Cathodic electrodeposition of Cu2S thin film for solar energy conversion

Cathodic electrodeposition in the presence of EDTA in aqueous solution was used to prepare Cu₂S thin film deposited on Ti substrate. The effect of deposition potential, concentration and deposition time was studied to determine the optimum condition for electro-deposition process. Cyclic voltammetry was performed to elucidate the electrodic processes that occur while potentials for electrodeposition were applied to determine the optimum potential for electrodeposition. The thin films are characterised by X-ray diffractometry. The photoactivity of the deposited films and their conduction types were evaluated using photoelectrochemical technique. The band gap energy and type of optical transitions were determined from optical absorbance data.     

Chemically and electrochemically deposited thin films for solar energy materials

Direct energy gap materials, e.g. CdTe, CuInSe₂, CuInGaSe₂, CdSe, ZnP₂ and Zn₃P₂, are the most interesting for thin-film solar cell applications. Among the various methods of preparation of these films, chemical bath deposition and electrodeposition deserve special attention because they have been shown to be inexpensive, low-temperature and non-polluting methods. Based on Pourbaix diagrams of CdS, CdTe, CuInSe₂, CdSe, etc., drawn from basic considerations, the best parameters for their electrodeposition are deduced. Theoretical considerations on the chemical-bath deposition of CdS, CdSe and Sb₂S₃ are also indicated. In particular, the role of the complexing agent and of the ligands in chemical bath deposition quality is discussed, as are the uniformity and stability of the films. The photoelectrochemical, Schottky barrier and heterojunction solar cell properties based on chemically and electrochemically deposited thin films with heteropolyacids are shown. Future trends for chemically and electrochemically deposited polycrystalline thin films are addressed. Results from very recent work done in the improvement of chemically and electrochemically deposited thin films are presented. Significant results obtained on advanced CdS/CdTe, CdS/CIS and CdS/CIGS solar cells developed by industry and by laboratory groups worldwide are indicated. Emerging low cost materials or/and less environmental hazards materials which may introduce solar cells into worldwide market are considered in the conclusion.     

Efficient hydrogen evolution catalysis triggered by electrochemically anchored platinum nano-islands on functionalized-MWCNT

We report the electrochemical deposition (ECD) of platinum nano-islands (Pt NIs) on functionalized multi-walled carbon nanotubes (ECD Pt NIs@f-MWCNT) as an efficient electrocatalyst for the hydrogen evolution reaction (HER). Pristine MWCNT was acid treated to induce the number of oxygen functional groups on the surface and enhances the wettability. Thereafter, Pt nanoparticles (Pt Nps) were deposited by a simple electrodeposition technique on the oxygen enriched MWCNT surface. The Pt NIs@f-MWCNT has been physicochemically characterized using X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy and X-ray photoelectron Spectroscopy (XPS). The TEM analysis showed the presence of Pt NIs on MWCNT wherein, the NIs were made up of small Pt nanoclusters of ～4 nm in dimension. The electrochemical HER studies were carried out using linear sweep voltammetry (LSV), Tafel polarization and electrochemical impedance spectroscopy (EIS). An overpotential (?) of ?84 mV was obtained at a current density (j) of ?10 mA/cm². The amount of Pt loading has been optimized through electrodeposition. Enhanced HER activity was observed with a Pt loading of 3.8 μg/cm². In order to ascertain the durability of the catalyst, accelerated degradation test (ADT) was carried out for 10,000 cycles at a scan rate (?) of 100 mV/s. The turnover frequency (TOF) was estimated to be 6.3 s^?1 at ? = ?70 mV.     

Electrodeposition and characterization of ZnSe semiconductor thin films

In this work, results on the preparation and characterization of ZnSe thin films obtained by electrodeposition are presented. Voltammetric curves were recorded in order to characterize the electrochemical behavior of the Zn⁺²/SeO₂ system on different substrates. Thin films were deposited potentiostatically from an unstirred, deareated aqueous solution onto titanium, glass substrates coated with fluorine doped tin oxide and ITO glass substrates. The effect of main parameters such as the deposition potential, SeO₂ concentration and annealing on film composition and structure were analyzed. The as-grown and treated layers were characterized by X-ray energy dispersive analysis, X-ray diffraction, scanning electron microscopy and photoelectrochemical studies. Optical measurements were done on these samples which gave a clear band edge near 2.6 eV quite close to the accepted room temperature value of 2.7 eV for ZnSe.     

