An investigation of chemical and electrochemical conversion of SILAR grown Mn3O4 into MnO2 thin films.

Manganese oxide is an interesting material for electrochemical properties. It is well known that Mn3O4 (spinel) can be electrochemically converted to MnO2 (birnessite) via the electrochemical route during cyclic voltammetry (CV) cycling in aqueous Na2SO4 solution. Herein, the novel way is represented for the growth of highly adherent and compact Mn3O4 thin films by using successive ionic layer adsorption and reaction (SILAR) method. As grown Mn3O4 thin films are converted into MnO2 after chemical treatment by hydrochloric acid (HCl) via a disproportionate reaction. Mn3O4 thin films are converted into MnO2 by both chemical and electrochemical paths. During chemical conversion, at acidic pH, the crystal water insertion (H3O+) in Mn3O4 crystal provides the necessary driving force to transform it into MnO2 crystal. During electrochemical transformation, the specific capacitance was found to increase from 72 (1st CV cycle) to 393 F/g (1600th CV cycle). On the other hand, the specific capacitance was increased from 72 to 258 F/g through chemical transformation. Electrochemical and chemical conversion leads to ~5.5 and ~3.5 fold, respectively, improved supercapacitive performance than pristine Mn3O4 thin films. Both chemical and electrochemical conversion routes are extremely useful to recycle battery waste for supercapacitor applications.

Atomic Layer Deposition from Dissolved Precursors.

We establish a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD) known with gaseous precursors toward precursors dissolved in a liquid. An established ALD reaction behaves similarly when performed from solutions. "Solution ALD" (sALD) can coat deep pores in a conformal manner. sALD offers novel opportunities by overcoming the need for volatile and thermally robust precursors. We establish a MgO sALD procedure based on the hydrolysis of a Grignard reagent.

Interplay between structure, stoichiometry, and electron transfer dynamics in SILAR-based quantum dot-sensitized oxides.

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor-acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

Effect in variation of the cationic precursor temperature on the electrical and crystalline properties of MnS growth by SILAR.

The crystallographic, optical, and electrical properties of manganese sulfide thin films depend on the control of the temperature precursors in the synthesis process, as shown by the results of this work. MnS thin films were deposited on glass substrates using the SILAR method and over an additional layer of CdS synthesized by chemical bath deposition (CBD) to acquire a p-n heterojunction. SILAR is an inexpensive method performed with a homemade robot in this case. Temperature in the solution precursors varied from 20 to 80 °C in four experiments. The morphology and structure of MnS and FTO/CdS/MnS thin films were studied through scanning electron microscopy (SEM) and grazing-incidence X-ray diffraction (GIXRD); the results indicate that materials showed a polycrystalline behavior, a diffraction peak of α- MnS cubic phase was observed with lattice constants values, ranging from 4.74 to 4.75 Å. Additionally, Raman spectroscopy showed a signal corresponding to the transversal optical phonons of MnS at a wavenumber near 300 cm-1. UV-vis spectroscopy showed optical bandgap values of 3.94, 4.0, 4.09, and 4.26 eV for thin films obtained at 20°, 40°, 60°, and 80 °C. respectively. Results indicated 80 °C as an optimal cationic precursor process temperature, achieving optical transmittance T% and good film quality according to SEM and GIXRD for the synthetization of MnS. The current-voltage (I-V) characterization in the heterojunction showed a characteristic diode curve with an open circuit voltage (VOC) of 300 mV under illumination, which indicated that the manganese sulfide behaves as p-type material contributing with positive charge carriers, while CdS behaves as n-type material.

Influence of solution pH dependency on structure, optical with photoelectrochemical characteristics of SILAR deposited copper oxide thin films.

