Synthesis of Zinc Oxide Nanostructures on Graphene/Glass Substrate via Electrochemical Deposition: Effects of Potassium Chloride and Hexamethylenetetramine as Supporting Reagents

The effects of the supporting reagents hexamethylenetetramine(HMTA)and potassium chloride(KCl)mixed in zinc nitrate hexahydrate(Zn(NO3)2 6H2O)on the morphological,structural,and optical properties of the resulting Zn O nanostructures electrodeposited on graphene/glass substrates were investigated.The supporting reagent HMTA does not increase the density of nanorods,but it does remarkably improve the smoothness of the top edge surfaces and the hexagonal shape of the nanorods even at a low temperature of 75°C.Hydroxyl(OH-)ions from the HMTA suppress the sidewall growth of non-polar planes and promote the growth of Zn O on the polar plane to produce vertically aligned nanorods along the c axis.By contrast,the highly electronegative chlorine(Cl-)ions from the supporting reagent KCl suppress the growth of Zn O on the polar plane and promote the growth on non-polar planes to produce vertical stacking nanowall structures.HMTA was found to be able to significantly improve the crystallinity of the grown Zn O structures,as indicated by the observation of much lower FWHM values and a higher intensity ratio of the emission in the UV region to the emission in the visible region.Equimolar mixtures of Zn(NO3)2 6H2O and the supporting reagents HMTA and KCl seem to provide the optimum ratio of concentrations for the growth of high-density,uniform Zn O nanostructures.The corresponding transmittances for such molar ranges are approximately 55–58%(HMTA)and 63–70%(KCl),which are acceptable for solar cell and optoelectronic devices.

High performance Cu2O film/ZnO nanowires self-powered photodetector by electrochemical deposition

Self-powered photodetectors based on nanomaterials have attracted lots of attention for several years due to their various advantages.In this paper,we report a high performance Cu2O/ZnO self-powered photodetector fabricated by using electrochemical deposition.ZnO nanowires arrays grown on indium-tin-oxide glass are immersed in Cu2O film to construct type-Ⅱband structure.The Cu2O/ZnO photodetector exhibits a responsivity of 0.288 mA/W at 596 nm without bias.Compared with Cu2O photoconductive detector,the responsivity of the Cu2O/ZnO self-powered photodetector is enhanced by about two times at 2 V bias.It is attributed to the high power conversion efficiency and the efficient separation of the photogenerated electron-hole pairs,which are provided by the heterojunction.The outstanding comprehensive performances make the Cu2O film/ZnO nanowires self-powered photodetector have great potential applications.

Thermoelectric properties of Indium doped skutterudite thick film synthesized by a facile technique of electrochemical deposition

Doped/filled skutterudites are much studied materials due to their excellent thermoelectric performance.However,their synthesis and preparation is complicated.This work synthesized indium(In)doped cobalt triantimonide(CoSb_(3))skutterudite thick films using a facile electrochemical deposition technique through chronoamperometric steps for 2 h.The nominal composition of In element is found in the range of 0.55e0.23 for a stoichiometric condition of In doped CoSb_(3)thick films.The early crystal growth of In doped films shows instantaneous nucleation and is controlled by the charge transfer process with diffusion coefficient,D of 10^(-5)cm^(2)/s.The incorporation of In into the interstitial sites of CoSb_(3)cages is evident from the lattice constant(a)expansion as observed in XRD.The optimum Seeback coefficient(S)of the 0.5 mmol In doped CoSb_(3)thick film is89.84 mV/K at 282 K,due to an increase in the carrier concentration(n~10^(20)cm^(-3)).The negative S is due to the electron donor behaviour of the In.Meanwhile,high electrical conductivity,s value(14.26 kS/m)contributes to a power factor(S2s)increment of 115.11 mW/(m$K2).The result shows a promising thermoelectric property of doped skutterudite synthesized by electrochemical deposition technique.