Mechanistic investigation on tuning the conductivity type of cuprous oxide (Cu2O) thin films via deposition potential

The conductivity type of cuprous oxide (Cu₂O) thin films is tuned by controlling the deposition potential of an electrochemical process in an acid cupric acetate solution containing sodium dodecyl sulfate. The morphology and chemical composition of the deposited Cu₂O films are studied by SEM, XRD and XPS. The change of the conductivity type of Cu₂O films is further studied through zero-bias photocurrent and Mott-Schottky measurements. The results indicate that the Cu₂O films behave as n-type semiconductors when the overpotentials are low (potentials higher than ?0.05 V) and p-type semiconductors when the overpotentials are high (potentials lower than ?0.10 V). The transformation of conductivity from n-type to p-type comes from the competition reactions between forming Cu₂O and forming metallic Cu from Cu²⁺. When the potential is lower than ?0.10 V, most of Cu²⁺ are consumed by the growth of metallic Cu at the film/solution interface, so that the Cu²⁺ provided to grow Cu₂O film are insufficient and copper vacancies form in the film, leading to the p-type conductivity.     

Preparation of carbon nanotube and graphene doped polyphenylene sulfide flexible film electrodes and the electrodeposition of Cu2O nanocrystals for hydrogen-generation

Through annealing and electrochemical reduction methods, we successfully fabricates reduced graphene oxide layer (RGOL) modified carbon nanotube and reduced graphene oxide (CNT + RGO) doped polyphenylene sulfide (PPS) flexible thin film electrodes. These composite structure films can not only overcome the brittle nature of PPS, but also make good use of the thermal stability of PPS. Furthermore, carbon nanotube and reduced graphene oxide enhance the electrical conductivity of the composite films. Truncated octahedral and cuboctahedral Cu₂O nanocrystals are synthesized on RGOL modified CNT + RGO doped PPS (RGOL@PPS/CNT + RGO) composite film by a facile electrodeposition method without using any surfactants or external heating. RGOL on the PPS/CNT + RGO substrate facilitates the formation of Cu₂O morphology. The obtained Cu₂O composite film shows a superior ability for the hydrogen evolution reaction (HER) compared with other Cu₂O electrocatalysts. The Cu₂O with a smaller loading less than 0.04 mg cm^?2 on the composite film exhibits excellent HER activities with a low onset potential of 0.05 V and large current densities. The results of the HER performance indicates that the RGOL@PPS/CNT + RGO composite film has a potential application in flexible hydrogen-producing devices.     

Application of CuS–ZnS PN junction for photoelectrochemical water splitting

A CuS thin film was prepared by the sulfurization of the electrodeposited copper layer on the FTO substrate using sulfur powder at 400 °C. Surface morphology and structure of the CuS thin film were investigated by scanning electron microscopy and X-ray diffraction. The surface morphology of the CuS thin film was worm-like with the diameter of 70 nm and its crystal structure was hexagonal. Band gap energy of the CuS thin film was obtained as 1.5 eV using absorption spectra. Photoelectrochemical response of the CuS thin film was analyzed under chopped illumination at negative and positive potentials. It showed photoelectrochemical response at negative potentials (ca. 2.6 μA cm^?2 at ?0.4 V vs. Ag/AgCl), but not at positive potentials, which confirmed its p-type semiconductivity. A ZnS thin film was synthesized by spray pyrolysis method and characterized using field emission scanning electron microscopy, X-ray diffraction and UV–vis spectrometer. It was shown that the surface morphology was smooth with the grain size of about 50–150 nm. Also, its crystal structure and band gap energy were hexagonal and 3.72 eV, respectively. In order to obtain PN (positive–negative) junction and increase photoelectrochemical response, the ZnS (n-type semiconductor) thin film was deposited on CuS (p-type semiconductor). Linear scan of elemental composition confirmed the presence of FTO, CuS and ZnS layers. Photoelectrochemical characterization showed more photoresponse than the CuS thin film at negative potentials (13.6 μA cm^?2 at ?0.4 V vs. Ag/AgCl) and no photoresponse at positive potentials. The results confirmed the synthesizing of PN junction at the interface of CuS and ZnS.     

Enhanced solar-driven water splitting by ZnO/CdTe heterostructure thin films-based photocatalysts

Solar-driven hydrogen production by water splitting using a photocatalyst is considered the most effective approach to produce hydrogen. Hydrogen is the most suitable renewable energy source. The efficiency of hydrogen production is still low. The efficiency of hydrogen production through photocatalysis can be enhanced by preparing a suitable and efficient photocatalyst. In this work, ZnO thin films were deposited on CdTe thin films at 600 °C, 650 °C, and 700 °C temperatures to form ZnO/CdTe heterostructure thin films by chemical vapor deposition (CVD) as photoelectrodes for water splitting. The photoelectrochemical properties showed that ZnO/CdTe heterostructure thin films have better photocurrent response compared to pristine ZnO and CdTe thin films. EIS results showed that the charge transfer at the electrode-electrolyte interface for ZnO/CdTe heterostructure thin films is much better than that of the pristine ZnO film. The ZnO/CdTe-700 °C heterostructure thin film has a 112-fold higher rate of photocatalytic hydrogen generation than pure ZnO.     