Photoelectrochemical (PEC) technology is a promising approach for converting solar energy into chemical energy, offering significant potential for renewable energy applications. In this work, the CuO thin film was fabricated with different pH value in between 8.5 ± 0.1 and 10.5 ± 0.1 via Successive Ionic Layer Adsorption and Reaction (SILAR) method. The Effect of pH on thickness, structural, morphological, elemental composition and optical properties were investigated by using stylus profilometry, XRD, SEM, TEM, EDX, UV-vis and PL. The XRD results showed that as the pH increased, the crystallite size increased from 19.24 nm to 25.62 nm, with a monoclinic phase along the (111) direction. The CuO film deposited at pH value 10.5 ± 0.1 exhibit well defined identical particle with its size in the range between 200 and 300 nm was confirmed by SEM and TEM analysis. As the pH increased from 8.5 ± 0.1 to 10.5 ± 0.1, the CuO film bandgap (Eg) value reduced from 1.52 eV to 1.42 eV with indirect transition. The CuO photocathode deposited at pH 10.5 ± 0.1 shows maximum photocurrent density of 1.45 mA/cm2 at -0.1 V vs. RHE in 0.5 M Na2SO4 solution. Furthermore, the Electrochemical Impedance Spectroscopy (EIS) analysis shows, the CuO (pH 10.5 ± 0.1) electrode have higher conductivity value of 0.6862 S/cm compared CuO at pH 8.5 ± 0.1 (0.2779 S/cm) and CuO at pH 9.5 ± 0.1 (0.4646 S/cm) electrodes.

Harnessing morphological alteration from microflowers to nanoparticles and cations synergy (Co:Ni) in binder-free cobalt nickel vanadate thin film cathodes synthesized via SILAR method for hybrid supercapacitor devices.

Electrode materials must be rationally designed with morphologies and electroactive sites manipulated through cations' synergy in bimetal compounds in order to maximize the performance of energy storage devices. Therefore, the present study emphasizes binder-free scalable preparation of cobalt nickel vanadate (CNV) thin films by a facile successive ionic layer adsorption and reaction (SILAR) approach with specific cations (Co:Ni) alternation. Increasing the Ni cation content in the CNV notably transforms its microflower structure comprising nanoflakes (252 nm) into nanoparticles (74 nm). An optimized S-CNV5 thin film cathode with Co:Ni molar ratio of âˆ¼ 0.4:0.6 and a high specific surface area of 340 m2 g-1, provided the excellent specific capacitance (Csp) and capacity (Csc) of 1382 F g-1 and 691 C g-1, respectively at 1 A g-1 current density. A hybrid aqueous supercapacitor (HASc) device with positive and negative electrodes comprising optimized CNV and reduced graphene oxide (rGO), respectively, in a 1 M KOH electrolyte delivered a Csp of 133 F g-1 and a specific energy (SE) of 53 Wh kg-1 at a specific power (SP) of 2261 kW kg-1. Additionally, a fabricated hybrid solid-state supercapacitor (HSSc) device with the same electrodes applying PVA-KOH gel electrolyte displayed a Csp of 119 F g-1, and SE of 46 Wh kg-1 at SP of 1184 W kg-1. This boosted electrochemical activity is due to the synergetic effects of Ni and Co species in the CNV thin film electrodes, emphasizing the potential of CNV electrodes as cathodes in hybrid energy storage devices.

Analyzing antimicrobial activity of ZnO/FTO, Sn-Cu-doped ZnO/FTO thin films: Production and characterizations.

In the developing field of nanotechnology, ZnO (zinc oxide) based semiconductor samples have emerged as the foremost choice due to their immense potential for advancing the development of cutting-edge nanodevices. Due to its excellent chemical stability, low cost, and non-toxicity to biological systems, it is also utilized in various investigations. In this study, the successive ionic layer adsorption and reaction (SILAR) method was used to generate FTO (fluorine-doped tin oxide)/ZnO, and tin (Sn)-copper (Cu)-doped ZnO thin films at varying concentrations on FTO substrates. After being stacked 40 times in varying concentrations on the FTO substrate, FTO/ZnO thin films and Sn-Cu-doped thin films were annealed at 300°C. Using Scanning Electron Microscopy (SEM) Energy Dispersive Spectroscopy-(EDS), the agar diffusion test, and the viability cell counting method, the minimum inhibitory concentration, structural properties, surface morphology, antibacterial properties, bacterial adhesion, and survival organism count of FTO/ZnO thin films and Sn-Cu-doped thin films were investigated. Both doped and FTO/ZnO films with varying Sn-Cu concentrations expanded harmonically on the FTO substrate, according to the SEM-EDS investigation. The doping concentration affected their morphological properties, causing changes depending on the doping level. Antibacterial activity was observed in the powder metals, but no antibacterial activity was found in the thin film form. The highest adhesion rate of bacterial organisms on the produced samples was observed when the FTO/ZnO/Sn-Cu doping rate was 1%. In addition, the lowest adhesion rate was observed when the FTO/ZnO/Sn-Cu additive ratio was 3%. RESEARCH HIGHLIGHTS: ZnO based semiconductors highlight significant potential in advancing nanodevice technology due to their chemical stability, cost-effectiveness, and biocompatibility. Employing the SILAR method, the study innovatively fabricates FTO/ZnO and Sn-Cu-doped ZnO thin films on FTO substrates, exploring a novel approach in semiconductor manufacturing. Post annealing at 300°C, the research examines the structural and surface morphological changes in the films, contributing to the understanding of semiconductor behavior under varying conditions. The study delves into the antibacterial properties of ZnO thin films, offering insights into the potential biomedical applications of these materials. SEM-EDS analysis reveals that doping concentrations crucially influence the morphological properties of ZnO thin films, shedding light on the optimization of semiconductor performance. Findings indicate a specific doping rate (1% Sn-Cu) enhances bacterial adhesion, while a 3% additive ratio minimizes it, suggesting implications for biomedical device engineering and antibacterial surface design.