Effect of Amino-,Methyl- and Epoxy-Silane Coupling as a Molecular Bridge for Formatting a Biomimetic Hydroxyapatite Coating on Titanium by Electrochemical Deposition

The objective of this study was to determine the role of functional groups of silane coupling on bioactive titanium(Ti) surface by electrochemical deposition, and calcium phosphate(CaP) coating, as well as bone cell adhesion and proliferation. Methyl group(—CH_3), amino group(—NH_2), and epoxy group(—glyph name—C(O)C) were introduced onto the bioactive Ti surface using self-assembled monolayers(SAMs)with different silane coupling agents as molecular bridges. The effect of the surface functional groups on the growth features of the CaP crystals was analyzed(including chemical compositions, element content,minerals morphology and crystal structure etc.). CH_3- terminated SAMs showed a hydrophobic surface and others were hydrophilic by contact angle measurement; NH_2-terminated SAMs showed a positive charge and others were negatively charged using zeta-potential measurement. Scanning electron microscopy results confirmed that flower-like structure coatings consisting of various pinpoint-like crystals were formatted by different functional groups of silane coupling, and the CaP coatings were multicrystalline consisting of hydroxyapatite(HA) and precursors. Ca P coating of CH_3- terminated SAMs exhibited more excellent crystallization property as compared to coatings of —NH_2 and —C(O)C groups. In vitro MC3T3-E1 cells adhesion and proliferation were performed. The results showed that CaP coatings on silane coupling functionalized surfaces supported cell adhesion and proliferation. Thus, these functional groups of silane coupling on Ti can form homogeneous and oriented nano-CaP coatings and provide a more biocompatible surface for bone regeneration and biomedical applications.

Intrinsic thermal stability of inverted perovskite solar cells based on electrochemical deposited PEDOT

Thermal stability of perovskite materials is an issue impairing the long-term operation of inverted perovskite solar cells(PSCs). Herein, the thermal attenuation mechanism of the MAPb I3films that deposited on two different hole transport layers(HTL), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS) and poly(3,4-ethylenedioxythiophene)(PEDOT), is comprehensively studied by applying a heat treatment at 85℃. The thermal stress causes the mutual ions migration of I, Pb and Ag through the device, which leads to the thermal decomposition of perovskite to form Pb I2. Interestingly, we find that I ions tend to migrate more towards electron transport layer(ETL) during heating, which is different with the observation of I ions migration towards HTL when bias pressure is applied. Moreover, the use of electrochemical deposited PEDOT as HTL significantly decreases the defect density of MAPb I3films as compared to PEDOT:PSS supported one. The electrochemical deposition PEDOT has good carrier mobility and low acidity, which avoids the drawbacks of aqueous PEDOT:PSS. Accordingly, the inverted PSCs based on PEDOT show superior durability than that with PEDOT:PSS. Our results reveal detailed degradation routes of a new kind of inverted PSCs which can contribute to the understanding of the failure of thermal-aged inverted PSCs.

Electrochemical deposition of uranium oxide with an electrocatalytically active electrode using double potential step technique

The development of effective uranium-removal techniques is of great significance to the environment and human health.In this work,a double potential step technique(DPST)was applied to remove U(VI)from uranium-containing wastewater using a carbon felt electrode modified by graphene oxide/phytic acid composite(GO-PA@CF).The application of DPST can inhibit water splitting and prevent GO-PA from adsorbing other interfering ions in wastewater.The GO-PA composite can effectively accelerate the electrochemical reduction rate of U(VI),which significantly improved the electrochemical deposition rate of uranium oxide.As a result,the maximum removal efficiency and maximum removal capacity of GOPA@CF electrode reached 98.7%and 1149.3 mg/g,respectively.The removal efficiency remained 97.2%after five cycles of reuse.Moreover,the removal efficiency of GO-PA@CF electrode can reach more than 70%in simulated wastewater.

