Experimental, theoretical and numerical simulation-based investigations on the fabricated Cu2ZnSn thin-film-based Schottky diodes with enhanced electron transport for solar cell.

Copper-zinc-tin Cu2ZnSn (CZT) thin films are promising materials for solar cell applications. This thin film was deposited on a fluorine-doped tin oxide (FTO) using an electrochemical deposition hierarchy. X-ray diffraction of thin-film studies confirms the variation in the structural orientation of CZT on the FTO surface. As the pH of the solution is increased, the nature of the CZT thin-film aggregate changes from a fern-like leaf CZT dendrite crystal to a disk pattern. The FE-SEM surface micrograph shows the dendrite fern leaf and sharp edge disks. The 2-D diffusion limitation aggregation under slippery conditions for ternary thin films was performed for the first time. The simulation showed that by changing the diffusing species, the sticking probability was responsible for the pH-dependent morphological change. Convincingly, diffusion-limited aggregation (DLA) simulations confirm that the initial structure of copper is responsible for the final structure of the CZT thin films. An experimental simulation with pH as a controlled parameter revealed phase transition in CZT thin films. The top and back contact of Ag-CZT thin films based on Schottky behavior give a better electronic mechanism in superstrate and substrate solar cells.

Enhanced Capability of Hydrogen Evolution Photocathode by Laminated Interface Engineering of Co/MoS2 QDs/pyramid-black Si.

We present a novel and stable laminated structure to enhance the performance and stability of silicon (Si) photocathode devices for photoelectrochemical (PEC) water splitting. First, by utilizing Cu nanoparticle catalysts to work on a n+p-black Si substrate via the metal-assisted chemical etching, we can achieve the black silicon with a porous pyramid structure. The low depth holes on the surface of the pyramid caused by Cu etching not only help enhance the light capture capability with quite low surface reflectivity (<5%) but also efficiently protect the p-n junction from damage. To improve the charge migration efficiency and mitigate parasitic light absorption from cocatalysts at the same time, we drop casted quantum dots (QDs) MoS2 with the size of nanometer scale as the first layer of catalyst. Hence, we then can safely electrodeposit cocatalyst Co nanoparticles to further enhance interface transfer efficiency. The synergistic effects of cocatalysts and optimized light absorption from the morphology and QDs contributed to the overall enhancement of PEC performance, offering a promising pathway for an efficient, low cost, and stable (over 100 h) hydrogen production photocathode.

Non-destructive and simultaneous development and enhancement of latent fingerprints on stainless steel based on the electrochromic effect of electrodeposited manganese oxides.

Latent fingerprints, as one of the most frequently encountered traces in crime scene investigation and also one of the largest sources of forensic evidence, can play a critical role in determining the identity of a person who may be involved in a crime. Due to the invisible characteristic of latent fingerprints, exploring efficient techniques to visualize them (especially the ones resided on metallic surfaces) while retain the biological and chemical information (e.g., touch DNA) has become a multidisciplinary research focus. Herein we reported a new and highly sensitive electrochemical interfacial strategy of simultaneously developing and enhancing latent fingerprints on stainless steel based on synchronous electrodeposition and electrochromism of manganese oxides in a neutral aqueous electrolyte. By utilizing a specially designed device for electrochemical testing and image capture, a series of electrochemical measurements, physical characterization and image analysis have been applied to evaluate the feasibility, development accuracy and enhancement efficacy of the proposed electrochemical system. The qualitative and quantitative analysis on the in situ and ex situ fingerprint images indicates that the three levels of fingerprint features can be precisely developed and effectively enhanced. Forensic DNA typing has also been performed to reveal actual impact of the proposed electrochemical system on subsequent analysis of touch DNA in fingerprint residues. The ratio of detected loci after electrochemical treatment reaches up to 98.5 %, showing non-destructive nature of this fingerprint development and enhancement technique.

A sensitive and selective voltammetric method for the detection of pyrogallol in tomato and water samples using platinum electrode modified with alizarin red S film.