Photoelectrochemical performance of BiOI/TiO2 nanotube arrays (TNAs) p-n heterojunction synthesized by SILAR-ultrasonication-assisted methods.

In order to extend the visible region activity of titania nanotube array (TNAs) films, the successive ionic layer adsorption and reaction (SILAR)-ultrasonication-assisted method has been used to prepare BiOI-modified TiO2 nanotube arrays (BiOI/TNAs). The band gap of BiOI/TNAs for all the variations reveals absorption in the visible absorption. The surface morphology of BiOI/TNAs is shown in the nanoplate, nanoflake and nanosheet forms with a vertical orientation perpendicular to TiO2. The crystalline structure of BiOI did not change the structure of the anatase TNAs, with the band gap energy of the BiOI/TNAs semiconductor in the visible region. The photocurrent density of the BiOI/TNAs extends to the visible-light range. BiOI/TNAs prepared with 1 mM Bi and 1 mM KI on TNAs 40 V 1 h, 50 V 30 min show the optimum photocurrent density. A tandem dye-sensitized solar cell (DSSC)-photoelectrochemical (PEC) was used for hydrogen production in salty water. BiOI/TNAs optimum was used as the photoanode of the PEC cell. The solar to hydrogen conversion efficiency (STH) of tandem DSSC-PEC reaches 1.34% in salty water.

Effect of the tri-sodium citrate as a complexing agent in the deposition of ZnS by SILAR.

Using the SILAR method Zinc sulfide coatings were deposited on glass slices. The physical properties and the chemical mechanism throughout the variation in concentration of tri-sodium citrate (TSC) as a chelating agent in the synthesis of thin films were investigated. Results shows that ZnS thin films exhibit an average transmittance of 16% in visible light spectra region and a zinc blende structure. The ZnS films synthesized using TSC as a complexing agent, present a smaller average particle size, an average transmittance of 85%, and an adsorption edge at 300-340 nm. Based on our experimental data and analysis, we conclude that the contribution of the oxychloride species, a subproduct in the chemical deposition, is suggested to be related as an impurity level former in the synthesis of ZnS thin films. TSC as a complexing agent in the SILAR technique is a non-toxic option to reduce the generation of the oxychloride species and synthesize a wide band gap semiconductor. Moreover, the use of complexing agents could be extended to other types of semiconductors deposited by SILAR.

SILAR-Deposited CuO Nanostructured Films Doped with Zinc and Sodium for Improved CO2 Gas Detection.

Gas sensing is of significant importance in a wide range of disciplines, including industrial safety and environmental monitoring. In this work, a low-cost SILAR (Successive Ionic Layer Adsorption and Reaction) technique was employed to fabricate pure CuO, Zn-doped CuO, and Na-doped CuO nanotextured films to efficiently detect CO2 gas. The structures, morphologies, chemical composition, and optical properties of all films are characterized using different tools. All films exhibit a crystalline monoclinic phase (tenorite) structure. The average crystallite size of pure CuO was 83.5 nm, whereas the values for CuO/Zn and CuO/Na were 73.15 nm and 63.08 nm, respectively. Subsequently, the gas-sensing capabilities of these films were evaluated for the detection of CO2 in terms of sensor response, selectivity, recovery time, response time, and limits of detection and quantification. The CuO/Na film offered the most pronounced sensitivity towards CO2 gas, as evidenced by a sensor response of 12.8% at room temperature and a low limit of detection (LoD) of 2.36 SCCM. The response of this sensor increased to 64.5% as the operating temperature increased to 150 °C. This study thus revealed a brand-new CuO/Na nanostructured film as a highly effective and economically viable sensor for the detection of CO2.

