to generate Mo⁴⁺ in the reported optimal potential range. Finally, if the oxide starts with any intrinsic Mo⁴⁺ defect, we provided evidence to show that Mo⁶⁺–Mo⁴⁺ remains the only possible site for Li insertion, thereby greatly reducing available active sites. This optical modulation from Li insertion into this aforementioned pair is also low when compared with the Mo⁶⁺–Mo⁶⁺ pair. We therefore conclude that the most effective modulation is achieved by the Mo⁶⁺–Mo⁶⁺ pair and defects creation will be detrimental to the electrochromic performance of MoO₃

Revealing the Role of Potassium Treatment in CZTSSe Thin Film Solar Cells

Potassium (K) post-treatment on CIGSSe has been shown to yield the highest efficiency reported to date. However, very little is known on the effect of K doping in CZTSSe and the mechanism behind the efficiency improvement. Here we reveal the mechanism by which K enhances the charge separation in CZTSSe. We show that K accumulates at the CdS/CZTSSe, passivating the recombination at the front interface and improving carrier collection. K is also found to accumulate at the CZTSSe/Mo interface and facilitates the diffusion of Cd into the absorber which affects the morphology and grain growth of CZTSSe. As revealed by the <i>C</i>–<i>V</i>, external quantum efficiency, and color <i>J</i>–<i>V</i> test, K doping significantly increases the carrier density, improves carrier collection, and passivates the front interface and grain boundaries, leading to the enhancement of <i>V</i>_oc and <i>J</i>_sc. The average power conversion efficiency has been promoted from 5% to above 7%, and the best 7.78% efficiency has been achieved for the 1.5 mol % K-doped CZTSSe device. This work offers some new insights into the K doping effects on CZTSSe via solution-based approach and demonstrates the potential of facile control of K doping for further improvement of CZTSSe thin film solar cells

Silicon Decorated with Amorphous Cobalt Molybdenum Sulfide Catalyst as an Efficient Photocathode for Solar Hydrogen Generation

The construction of viable photoelectrochemical (PEC) devices for solar-driven water splitting can be achieved by first identifying an efficient independent photoanode for water oxidation and a photocathode for hydrogen generation. These two photoelectrodes then must be assembled with a proton exchange membrane within a complete coupled system. Here we report the preparation of a Si/<i>a</i>-CoMoS_<i>x</i> hybrid photocathode which shows impressive performance (onset potential of 0.25 V <i>vs</i> RHE and photocurrent <i>j</i>_sc of 17.5 mA cm^–2 at 0 V <i>vs</i> RHE) in pH 4.25 phosphate solution and under simulated AM 1.5 solar illumination. This performance is among the best reported for Si photocathodes decorated with noble-metal-free catalysts. The electrode preparation is scalable because it relies on a photoassisted electrodeposition process employing an available p-type Si electrode and [Co(MoS₄)₂]^2– precursor. Investigation of the mechanism of the Si/<i>a</i>-CoMoS_<i>x</i> electrode revealed that under conditions of H₂ photogeneration this bimetallic sulfide catalyst is highly efficient in extracting electrons from illuminated Si and subsequently in reducing protons into H₂. The Si/<i>a</i>-CoMoS_<i>x</i> photocathode is functional over a wide range of pH values, thus making it a promising candidate for the construction of a complete solar-driven water splitting PEC device

Minimizing Isolate Catalyst Motion in Metal-Assisted Chemical Etching for Deep Trenching of Silicon Nanohole Array

The instability of isolate catalysts during metal-assisted chemical etching is a major hindrance to achieve high aspect ratio structures in the vertical and directional etching of silicon (Si). In this work, we discussed and showed how isolate catalyst motion can be influenced and controlled by the semiconductor doping type and the oxidant concentration ratio. We propose that the triggering event in deviating isolate catalyst motion is brought about by unequal etch rates across the isolate catalyst. This triggering event is indirectly affected by the oxidant concentration ratio through the etching rates. While the triggering events are stochastic, the doping concentration of silicon offers a good control in minimizing isolate catalyst motion. The doping concentration affects the porosity at the etching front, and this directly affects the van der Waals (vdWs) forces between the metal catalyst and Si during etching. A reduction in the vdWs forces resulted in a lower bending torque that can prevent the straying of the isolate catalyst from its directional etching, in the event of unequal etch rates. The key understandings in isolate catalyst motion derived from this work allowed us to demonstrate the fabrication of large area and uniformly ordered sub-500 nm nanoholes array with an unprecedented high aspect ratio of ∼12