In contrast to the hyperactive platinum electrode, ARS modified platinum electrode presents a remarkable inertness toward adsorption and surface processes and lends it for further voltammetric applications. Measuring pyrogallol levels in samples is significant for assessing their antioxidant activity, which is crucial for understanding their potential health benefits and ability to combat oxidative stress. In addition, the excess consumption of pyrogallol can have significant negative effects on human health. A voltammetric sensor has been developed for the determination of pyrogallol using ARS modified platinum electrode. The electrode was prepared by electrodeposition of alizarin red S on a platinum electrode using cyclic voltammetry with a potential scan range of - 0.4 to 1.2 V against an Ag/AgCl quasi reference electrode for 60 cycles as optimum number of cycles. The modified electrode was characterized by CV and SEM techniques. This modified alizarin red S platinum electrode showed remarkable electrocatalytic performance and stability, resulting in a significant increase in pyrogallol oxidation current by 11.05% compared to the pyrogallol oxidative current at the unmodified platinum electrode. A well-defined oxidation peak was observed at ~ 0.40 V. The sensor exhibited a low limit of detection (LOD) of 0.28 µM and a linear standard curve covering the ranges of 1.0-40 µM and 0.01-10.0 mM pyrogallol. Extensive studies were performed to evaluate possible interferences from various organic and inorganic compounds and yielded satisfactory results that confirm the selectivity of the developed sensor for pyrogallol determination. In addition, the ARS-Pt electrode provided consistently reliable results for the accurate detection of pyrogallol in water and tomato samples.

The Roles of Microprobe in Localized Electrodeposition: Electrolyte Localized Transport and Force-Displacement Sensitivity.

Facing the rapid development of 6G communication, long-wave infrared metasurface and biomimetic microfluidics, the performance requirements for microsystems based on metal tiny structures are gradually increasing. As one of powerful methods for fabrication metal complex microstructures, localized electrochemical deposition microadditive manufacturing technology can fabricate copper metal micro overhanging structures without masks and supporting materials. In this study, the role of the microprobe cantilever (MC) in localized electrodeposition was studied. The MC can be used for precise deposition with electrolyte localized transport function and high accuracy force-displacement sensitivity. To prove this, the electrolyte flow was simulated when the MC was in bending or normal state. The simulation results can indicate the influence of turbulent flow on the electrolyte flow velocity and the pressure at the end of the pyramid. The results show that the internal flow velocity increased by 8.9% in the bending probe as compared with normal. Besides, this study analyzed the force-potential sensitivity characteristics of the MC. Using the deformation of the MC as an intermediate variable, the model of the probe tip displacement caused by the growth of the deposit and the voltage value displayed by the photodetector was mathematically established. In addition, the deposition of a single voxel was simulated by simulation process with the simulated height of 520 nm for one voxel, and the coincidence of simulation and experimental results was 93.1%. In conclusion, this method provides a new way for localized electrodeposition of complex microstructures.

Electrochemical Deposition and Etching of Quasi-Two-Dimensional Periodic Membrane Structure.

In this paper, two experimental procedures are reported, namely electro-deposition in the ultrathin liquid layer and chemical micro-etching. Firstly, a large area quasi-two-dimensional periodic membrane with adjustable density is deposited on a Si substrate driven by half-sinusoidal voltage, which is composed of raised ridges and a membrane between the ridges. The smaller the voltage frequency is, the larger the ridge distance is. The height of a raised ridge changes synchronously with the amplitude. The grain density distribution of membrane and raised ridge is uneven; the two structures change alternately, which is closely related to the change of growth voltage and copper ion concentration during deposition. The structural characteristics of membrane provide favorable conditions for micro-etching; stable etching speed and microscope real-time monitoring are the keys to achieve accurate etching. In the chemical micro-etching process, the membrane between ridges is removed, retaining the raised ridges, thus a large scale ordered micro-nano wires array with lateral growth was obtained. This method is simple and controllable, can be applied to a variety of substrates, and is the best choice for designing and preparing new functional materials. This experiment provides a basis for the extension of this method.

Advanced Synthesis and Characterization of CdO/CdS/ZnO Heterostructures for Solar Energy Applications.