Integrated synthesis and comprehensive characterization of TiO2/AgBi2S3 ternary thin films via SILAR method.

AgBi2S3, a copious and innocuous ternary metal chalcogenide affiliated with the I-V-IV group of semiconductors, was synthesized. With an energy gap of 1.2eV, it closely matches the optimal 1.39eV for solar cell absorbers. Importantly, this chalcogenide exhibits a high absorption coefficient of 105 cm-1 at 600 nm. Using the successive ionic layer adsorption and reaction (SILAR) method; we deposited an AgBi2S3 thin film onto a titanium dioxide (TiO2) thin film. Characterization techniques encompassed XRD, SEM, EDXS, UV-Vis, EIS, and PEC performance analyses. The resulting TiO2/AgBi2S3 composite film ranged in thickness from 8 µm to 13 µm, with particle sizes spanning 20 nm-265 nm. Notably, the deposition of AgBi2S3 onto the TiO2 film caused depreciation in the TiO2 energy gap from 3.1eV to 1.7eV. Furthermore, it significantly enhanced the TiO2 film's absorbance across the visible and near-infrared regions. Intriguingly, the TiO2/AgBi2S3 composite film also exhibited discernible photoelectrochemical behavior.

SnapFib: An easy build Arduino based tabletop prototype for thin film deposition by Successive Ionic Layer Adsorption and Reaction method.

Non-vacuum-based techniques are suitable for thin-film deposition with precision stoichiometric control. Among those, the Successive Ionic Layer Adsorption and Reaction (SILAR) method is gaining popularity for its aqueous-based almost room temperature deposition option. This method has many advantages, including the ability to control the elemental composition and stoichiometry of precursors. It is also suitable for large-area deposition. It has many runtime parameters, e.g., the number of cycles, dip time, rinse time, etc., that control the quantitative and qualitative physical properties of the deposited film. But manually controlling all these parameters for the whole process is very difficult and cumbersome. Although there are several reports published on this similar type of home-built prototype, for fast, accurate, and economically affordable deposition operations, we need to develop a machine that maintains all the properties of the SILAR process and can be made using cheap technologies. Here we report the SnapFib, a cost-effective automated tabletop prototype machine that is easy to build for thin-film deposition on soda-lime glass substrates by the SILAR method without almost any human intervention. SnapFib is built using linear actuators, an ATmega328P (a microcontroller available on Arduino boards), and some other parts collected from laboratory sites. The whole firmware needed for this device has been developed and maintained using the Arduino IDE (Integrated Development Environment). All required functional features and control parameters are encoded in the microcontroller firmware. The construction cost of this prototype is around 600 USD. We validated our construction through XRD (X-ray Diffraction) and FESEM (Field Emission Scanning Electron Microscope) characterizations of thin films that were deposited by SnapFib. Since this is built under the CC-BY license, students and researchers can freely perform and validate their experiments and modify the hardware and software as required. With how easy it is to make and how much it costs; we hope that many thin-film deposition labs will quickly start using SnapFib as an added benefit.

MoO3, TiO2, and MoTiO5 based oxide semiconductor for photovoltaic applications.

Topographic essential synthesis of nanomaterials by adjusting easy preparatory factors is an effective way to improve a variety of nanostructured materials. The SILAR technique is used to evaluate the manufacturing samples of MoO3, TiO2, and MoTiO5 nanostructures. These nanostructures of MoO3, TiO2, and MoTiO5 are used as electrode materials in photovoltaic systems. The link between photoelectrochemical characteristics and MoO3, TiO2, and MoTiO5 nanostructures is studied in depth. The photoelectrochemical characteristics of MoO3, TiO2, and MoTiO5 nanostructures are discovered to be highly dependent. At a 5mV/s scan rate, the photocurrent of MoO3, TiO2, and MoTiO5 electrodes surged fast when sunlight was turned on, reaching values of 1.03 mA cm-2, 1.68 mA cm-2, and 14.20 mA cm-2, respectively. As soon as the solar illumination was turned off, the photocurrent value dropped to zero. Photocurrent transitions showed a quick, homogeneous photocurrent counterpart; this suggested that charge transfer in these ingredients is speedy and possibly related to the crystal buildings of MoO3, TiO2, and MoTiO5. MoTiO5 nano-belt and nano-disc thin films have typical uses in the photoelectrochemical sector because they have the best photoresponse and stability.

Photoconversion efficiency of In2S3/ZnO core-shell heterostructures nanorod arrays deposited via controlled SILAR cycles.