CuO/Pd composite photocathodes for photoelectrochemical hydrogen evolution reaction

CuO has been considered as a promising photocathodic material for photoelectrochemical (PEC) hydrogen evolution reaction (HER). In this work, CuO films were prepared by a facile and cost-effective method that involves solution synthesis, spin-coating and thermal treatment processes. The resulting CuO films had a monoclinic crystal structure with bandgap energy of 1.56 eV and a conduction band position of 3.73 eV below the vacuum level in borate buffer solution. The CuO films exhibited good PEC activity toward HER and the preparation conditions had great effect on the activity. The photoactivity of the CuO film decayed to approximately 19% of its original value after reaction for 10 h under illumination. The reduction of CuO to Cu₂O has been confirmed to be a parallel competitive reaction against HER. The mismatched band structure of the resulting CuO/Cu₂O heterojunction was believed to be the main cause of the decay of photoactivity. The photo-assisted electrodeposition method was developed to prepare CuO/Pd composite photocathode. The presence of Pd on CuO greatly increased the photocurrent especially at low overpotentials. In addition, the CuO/Pd composite exhibited significantly improved photostability compared to CuO. This work demonstrates the feasibility of increasing PEC activity and stability of CuO-based photocathodes by combining CuO with noble metal nanoparticles.     

Fabrication of Mo-modified carbon felt as candidate substrate for electrolysis: Optimization of pH,current and metal amount

Mo was electrochemically deposited over a carbon felt (C) support in order to enhance hydrogen evolution activity of the support and make it a candidate for further modifications. For this aim, the effects of pH of deposition bath solution, deposition current and amount of deposited Mo were studied and optimized. Hydrogen evolution activity of the electrodes was evaluated in 1 M KOH solution with the help of electrochemical techniques. Surface structures of the electrodes were examined by scanning electron microscopy (SEM). It was found that 1 g Mo/g C modified electrode at pH 6 and 50 mA current exhibits the best hydrogen releasing performance. The enhanced current density at this electrode under ?1.60 V(Ag/AgCl) was 59.6% with respect to the bare support, which demonstrates that modifying the support by a thin Mo layer favors the hydrogen evolution reaction (HER) and reduces the energy requirement. The high hydrogen evolution performance of this modified substrate was assigned to its excellent structure, large surface area as well as high intrinsic catalytic activity of Mo. According to experimental findings, the Mo-modified C substrate was suggested for preparation of further modified electrode materials, especially with trace amounts of precious metals.     

Porous NiO/poly(3,4-ethylenedioxythiophene) films as anode materials for lithium ion batteries

NiO/poly(3,4-ethylenedioxythiophene) (PEDOT) films are prepared by chemical bath deposition and electrodeposition techniques using nickel foam as the substrate. These composite films are porous, and constructed by many interconnected nanoflakes. As anode materials for lithium ion batteries, the NiO/PEDOT films exhibit weaker polarization and better cycling performance as compared to the bare NiO film. Among these composite films, the NiO/PEDOT film deposited after 2 CV cycles has the best cycling performance, and its specific capacity after 50 cycles at the current density of 2 C is 520 mAh g⁻¹. The improvements of these electrochemical properties are attributed to the PEDOT, a highly conductive polymer, which covers on the surfaces of the NiO nanoflakes, forming a conductive network and thus enhances the electrical conduction of the electrode.     

Properties of spray deposited titanium dioxide thin films and their application in photoelectrocatalysis

Thin films of titanium dioxide were deposited onto optically transparent, electrically conducting substrates (fluorine doped tin oxide on glass). The two oxide layers, SnO₂ and TiO₂, were deposited sequentially by spray pyrolysis. TiO₂ films of up to 800 nm thickness were prepared by varying the quantity of sprayed solution (titanyl acetylacetonate in methanol), at a growth rate of 0.15 nm/s.The effect of film thickness on the structural, optical and photoelectrochemical properties of TiO₂ films was studied. Scanning electron microscopy showed that the polycrystalline anatase films were compact. The grain size increased up to 1100 nm with increase in film thickness, whereas the crystallite size remained constant (40 nm) as shown by X-ray diffraction. The films had a transmittance of more than 70% in the visible region.Junctions of the semiconducting films with aqueous electrolytes were rectifying and photoactive. Films of 330 or 600 nm were thick enough to exhibit maximum photoelectrochemical response for light of a wavelength of 313 or 365 nm, respectively. Under depletion conditions, an IPCE (incident photon to current conversion efficiency) of 0.8 for a 330 nm thick film at 313 nm was obtained.Oxalic acid degradation under UVA light and under sunlight, applying electrical bias, was demonstrated using these electrodes.     