This study introduces an innovative method for synthesizing Cadmium Oxide /Cadmium Sulfide/Zinc Oxide heterostructures (CdO/CdS/ZnO), emphasizing their potential application in solar energy. Utilizing a combination of electrochemical deposition and oxygen annealing, the research provides a thorough analysis of the heterostructures through scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, and photoluminescence (PL) spectroscopy. The findings reveal a complex surface morphology and a composite structure with significant contributions from hexagonal CdS and cubic CdO phases. The study highlights the uniformity in the distribution of luminescent centers and the crystalline quality of the heterostructures, which is evident from the PL analysis. The redshift observed in the emission peak and the additional peaks in the excitation spectrum indicate intricate optical properties influenced by various factors, including quantum confinement and lattice strain. The research demonstrates these heterostructures' potential in enhancing solar cells' efficiency and applicability in optoelectronic devices. This comprehensive characterization and analysis pave the way for future optimization and application in efficient and sustainable solar energy solutions.

Oyster Pearl-Shaped Ternary Iron Chalcogenide, FeSe0.5Te0.5, Films on FTO through Electrochemical Growth from the Exchange of Chalcogens Boosted the Enzyme-Free Urea-Sensing Ability toward Real Analytes.

Here, iron chalcogenide thin films were developed for the first time by using the less hazardous electrodeposition technique at optimized conditions on an FTO glass substrate. The chalcogenides have different surface, morphological, structural, and optical properties, as well as an enzyme-free sensing behavior toward urea. Numerous small crystallites of about ∼20 to 25 nm for FeSe, ∼18 to 25 nm for FeTe, and ∼18 to 22 nm in diameter for FeSeTe are observed with partial agglomeration under an electron microscope, having a mixed phase of tetragonal and orthorhombic structures of FeSe, FeTe, and, FeSeTe, respectively. Profilometry, XRD, FE-SEM, HR-TEM, XPS, EDX, UV-vis spectroscopy, and FT-IR spectroscopy were used for the analysis of binary and ternary composite semiconductors, FeSe, FeTe, and FeSeTe, respectively. Electrochemical experiments were conducted with the chalcogenide thin films and urea as the analyte in phosphate-buffered media at a pH of ∼ 7.4 in the concentration range of 3-413 µM. Cyclic voltammetry was performed to determine the sensitivity of the prepared electrode at an optimized scan rate of 50 mV s-1. The electrodeposited chalcogenide films appeared with a low detection limit and satisfactory sensitivity, of which the ternary chalcogenide film has the lowest LOD of 1.16 µM and the maximum sensitivity of 74.22 µA µM-1 cm-2. The transition metal electrode has a very wide range of detection limit of 1.25-2400 µM with a short response time of 4 s. This fabricated biosensor is capable of exhibiting almost 75% of its starting activity after 2 weeks of storage in the freezer at 4 °C. Simple methods of preparation, a cost-effective process, and adequate electrochemical sensing of urea confirm that the prepared sensor is suitable as an enzyme-free urea sensor and can be utilized for future studies.

Revitalizing Oxygen Reduction Reactivity of Composite Oxide Electrodes via Electrochemically Deposited PrOx Nanocatalysts.

Solid oxide fuel cells that operate at intermediate temperatures require efficient catalysts to enhance the inherently poor electrochemical activity of the composite electrodes. Here, a simple and practical electrochemical deposition method is presented for fabricating a PrOx overlayer on lanthanum strontium manganite-yttria-stabilized zirconia (LSM-YSZ) composite electrodes. The method requires less than four minutes for completion and can be carried out under at ambient temperature and pressure. Crucially, the treatment significantly improves the electrode's performance without requiring heat treatment or other supplementary processes. The PrOx-coated LSM-YSZ electrode exhibits an 89% decrease in polarization resistance at 650 °C (compared to an untreated electrode), maintaining a tenfold reduction after ≈400 h. Transmission line model analysis using impedance spectra confirms how PrOx coating improved the oxygen reduction reaction activity. Further, tests with anode-supported single cells reveal an outstanding peak power density compared to those of other LSM-YSZ-based cathodes (e.g., 418 mW cm-2 at 650 °C). Furthermore, it is demonstrated that multicomponent coating, such as (Pr,Ce)Ox, can also be obtained with this method. Overall, the observations offer a promising route for the development of high-performance solid oxide fuel cells.