This paper reports the structures, morphologies, optical properties, and photoconversion efficiency (η%) of the In2S3/ZnO core-shell heterostructures nanorod arrays (IZCSHNRAs) produced via the controlled successive ionic layer absorption and reaction (SILAR) cycles. As-produced samples were characterized using XRD, FESEM, TEM, UV-Vis, PL, XPS and FTIR techniques. The proposed IZCSHNRAs revealed nearly double photocurrent density and η% values compared to the pure ZnO nanorod arrays (ZNRAs). In addition, the light absorption, crystallinity and microstructures of the specimens were appreciably improved with the increase of the SILAR cycles. The deposited nanoparticles of In2S3 (ISNPs) on the ZNRAs surface was responsible for the improvement in the heterostructures, light absorption and photogenerated electron-hole pairs separation, thus enhancing the photoconversion performance. It is established that a simple SILAR approach can be very useful to produce good quality IZCSHNRAs-based photoelectrodes required for the future development of high performance photoelectrochemical cells (PECs).

Amorphous nickel tungstate films prepared by SILAR method for electrocatalytic oxygen evolution reaction.

Development of electrocatalyst using facile way from non-noble metal compounds with high efficiency for effective water electrolysis is highly demanding for production of hydrogen energy. Nickel based electrocatalysts were currently developed for electrochemical water oxidation in alkaline pH. Herein, amorphous nickel tungstate (NiWO4) was synthesized using the facile successive ionic layer adsorption and reaction method. The films were characterized by X-ray diffraction, Raman spectroscopy, Fourier transfer infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy techniques. The electrochemical analysis showed 315 mV of overpotential at 100 mA cm-2 with lowest Tafel slope of 32 mV dec-1 for oxygen evolution reaction (OER) making films of NiWO4 compatible towards electrocatalysis of water in alkaline media. The chronopotentiometry measurements at 100 mA cm-2 over 24 h showed 97% retention of OER activity. The electrochemical active surface area (ECSA) of NW120 film was 25.5 cm-2.

Quick NO Gas Sensing by Ti-Doped Flower-Rod-like ZnO Structures Synthesized by the SILAR Method.

In this study, Ti-doped ZnO films with flower-rod-like nanostructures were synthesized by the successive ionic layer adsorption and reaction (SILAR) method for enhanced NO gas-sensing applications. The stoichiometric ratio of Ti in the host ZnO lattice was confirmed by atomic absorption and energy-dispersive X-ray spectroscopies. All of the synthesized films exhibited a pure wurtzite hexagonal structure that seemed to deteriorate at high Ti doping contents as was manifested by the measured X-ray diffraction patterns. Scanning electron microscopy images of ZnO revealed the coexistence of porous flower- and rod-like structures, which became finer, denser, and more compact with Ti doping. By UV-vis measurements, the transmittance of the synthesized pure ZnO thin film in the visible region (∼75%) increased by about 10% with Ti doping, and the energy band gap seemed to decrease up to some limit of Ti content. Among the fabricated sensors (based on pure ZnO, 1% Ti-doped, 3% Ti-doped, and 5% Ti-doped ZnO films), the best sensing performance was observed for the 1% Ti-doped ZnO film. At first, this was associated with its high density of oxygen vacancies present on the surface of the film and ionized oxygen vacancies present in the ZnO lattice (confirmed, respectively, by X-ray photoelectron and photoluminescence spectroscopies). Nonetheless, this may also be due to its increased crystallinity (confirmed by X-ray diffraction and photoluminescence spectroscopy), high area-to-volume ratio (confirmed by scanning electron microscopy images), high specific surface area (confirmed by Brunauer-Emmett-Teller measurements) as well as high mobility and carrier concentration (confirmed by Hall measurements). The sensor was highly selective to NO gas and showed notable stability as well as very short response and recovery times, which makes it eligible for the early detection of any indoor or outdoor NO gas leakages.

Effect of In-Incorporation and Annealing on CuxSe Thin Films.

A study of indium-incorporated copper selenide thin-film deposition on a glass substrate using the successive ionic adsorption and reaction method (SILAR) and the resulting properties is presented. The films were formed using these steps: selenization in the solution of diseleniumtetrathionate acid, treatment with copper(II/I) ions, incorporation of indium(III), and annealing in an inert nitrogen atmosphere. The elemental and phasal composition, as well as the morphological and optical properties of obtained films were determined. X-ray diffraction data showed a mixture of various compounds: Se, Cu0.87Se, In2Se3, and CuInSe2. The obtained films had a dendritic structure, agglomerated and not well-defined grains, and a film thickness of ~90 µm. The band gap values of copper selenide were 1.28-1.30 eV and increased after indium-incorporation and annealing. The optical properties of the formed films correspond to the optical properties of copper selenide and indium selenide semiconductors.