H_2S Gas Sensor Based on Nanocrystalline ZnO Synthesized by Electrochemical-Deposition

ZnO nanocrystals were prepared by a direct current electrochemical deposition process under 3.0V working voltage and 30A/m^2 current density using zinc sulfate as raw materials.The nanocrystals were characterized by X-ray diffraction (XRD)and transmission electron microscopy(TEM).The results indicated that the nanocrystals are hexagonal wurtzite ZnO with particle size range of 25nm～40nm without any treating.Gas sensing properties of the sensors were tested by mixing a gas in air at static state;the tested results showed that the sensors based on nanocrystalline ZnO had satisfied gas sensing properties to H_2S gas at rather low temperature.

Corrosion Study of Two-step Deposition Coatings on Copper Foil

To improve corrosion inhibition performance of copper foil with a novel two-step electrochemical modification processes,the surface of 35μm copper foils was coated with graphene oxide(GO)via electrochemical method at first step,then was further coated with 3-aminopropyltrimethoxysilane(APTS)at the second step.For the first step the copper foil acted as anode,and as cathode for the second one(we labeled it as E-GO).Optimum coating parameters for the preparation of E-GO coating are 5 V and 1 min with ratio of APTS/deionized water(DI)1.5/98.5(v/v).The physicochemical properties of modified coating were studied by X-ray diffraction(XRD),scanning electron microscopy(SEM)and hydrophilicity test.Electrochemical behavior of different samples were also investigated.The experimental results indicate that anti-corrosion performance is significantly improved with two-step modified coating.And E-GO coating shows more positive corrosion potential and the highest corrosion resistance rate than others according to the Tafel curve.It is also found that surface hydrophobicity of E-GO coating is significantly improved.

Localized electrodeposition micro additive manufacturing of pure copper microstructures

The fabrication of pure copper microstructures with submicron resolution has found a host of applications,such as 5G communications and highly sensitive detection.The tiny and complex features of these structures can enhance device performance during high-frequency operation.However,manufacturing pure copper microstructures remain challenging.In this paper,we present localized electrochemical deposition micro additive manufacturing(LECD-μAM).This method combines localized electrochemical deposition(LECD)and closed-loop control of atomic force servo technology,which can effectively print helical springs and hollow tubes.We further demonstrate an overall model based on pulsed microfluidics from a hollow cantilever LECD process and closed-loop control of an atomic force servo.The printing state of the micro-helical springs can be assessed by simultaneously detecting the Z-axis displacement and the deflection of the atomic force probe cantilever.The results showed that it took 361 s to print a helical spring with a wire length of 320.11μm at a deposition rate of 0.887μm s^(-1),which can be changed on the fly by simply tuning the extrusion pressure and the applied voltage.Moreover,the in situ nanoindenter was used to measure the compressive mechanical properties of the helical spring.The shear modulus of the helical spring material was about 60.8 GPa,much higher than that of bulk copper(~44.2 GPa).Additionally,the microscopic morphology and chemical composition of the spring were characterized.These results delineate a new way of fabricating terahertz transmitter components and micro-helical antennas with LECD-μAM technology.

Cadmium selenide-sensitized upright-standing mesoporous zinc oxide nanosheets for efficient photoelectrochemical H_2 production

Cadmium selenide(Cd Se)-sensitized upright-standing mesoporous zinc oxide(ZnO) nanosheets were prepared via a chemical bath deposition followed by annealing and electrochemical deposition of Cd Se quantum dots(QDs). The Cd Se QDs absorb visible photons under sunlight illumination, promoting electrons from the valence band to the conduction band of Cd Se, which then quickly transfer to ZnO followed by the external load to the Pt counter electrode for water reduction. The as-prepared Cd Se/ZnO nanosheets show promising photoelectrochemical activities for hydrogen generation.