Synthesis of Orthorhombic Tin Dioxide Nanowires in Track Templates.

Electrochemical deposition into a prepared SiO2/Si-p ion track template was used to make orthorhombic SnO2 vertical nanowires (NWs) for this study. As a result, a SnO2-NWs/SiO2/Si nanoheterostructure with an orthorhombic crystal structure of SnO2 nanowires was obtained. Photoluminescence excited by light with a wavelength of 240 nm has a low intensity, arising mainly due to defects such as oxygen vacancies and interstitial tin or tin with damaged bonds. The current-voltage characteristic measurement showed that the SnO2-NWs/SiO2/Si nanoheterostructure made this way has many p-n junctions.

Local Heating Induced Single-Crystalline Phase Control in Electrochemical Synthesis of Nanomaterials.

Development of synthetic strategies selectively yielding single crystals is desired owing to the facet-dependent chemical reactivities. Recent advances in electrochemical materials synthesis yielded nanomaterials that are surfactant-free, however, typically in polycrystalline forms. In this work, an electrochemical synthetic strategy selectively yielding single-crystalline nanoparticles by implementation of surface-selective heating of the working electrode is developed. Single crystals of copper, silver, gold, and platinum are afforded, and the crystallinity verified by electron diffraction and chemical reactivity studies. Notably, Cu (100) surface prepared by electrochemical synthesis yielded high single product selectivity when applied to electrochemical CO2 reduction catalysis.

Synthesis and characterization of Cu-Doped ZnO nanostructures for UV sensing application.

In this work, Fabrication, and characterization of Cu-doped ZnO thin films deposited on porous silicon (PSi) substrates have been reported using electrochemical deposition (ECD) technique. The influence of Cu-doping concentrations on morphology, structure, and electrical characteristics of zinc oxide (ZnO) thin films were presented. X-ray diffraction analysis (XRD) has been used to characterize the lattice constants, average size, in-plane (along a-axis) and out of plane (along c-axis) strains for the Cu-ZnO crystals. The effects of Cu-doping concentration on crystal parameters were also investigated from the XRD analysis. The samples were used for UV-sensing applications. In addition, Cu-doped ZnO and pure ZnO metal-semiconductor-metal photodetector, with Cu as electrode contacts were successfully produced for ultraviolet (UV) detection. The I-V (current-voltage) characteristics were used to study the sensing enhancement. Finally, the UV photodetector based on Cu-doped ZnO films was successfully fabricated and shows a five times enhancement in the sensitivity to UV light compared to that of pure ZnO photodetector.

Preparation and characterizations of antibacterial iodine-containing coatings on pure Ti.

Iodine-containing coatings were prepared on pure Ti surfaces via electrochemical deposition to enhance their antibacterial properties. The factors influencing iodine content were analyzed using an orthogonal experiment. The electrochemically deposited samples were characterized using scanning electron microscopy with energy dispersive spectroscopy and X-ray photoelectron spectroscopy, and their antibacterial properties and cytotoxicity were evaluated. The results showed that changing the deposition time is an effective way to control the iodine content. The iodine content, coating thickness, and adhesion of the samples increased with deposition time. Iodine in the coatings mainly exists in three forms, which are I2, I3-, and pentavalent iodine. For samples with iodine-containing coatings, the antibacterial ratios against E. coli and S. aureus were greater than 90% and increased with increasing iodine content. Although the samples with iodine-containing coatings showed some inhibition of the proliferation of MC3T3-E1 cells, the cell viabilities were all higher than 80%, suggesting that iodine-containing coatings are biosafe.

Strategically Designed Pd-Induced Changes in Alkaline Hydrogen Evolution Reaction and Oxygen Evolution Reaction Performances of Electrochemical Water Oxidation by the Galvanically Synthesized MoO2/MoO3 Composite Thin Film.