Comparison of Different Synthetic Routes of Hybrid Hematite-TiO2 Nanotubes-Based Electrodes.

Nowadays, green hydrogen is an important niche of interest in which the search for a suitable composite material is indispensable. In this sense, titanium oxide nanotubes (TiO2 nanotube, TNTs) were prepared from double anodic oxidation of Ti foil in ethylene glycol electrolyte. The morphology of the nanotubes was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Once characterized, nanotubes were used as templates for the deposition of hematite. The use of three synthetic procedures was assayed: Chemical Vapor Deposition (CVD), Successive Ionic Layer Adsorption and Reaction (SILAR), and electrochemical synthesis. In the first case, CVD, the deposition of hematite onto TiO2 yielded an uncovered substrate with the oxide and a negative shift of the flat band potential. On the other hand, the SILAR method yielded a considerable amount of hematite on the surface of nanotubes, leading to an obstruction of the tubes in most cases. Finally, with the electrochemical synthesis, the composite material obtained showed great control of the deposition, including the inner surface of the TNT. In addition, the impedance characterization showed a negative shift, indicating the changes of the interface electrode-electrolyte due to the modification with hematite. Finally, the screening of the methods showed the electrochemical synthesis as the best protocol for the desired material.

Anion exchange and successive ionic layer adsorption and reaction-assisted coating of BiVO4 with Bi2S3 to produce nanostructured photoanode for enhanced photoelectrochemical water splitting.

Photoelectrochemical water splitting is an environmentally benign way to store solar energy. Properties such as fast charge recombination and poor charge transport rate severely restrict the use of BiVO4 as a photoanode for photoelectrochemical water splitting and many attempts were made to improve the current performance limit of the photoanode. To address these disadvantages, a highly efficient BiVO4/Bi2S3 heterojunction was fabricated applying facial anion-exchange (AE) and successive ionic layer adsorption and reaction (SILAR). The deposition of Bi2S3 on BiVO4 nanoworms by both AE and SILAR was confirmed through morphological, structural, and optical analyses. The morphological analysis indicated that Bi2S3 grown through SILAR has relatively more crystalline-amorphous phase boundaries than Bi2S3 generated using the anion-exchange method. The highest photocurrent density was observed for the SILAR-coated Bi2S3 on BiVO4, which is three times the value of the pristine BiVO4 measured under 1 sun illumination (100 mW cm-2 with Air mass (AM) 1.5 filter) in a 0.5 M Na2SO4 electrolyte at 1.6 V vs. RHE. In addition, the deposition of Bi2S3 through AE results in a twofold higher photocurrent density compared to uncoated BiVO4. The comparison of the two cost-effective AE and SILAR methods to deposit Bi2S3 on BiVO4 showed a negative shift in the flat band Mott-Schottky values, which coincides with the drifted onset potential values of the current density-voltage (J-V) curve. Furthermore, photoelectrochemical impedance spectroscopy (PEIS) analyses and band alignment studies revealed that SILAR-grown Bi2S3 creates an effective heterojunction with BiVO4, which leads to an efficient charge transfer.

SILAR deposited iron phosphate as a bifunctional electrocatalyst for efficient water splitting.

The development of efficient and earth-abundant electrocatalysts for overall water splitting is important but still challenging. Herein, iron phosphate (FePi) electrode is synthesized using a successive ionic layer deposition and reaction (SILAR) method on a nickel foam substrate at room temperature and is used as a bifunctional electrocatalyst for water splitting. The prepared FePi electrodes show excellent electrocatalytic activity and stability for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The FePi electrode exhibits low overpotential of 230 mV and 157 mV towards the OER and HER, respectively, with superior long-term stability. As a result, an electrolyzer that exploits FePi as both the anode and the cathode is constructed, which requires a cell potential of 1.67 V to deliver a 10 mA cm-2 current density in 1 M KOH solution. The exceptional features of the catalyst lie in its structure and active metal sites, increasing surface area, accelerated electron transport and promoted reaction kinetics. This study may provide a facile and scalable approach to design a high-efficiency, earth-abundant electrocatalyst for water splitting.