Effect of alkaline-doping on photoelectrochemical activity of electrodeposited cuprous oxide films

P-type Cu₂O films with alkaline ions (Li⁺, Na⁺ and K⁺) of unintentional dopants on indium tin oxide coated glass substrate are successfully fabricated via a simple electrodeposition method for photoelectrochemical (PEC) hydrogen generation. The SEM and XRD analysis show the as-grown films with the pyramid-like morphology and cubic structure, and the composition of alkaline-doped Cu₂O films are examined using XPS spectroscopy to demonstrate the substitution of alkaline ions in the Cu₂O lattice. The optical analyses, including the absorbance and low-temperature photoluminescence spectra, confirm a bandgap of 2.3 eV and the presence of structural defects in alkaline-doped Cu₂O films. The Mott-Schottky plot shows the flat band potentials of the alkaline-doped Cu₂O films to be approximately ?0.1 V and the hole concentrations in the order of 10¹⁷ cm^?3. Significantly, the Cu₂O:Li film photocathode exhibits a higher photocurrent of ?2.2 mA cm^?2 at a potential of ?0.6 V vs Ag/AgCl which are greater than those of Cu₂O:K and Cu₂O:Na films due to greater preferred orientation degrees along (111) and less structural defects, because the ionic radii of Cu and Li is similar. These results demonstrate the great potential of alkaline doped Cu₂O films in solar-related applications.     

Different interesting enhanced influence from polyaniline and poly(o-toluidine) on electrocatalytic activities of Pt on them toward electrooxidation of methanol

Polyaniline (PANI) and poly(o-toluidine) (POT) with various film thickness were electropolymerized using potentiostatic method at the surface of GC electrode. The two conducting polymers were characterized by CV, in situ UV–vis spectroscopy and electrochemical impedance spectroscopy. Two composite catalysts (Pt/PANI/GC and Pt/POT/GC) with various film growth charge have been fabricated by the electro deposition of Pt on the PANI/GC and POT/GC at ?0.1 V. then they were used for the electrooxidation of methanol in 0.5 M H₂SO₄ containing 1.0 M methanol. The properties of both the polymers change with the increase of film growth charge. As-formed composite catalysts were characterized by SEM and the electrochemical methods. The Pt nanoparticles deposited at ?0.1 V exhibit thorns morphology and good dispersion on the POT with the film growth charge of 4.5 mC. The electrocatalytic activity for methanol oxidation of Pt/POT/GC is higher than Pt/PANI/GC for all the film charge, and they both exhibit the largest electrocatalytic activity at film charge of 4.5 mC. The present study shows that Pt/POT/GC would be a promising choice for methanol electrooxidation in comparison with Pt/PANI/GC.     

CuO-TiO2 nanostructures prepared by chemical and electrochemical methods as photo electrode for hydrogen production

In present study, copper (II) oxide (CuO) nanostructures were separately synthesized via chemical and electrochemical methods. CuO were coated with chemically synthesized titanium dioxide (TiO₂). Morphological and structural properties of CuO and TiO₂ coated CuO (CuO-TiO₂) materials were examined via field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD). FESEM images showed that nanowire like CuO formed at both chemical and electrochemical techniques. TiO₂ nanoparticles were homogenously distributed all over CuO surfaces. XRD pattern revealed CuO has monoclinic crystal structure with metallic Cu. Moreover, rutile TiO₂ crystallized in the tetragonal crystal structure. Electrochemical impedance spectroscopy (EIS) and potentiodynamic (PD) polarization measurements were utilized to study electro catalytic performance of the materials towards hydrogen evolution reaction (HER). The values of both energy consumption, and energy efficiency were determined as 329.43 kJ mol^?1 and 86.0% at ?50 mA cm^?2 current density for HER on electrochemically synthesized CuO-TiO₂ at 25 °C.     

