Electrodeposition of P-type BixSb2−xTey thermoelectric film from dimethyl sulfoxide solution

The electrochemical behaviors of Bi(III), Te(IV), Sb(III) and their mixtures in DMSO solutions were investigated using cyclic voltammetry and linear sweep voltammetry measurements. On this basis, Bi_xSb_2−xTe_y film thermoelectric materials were prepared by potentiodynamic electrodeposition technique from mixed DMSO solution, and the compositions, structures, morphologies as well as the thermoelectric properties of the deposited films were also analyzed. The results show that Bi_xSb_2−xTe_y compound can be prepared in a very wide potential range by potentiodynamic electrodeposition technique in the mixed DMSO solutions. After anneal treatment, the deposited film prepared in the potential range of −200 to −400 mV shows the highest Seebeck coefficient (185 μV/K), the lowest resistivity (3.34 × 10⁻⁵ Ω m), the smoothest surface, the most compact structure and processes the stoichiometry (Bi_0.49Sb_1.53Te_2.98) approaching to the Bi_0.5Sb_1.5Te₃ ideal material most. This Bi_0.49Sb_1.53Te_2.98 film is a kind of nanocrystalline material and (0 1 5) crystal plane is its preferred orientation.     

One-step electrochemical preparation of the ternary (BixSb1−x)2Te3 thin films on Au(1 1 1): Composition-dependent growth and characterization studies

This study reports on the synthesis of ternary semiconductor (Bi_xSb_1−x)₂Te₃ thin films on Au(1 1 1) using a practical electrochemical method, based on the simultaneous underpotential deposition (UPD) of Bi, Sb and Te from the same solution containing Bi³⁺, SbO⁺, and HTeO₂⁺ at a constant potential. The thin films are characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS) and reflection absorption-FTIR (RA-FTIR) to determine structural, morphological, compositional and optic properties. The ternary thin films of (Bi_xSb_1−x)₂Te₃ with various compositions (0.0 ≤ x ≤ 1.0) are highly crystalline and have a kinetically preferred orientation at (0 1 5) for hexagonal crystal structure. AFM images show uniform morphology with hexagonal-shaped crystals deposited over the entire gold substrate. The structure and composition analyses reveal that the thin films are pure phase with corresponding atomic ratios. The optical studies show that the band gap of (Bi_xSb_1−x)₂Te₃ thin films could be tuned from 0.17 eV to 0.29 eV as a function of composition.     

Electrodeposition of Sb, Bi, Te, and their alloys in AlCl3-NaCl-KCl molten salt

The Electrochemistry of Sb, Bi, and Te in AlCl₃-NaCl-KCl molten salt containing SbCl₃, BiCl₃, and/or TeCl₄ at 423 K was investigated by voltammetry, and electrodeposition of the three metals was performed under constant potential control in the melt. The voltammogram on a glassy carbon (GC) electrode in a melt containing 0.025 mol dm⁻³ [M] SbCl₃ showed a couple of redox peak corresponding to the Sb/Sb(III) redox reaction, and a stable layer of pure Sb was deposited under the constant potential control. The voltammograms in the melt containing 0.025 M BiCl₃ or 0.025 M TeCl₄ showed several redox couples. Stable deposit layers of pure Bi and Te were not obtained under the constant potential control, as the deposited layers detached from the electrode and immediately dissolved into the molten salt. Binary alloy deposition was possible in a melt containing BiCl₃ and SbCl₃, and also with BiCl₃ and TeCl₄. A stable Bi-Sb alloy deposit of metallic Sb and Bi-Sb solid solution was obtained at 0.8 and 0.9 V versus Al/Al(III) in the melt containing BiCl₃ and SbCl₃. The atomic ratio of Bi in the deposit was 37% at 0.9 V and 57% at 0.8 V. A stable Bi-Te alloy deposit was also obtained with the molten salt containing BiCl₃ and TeCl₄. The deposited Bi-Te alloy consisted of a mixture of Bi₂Te₃, BiTe, and Bi₂Te. The alloy deposit had good crystallinity and the preferential orientation was the (1 1 0) plane.     