High-performance magnesium ion asymmetric Ppy@FeOOH//Mn3O4 micro-supercapacitor

Micro-supercapacitors(MSCs)are attractive electrochemical energy storage devices owing to their high power density and extended cycling stability.However,relatively low areal energy density still hinders their practical applications.Here,an asymmetric Mg ion MSC with promising high energy density is fabricated.Firstly,indium tin oxide(ITO)NWs were synthesized by chemical vapor deposition as the excellent current collector.Subsequently,nanostructured Mn_(3)O_(4)and Ppy@FeOOH were deposited on the laser-engraved interdigital structure ITO NWs electrodes as the positive and negative electrodes,respectively.Beneficial from the hierarchical micro-nano structures of active materials,high conductive electron transport pathways,and charge-balanced asymmetric electrodes,the obtained MSC possesses a high potential window of 2.2 V and a high areal capacitance of 107.3 mF cm^(-2)at 0.2 mA cm^(-2).The insitu XRD,VSM,and ex-situ XPS results reveal that the primary energy storage mechanism of Mg ions in negative FeOOH electrode is Mg ions de-/intercalation and phase transition reaction of FeOOH.Furthermore,the MSC exhibits a high specific energy density of 71.18μWh cm^(-2)at a power density of 0.22 mWh cm^(-2)and capacitance retention of 85%after 5000 cycles with unvaried Coulombic efficiency.These results suggest promising applications of our MSC in miniaturized energy storage devices.

Anti-corrosive mechanism of poly(N-ethylaniline)/sodium silicate electrochemical composites for copper:Correlated experimental and in-silico studies

Poly(N-ethylaniline)(PNEA)composites with varying silicate content were fabricated on copper through a novel electropolymerized strategy in acidic solution.Thickness,compactness,conductivity and adhesive strength of the composite(PNEA-10 Si)were optimized as silicate content reached 10 m M.Electrochemical,morphological and solution analyses were employed to evaluate the protective performance of PNEA and PNEA-10 Si coatings for copper in 3.5%Na Cl solution.Results of electrochemical analyses indicated that as-prepared coatings retarded the oxygen reduction process efficiently for copper in 3.5%Na Cl solution,drained corrosion current density and elevated interfacial charge transfer resistance.Due to favorable barrier effect,compact structure and low porosity index,PNEA-10 Si composite exhibited superior anti-corrosive performance,which was more tolerant than PNEA during long-time immersion.PNEA-10 Si coated sample exhibited a stable topography after 144 h immersion with the minimum concentration of released ions revealing the improved protection capacity.Electronic/atomic-multiscale calculations were conducted to clarify the deposition and protection mechanism of as-prepared coatings.Outcomes of density functional theory corroborated that silicate is stabilized in the PNEA layer via electrostatic force;and immobile silicate positively contributed to the charge transfer barrier of the composite.Molecular dynamics simulations evidenced that the favorable compatibility between PNEA and silicate facilitated polymer deposition and confined in-situ ions diffusion.

Electrochemical Preparation of WO_3 Nanowire Arrays

1 Results Ordered WO3 nanowires arrays have been fabricated by electrochemical deposition with anodic aluminum oxide (AAO) templates and annealing the W nanowire arrays in air at 400 ℃. The morphology and the chemical composition of WO3 nanowires arrays were characterized by Scanning Electron Microscopy (SEM),Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and X-ray diffraction (XRD). The results show that the diameters of the WO3 nanowires are about 90 nm, which is in go...

Wafer-scale quasi-layered tungstate-doped polypyrrole film with high volumetric capacitance

Layered materials are particularly attractive for supercapacitors because of their unique physical,electrical and chemical properties.Here,we demonstrate a facile and scalable electrochemical deposition method for wafer-scale synthesis of quasilayered tungstate-doped polypyrrole films(named TALPy)with controllable thickness and size.The as-prepared TALPy film exhibits a high gravimetric density and excellent volumetric capacitance,exceeding many high-performing carbon-and polymerbased film electrodes.Based on combined results of ex-situ X-ray diffraction(XRD),Raman and X-ray photoelectron spectroscopy(XPS),it is determined that TALPy stores charge through an ion intercalation process accompanied by change in oxidation states of polypyrrole backbone,which is referred as intercalation pseudocapacitance.All these results suggest the great promise of electrochemical deposition as a scalable and controllable bottom-up approach for synthesizing quasi-layered conductive organic-inorganic hybrid films for electrochemical energy storage applications with high volumetric performance.