Electrochemical water oxidation is believed to be an effective pathway to produce clean, carbon-free, and environmentally sustainable green energy. In this work, we report a simple, easy-to-construct, facile, low-cost, and single-step galvanic technique to synthesize a Pd-supported temperature-assisted MoOx thin film nanocomposite for effective water oxidation. The most suitable nanocomposite exhibits very low overpotential at 10 mA/cm2 with smaller Tafel slope values for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) processes in an alkaline medium. The formation of a metal oxide-metal junction accelerates the growth of more active sites, promoting induced electronic synergism at the MoOx-Pd interface. This endows higher electrical conductivity and faster electron transfer kinetics, thus accelerating the faster water dissociation reaction following the Tafel-Volmer mechanism to boost the HER process in an alkaline medium. The excellent electrochemical HER and OER performances of our electrocatalyst even supersede the accomplishments of the benchmark catalysts Pt/C and RuO2. Moreover, neither of these two catalysts demonstrates both catalytic reactions, i.e., HER and OER at the same time, which have been observed for our synthesized catalyst. Our findings illustrate the potential of a thin-film MoOx-Pd nanocomposite to be an exceedingly effective electrocatalyst developed by interface engineering strategies. This also provides insight into designing several other semiconductor composite catalysts using simple synthesis techniques for highly efficient HER/OER processes that could be alternatives to benchmark electrocatalysts for water electrolysis.

Composition-Tunable Properties of Cu(Ag) Alloy for Hybrid Bonding Applications.

In the present study, the properties of Cu(Ag) alloy films were studied to evaluate their potential use as an alternate material for interconnection in hybrid bonding. Thin alloy films of Cu(Ag) were deposited by pulsed electrochemical deposition (PED) using a sulfuric acid-based bath, rotating disk electrode, and hot entry. Secondary ion mass spectrometry (SIMS) was used to measure the silver content of the films, with us finding that it decreases with increasing duty cycle. Thereafter, bright field scanning transmission electron microscope (STEM) imaging in combination with energy-dispersive x-ray spectroscopy (EDS) was used to visualize the thin film microstructure and to confirm the uniform distribution of silver throughout the film, with no bands being seen despite the pulsed nature of the deposition. Film resistance was measured by a four-point probe to quantify the impact of Ag content on resistivity, with us finding the expected linear relationship with the Ag content in the film. Furthermore, the coefficient of thermal expansion (CTE) of the films was measured using X-ray diffraction, and modulus and hardness were measured via nanoindentation, revealing linear dependences on the Ag content as well. Notably, the addition of 1.25 atom% Ag resulted in a significant increase in the CTE from 17.9 to 19.3 ppm/K, Young's modulus from 111 to 161 GPa, and film hardness from 1.70 to 3.99 GPa. These simple relationships offer a range of properties tunable via the duty cycle of the pulsed plating, making Cu(Ag) a promising candidate for engineering wafer-to-wafer metal interconnections.

Study of the Structural, Morphological, Strength and Shielding Properties of CuBi2O4 Films Obtained by Electrochemical Synthesis.

In this research, the formation processes of CuBi2O4 films were examined using atomic force microscopy, energy dispersive analysis and X-ray diffraction analysis methods. The films were synthesized through electrochemical deposition from sulfuric acid solutions at a potential difference of 3.5 V. The duration of film growth was set to between 10 and 90 min to assess the possibility of controlled film growth and preserve the stability of their structural properties during growth over an extended period. An analysis of the data obtained by X-ray diffraction revealed that the resulting film samples are highly ordered structures with a tetragonal CuBi2O4 phase. The results of the connection between the thickness of CuBi2O4 films and strength properties depending on the time of film deposition were obtained. The results of the shielding efficiency of low-energy γ-quanta using CuBi2O4 films were obtained.

Braided scaffolds with polypyrrole/polydopamine/hydroxyapatite coatings with electrical conductivity and osteogenic properties for bone tissue engineering.