Damage-Free Smooth-Sidewall InGaAs Nanopillar Array by Metal-Assisted Chemical Etching

Producing densely packed high aspect ratio In_0.53Ga_0.47As nanostructures without surface damage is critical for beyond Si-CMOS nanoelectronic and optoelectronic devices. However, conventional dry etching methods are known to produce irreversible damage to III−V compound semiconductors because of the inherent high-energy ion-driven process. In this work, we demonstrate the realization of ordered, uniform, array-based In_0.53Ga_0.47As pillars with diameters as small as 200 nm using the damage-free metal-assisted chemical etching (MacEtch) technology combined with the post-MacEtch digital etching smoothing. The etching mechanism of In<i>_x</i>Ga_1−<i>x</i>As is explored through the characterization of pillar morphology and porosity as a function of etching condition and indium composition. The etching behavior of In_0.53Ga_0.47As, in contrast to higher bandgap semiconductors (<i>e</i>.<i>g</i>., Si or GaAs), can be interpreted by a Schottky barrier height model that dictates the etching mechanism constantly in the mass transport limited regime because of the low barrier height. A broader impact of this work relates to the complete elimination of surface roughness or porosity related defects, which can be prevalent byproducts of MacEtch, by post-MacEtch digital etching. Side-by-side comparison of the midgap interface state density and flat-band capacitance hysteresis of both the unprocessed planar and MacEtched pillar In_0.53Ga_0.47As metal-oxide-semiconductor capacitors further confirms that the surface of the resultant pillars is as smooth and defect-free as before etching. MacEtch combined with digital etching offers a simple, room-temperature, and low-cost method for the formation of high-quality In_0.53Ga_0.47As nanostructures that will potentially enable large-volume production of In_0.53Ga_0.47As-based devices including three-dimensional transistors and high-efficiency infrared photodetectors

Self-Anchored Catalyst Interface Enables Ordered Via Array Formation from Submicrometer to Millimeter Scale for Polycrystalline and Single-Crystalline Silicon

Defying text definitions of wet etching, metal-assisted chemical etching (MacEtch), a solution-based, damage-free semiconductor etching method, is directional, where the metal catalyst film sinks with the semiconductor etching front, producing 3D semiconductor structures that are complementary to the metal catalyst film pattern. The same recipe that works perfectly to produce ordered array of nanostructures for single-crystalline Si (c-Si) fails completely when applied to polycrystalline Si (poly-Si) with the same doping type and level. Another long-standing challenge for MacEtch is the difficulty of uniformly etching across feature sizes larger than a few micrometers because of the nature of lateral etching. The issue of interface control between the catalyst and the semiconductor in both lateral and vertical directions over time and over distance needs to be systematically addressed. Here, we present a self-anchored catalyst (SAC) MacEtch method, where a nanoporous catalyst film is used to produce nanowires through the pinholes, which in turn physically anchor the catalyst film from detouring as it descends. The systematic vertical etch rate study as a function of porous catalyst diameter from 200 to 900 nm shows that the SAC-MacEtch not only confines the etching direction but also enhances the etch rate due to the increased liquid access path, significantly delaying the onset of the mass-transport-limited critical diameter compared to nonporous catalyst c-Si counterpart. With this enhanced mass transport approach, vias on multistacks of poly-Si/SiO₂ are also formed with excellent vertical registry through the polystack, even though they are separated by SiO₂ which is readily removed by HF alone with no anisotropy. In addition, 320 μm square through-Si-via (TSV) arrays in 550 μm thick c-Si are realized. The ability of SAC-MacEtch to etch through poly/oxide/poly stack as well as more than half millimeter thick silicon with excellent site specificity for a wide range of feature sizes has significant implications for 2.5D/3D photonic and electronic device applications