Photoanode Activity of ZnO Nanotube Based Dye-Sensitized Solar Cells

Vertical ZnO nanotube (ZNT) arrays were synthesized onto an indium doped tin oxide (ITO) glass substrate by a simple electrochemical deposition technique followed by a selective etching process. Scanning electron microscopy (SEM) showed formation of well-faceted hexagonal ZNT arrays spreading uniformly over a largearea. X-ray diffraction (XRD) of ZNT layer showed substantially higher intensity for the (0002) diffractionpeak, indicating that the ZnO crystallites were well aligned with their c-axis. Profilometer measurements ofthe ZNT layer showed an average thickness of ～7 μm. Diameter size distribution (DSD) analysis showedthat ZNTs exhibited a narrow diameter size distribution in the range of 65–120 nm and centered at ～75nm. The photoluminescence (PL) spectrum measurement showed violet and blue luminescence peaks thatwere centered at 410 and 480 nm, respectively, indicating the presence of internal defects. Ultra-violet (UV)spectroscopy showed major absorbance peak at ～348 nm, exhibiting an increase in energy gap value of 3.4 eV.By employing the formed ZNTs as the photo-anode for a dye-sensitized solar cell (DSSC), a full-sun conversion efficiency of 1.01% was achieved with a fill factor of 54%. Quantum efficiency studies showed the maximumof incident photon-to-electron conversion efficiency in a visible region located at 520–550 nm range.

High-efficiency technique based on dielectrophoresis for assembling metal,semiconductor,and polymer nanorods

This paper presents a high-efficiency technique based on dielectrophoresis (DEP) for assembling metal, semiconductor, and polymer nanorods, which are synthesized by electrochemical deposition (ECD). The assembly patterns of these nanorods (width: 20 nm; length: 7 μm) were designed using a finite element method (FEM) simulation tool. Further, these nanorods were used in our experiment after their assembly patterns were fabricated. The assembly yield was found to be approximately 70% at an AC voltage of 30 Vp-p and at frequencies of 20 and 30 kHz, and the DC voltage prevented the random alignment of the nanorods at the edge of the assembly pattern. Moreover, the above-mentioned nanorods, which had different permittivities, were found to have similar assembly yields. The proposed method can be improved and applied to nanostructure device fabrication.

Cathodic behavior of scandium(Ⅲ) on reactive copper electrodes in LiF-CaF_(2)eutectic molten salt

The electrochemical formation of Sc-Cu alloy was investigated in LiF-CaF_(2) eutectic molten salt employing various electrochemical methods.Cyclic voltammetry and square wave voltammetry indicate that the reduction of scandium(Ⅲ) on the tungsten electrode is a one-step reduction process with three electrons transfer.And underpotential deposition of scandium on the copper electrode occurs owing to the depolarization effect,i.e.,forming Sc-Cu intermetallic compounds.The thermodynamic properties of the Sc-Cu intermetallic compounds ScCu_(4),ScCu_(2),and ScCu in the temperature range of 1153-1223 K were estimated by open-circuit chronopotentiometry.Moreover,the Sc-Cu alloys were prepared by potentiostatic electrolysis and characterized by optical microscope,X-ray diffraction,scanning electron microscopy,and energy dispersive spectroscopy.The results reveal that only Sc-Cu alloy composed of Cu-ScCu_(4) can be synthesized at low cathodic current density and above eutectic temperature.