When impaired bones are grafted with bone scaffolds, the behaviors of osteoblast are dependent on the implant materials and surface morphology. To this end, we modulated the surface morphology of scaffolds that promote cell growth. In this study, ice-template and spraying method methods are employed to coat different proportions of PDA and PPy over the PLA/PVA weaving scaffolds, after which HA is Coated over via the electrochemical deposition, forming weaving scaffolds with electrically conductive PDA/PPy/HA coating. The test results indicate that with a PPy/PDA concentration ratio is 30, the PPy particles are more uniformly distributed on the fiber surface. The scaffolds are wrapped in a HA coating layer with a high purity, and calcium and phosphorus elements are evenly dispersed with a Ca/P ratio being 1.69. Owing to the synergistic effect between PDA and PPy coating, the scaffolds demonstrate excellent electrochemical stability and electrochemical activity. The biological activity of the scaffold increased to 274.66% under electrical stimulation. The new thinking proposed by this study extends the worth of applying textile structure to the medical field, the application of which highly increases the prospect of bone tissue engineering.

Photoelectrocatalytic Activity of ZnO-Modified Hematite Films in the Reaction of Alcohol Degradation.

Thin-film nanocrystalline hematite electrodes were fabricated by electrochemical deposition and loaded with electrodeposited zinc oxide in various amounts. Under visible light illumination, these electrodes demonstrate high activity in the photoelectrochemical degradation of methanol, ethylene glycol and, in particular, glycerol. Results of intensity-modulated photocurrent spectroscopy show that the photoelectrocatalysis efficiency is explained by the suppression of the electron-hole pair recombination and an increase in the rate of photo-induced charge transfer. Thus, zinc oxide can be considered an effective modifying additive for hematite photoanodes.

Liquid Metal Interface for Two-Precursor Autogenous Deposition of Metal Telluride-Tellurium Networks.

Liquid metal-electrolyte can offer electrochemically reducing interfaces for the self-deposition of low-dimensional nanomaterials. We show that implementing such interfaces from multiprecursors is a promising pathway for achieving nanostructured films with combinatory properties and functionalities. Here, we explored the liquid metal-driven interfacial growth of metal tellurides using eutectic gallium-indium (EGaIn) as the liquid metal and the cation pairs Ag+-HTeO2+ and Cu2+-HTeO2+ as the precursors. At the EGaIn-electrolyte interface, the precursors were reduced and self-deposited autogenously to form interconnected nanoparticle networks. The deposited materials consisted of metal telluride and tellurium with their relative abundance depending on the metal ion type (Ag+ and Cu2+) and the metal-to-tellurium ion ratios. When used as electrode modifiers, the synthesized materials increased the electroactive surface area of unmodified electrodes by over 10 times and demonstrated remarkable activity for model electrochemical reactions, including HexRu(III) responses and dopamine sensing. Our work reveals the promising potential of the liquid metal-templated deposition method for synthesizing complex material systems for electrochemical applications.

Monitoring of Pore Orientation by in Operando Grazing Incidence Small-Angle X-ray Scattering during Templated Electrodeposition of Mesoporous Pt Films.

We have used in operando grazing incidence small-angle X-ray scattering (GISAXS) to monitor structural changes during templated electrodeposition of mesoporous platinum films on gold electrodes from a ternary lyotropic liquid crystalline mixture of aqueous hexachloroplatinic acid and the diblock copolymer surfactant Brij56. While the cylindrical micelles of the lyotropic liquid crystal (LLC) in the hexagonal phase have a center-to-center distance of 7.5 nm with a preferential alignment parallel to the electrode surface, the electrodeposited platinum films contain highly ordered mesopores arranged in a 2D hexagonal structure, with a center-to-center distance of about 8.5 nm and a preferential orientation perpendicular to the electrode surface. The progression of structural changes of the LLC template and the deposited mesoporous Pt could be monitored for the first time in operando by GISAXS: within the first 14 s of deposition, a nucleation burst of Pt coincides with a loss of preferential alignment of the LLC. Initially, the morphology of the 2-dimensionally nucleated Pt replicates the Au substrate. During the following 5 to 7 min, the growth morphology of the Pt film changes, and vertically aligned mesopores form. Our results indicate mutual interaction between the species involved in the electrodeposition and the LLC template, leading to a partial loss of horizontal orientation of the LLC during Pt nucleation before vertical rearrangement of the micelles to the electrode surface. The vertically aligned mesopores in the Pt and the possibility to produce freestanding films make these materials interesting in fields such as electrocatalysis, energy harvesting, and nanofluidics.