Electrochemical performance of amorphous-silicon thin films for lithium rechargeable batteries

The effect of deposition temperature and film thickness on the electrochemical performance of amorphous-Si thin films deposited on a copper foil is studied. The electrochemical properties show optimum conditions at 200 °C deposition, and thinner films exhibit superior electrochemical performance than thicker ones. A film of 200 nm Si deposited at 200 °C exhibits excellent cycleability with a specific capacity of ∼3000 mAh g⁻¹. This is probably due to optimization between the strong adhesion by Si/Cu interdiffusion and the film stress.     

Surface modification of ZnO microrod arrays films by ion-exchange approach and their photoelectrochemical performances

ZnO microrod arrays films with the surface modification by two steps ion-exchange approach have been investigated as photoanodes in photoelectrochemical (PEC) cells. X-ray diffraction, Raman, scanning electron microscope, energy dispersive X-ray detector, UV–vis techniques and PEC measurement have been used in the pristine and surface modified ZnO microrod films. The results show that ZnS and CdS layer can be deposited on ZnO microrod surface through a two steps ion-exchange procedure. What's more, it is found that ion-exchange method is a simple approach to adjust CdS content on the samples surface via changing experimental temperature. Consequently, the PEC property of films can be improved through optimizing CdS content on the ZnO microrods surface. In this experiment, it is found that the optimized condition for preparing film is 70 °C (first step) and 100 °C (second step). These results suggest that surface tuning via ion-exchange method should represent a viable strategy to further improve the efficiency of ZnO microrods photoanodes.     

Electrochemical template synthesis of Ni–Cu bilayer hollow microtubes for green hydrogen production through electrocatalytic reforming of ethanol

This article is devoted to the investigation of the processes occurring at the synthesis of Ni–Cu hollow tubes (NC-HT) and their application as an electrocatalyst in the hydrogen evolution reaction from water-ethanol solution. The reactions at the electrochemical reduction of CuO to Cu and during the electrodeposition of nickel were investigated by chronopotentiometry. Depending on the thickness of the nickel layer, morphology (SEM) and chemical composition (EDX-mapping, XRD) of tubes, as well as electrocatalytic activity (CVA, ECSA, TOF, and stability tests) were studied. The synthesized materials have a structure with a high electrochemically active surface area (ECSA) from 1.38 to 3.50 m²g^-1, which makes it possible to fulfill low activation overpotential values equal to ?86 and ?250 mV at 10 and 50 mAcm^?2 after 100 cycles. The stability test results demonstrate the overpotential values ?160, ?183, ?265 mV for NC-HT15, NC-HT30, and NC-HT60, respectively, after 24 h examinations.     

Three dimensional assembly of electrocatalytic platinum nanostructures on reduced graphene oxide – An electrochemical approach for high performance catalyst for methanol oxidation

By means of co-electrodeposition, we fabricated 3D assembly of Pt nanostructures with dominant (100) plane on reduced graphene oxide (rGO) modified graphite electrode. The strong metal-support interaction at the atomic level makes the nanostructure highly durable and this modified electrode exhibited high electrocatalytic activity towards methanol oxidation. It has been found that the morphology, active site and the electrochemical activity of Pt are highly dependent on the substrate and the number of electrochemical cycling used for the deposition. rGO-Pt composite deposited using one cycle showed a high mass activity of 2.54 A/mg at 0.67 V for methanol oxidation in acidic condition and 1.84 A/mg at ?0.03 V in alkaline medium. This simple and single step approach using electrodeposition to grow the morphology controlled Pt nanostructure on rGO, will aid in the development of active and stable catalyst for fuel cell applications.     

Electrochemical deposited Mg-PPy multilayered film to store hydrogen

The stability of magnesium and its hydride (Mg/MgH₂) against moisture and oxygen can be improved by forming a multilayered structure with a protective polymeric layer. Herein, we report for the first time the fabrication of such a multilayered structure via an electrochemical deposition method consisting of the successive depositions of Mg on electropolymerised polypyrrole (PPy) films. The thickness of the PPy and the Mg layers was ～1 μm, which is larger than the Mg/Pd multilayers prepared via physical deposition methods, owing to the higher surface roughness of electropolymerised films. However, such films displayed remarkable hydrogen storage properties. Hydrogenation of the PPy/Mg film was achieved at 100 °C and hydrogen release started from 125 °C with a peak at ～215 °C. When covered by a second PPy layer, the hydrogen desorption temperature increased slightly to 230 °C. These hydrogen absorption and desorption temperatures are significantly lower than that of pristine Mg/MgH₂ micron sized powders and this was achieved without any additional catalyst. Furthermore, such hydrogenated PPy/Mg/PPy film structures were found to be stable in air even after one week.