A mechanistic study of electrodeposition of bismuth telluride on stainless steel substrates

Miniaturization of Bi₂Te₃ compounds is of great interest in semiconductor industries due to their distinct anisotropic thermoelectric properties at room temperature. The aim of the present work was to investigate the mechanism of the electrodeposition of Bi₂Te₃ compounds on stainless steel substrates and relate the morphology and composition of the resulting deposits to experimental parameters. Cyclic voltammetry (CV) experiments in acidic solutions containing Bi³⁺ and/or HTeO₂⁺ ions show that the deposition potential for the Bi₂Te₃ compound is more positive than either of the single elements alone. A detailed mechanism of the co-deposition was obtained by varying the concentrations of the two elements and evaluating the corresponding morphological and compositional changes of the deposits. The results show that the deposition of Te is kinetically hindered and that Bi deposition plays a major role during the co-deposition.     

Composition-dependent characterization and optimal control of electrodeposited Bi2Te3 films for thermoelectric application

A method to control composition of Bi₂Te₃ films by mass transfer manipulation has been developed. The film composition can be varied by a diffusion-controlled method, which is related to the change of Bi³⁺/HTeO₂⁺ ratios in a controlled diffusion layer. A homogeneous and dense film with precise chemical composition could thus be obtained under constant electrode polarization. Meanwhile, the solo dependence of film properties on composition change of both Te-rich and Bi-rich films were investigated. Firstly, the studies of XRD and FE-SEM showed that different Te contents in deposit would lead to different dimensions of unit cell and grain sizes. The Seebeck coefficient increased apparently when the Te content was over 60 at.% Te. Te-rich films had higher carrier concentration but slower mobility than Bi-rich films. Inverse relations were observed between carrier concentration and carrier mobility and between Seebeck coefficient and conductivity. Therefore, an optimal power factor of 7 × 10⁻⁴ W/m K² was realized near the stoichiometric Bi₂Te₃.     

Electrodeposition of Ag and Pd on a reconstructed Au(1 1 1) electrode surface studied by in situ scanning tunneling microscopy

Electrochemical deposition of Ag and potential-induced structural change of the deposited Ag layer on a reconstructed surface of Au(1 1 1) electrode were followed by in situ scanning tunneling microscope (STM). A uniform Ag monolayer was formed on a reconstructed Au(1 1 1) surface in a 50-mM H₂SO₄ solution at +0.3 V (vs. Ag/AgCl) after adding a solution containing Ag₂SO₄ so that the concentration of Ag⁺ in the STM cell became ca. 2 μM. No characteristic height corrugation such as the Au reconstruction was observed on the surface, indicating that the lifting of the substrate Au reconstruction occurred by Ag deposition. The formed Ag monolayer was converted to a net-like shaped Ag nano-pattern of biatomic height when the potential was stepped from +0.3 to −0.2 V in the solution containing 2 μM Ag⁺. This result indicates that the substrate Au(1 1 1)-(1 × 1) surface was converted to the reconstructed surface even in the presence of Ag adlayer. Quite different structure was observed for Pd deposition on a reconstructed surface of Au(1 1 1) electrode at +0.3 V and the origin for this difference between Ag and Pd deposition is discussed.     

Orientation-controlled synthesis and characterization of Bi2Te3 nanofilms, and nanowires via electrochemical co-deposition

An electrochemical deposition technique based on co-deposition was used to deposit preferentially oriented Bi₂Te₃ nanostructures (nanofilm, and nanowire). The shared underpotential deposition (UPD) potentials for both Bi and Te co-deposition were determined by cyclic voltammetric measurements. The scanning probe microscopy (scanning tunneling microscopy (STM) and atomic force microscopy (AFM)) and the X-ray diffraction (XRD) data indicated that the electrodeposition of Bi₂Te₃ results in nanofilm-structured deposits with a preferential orientation at (0 1 5) and nanowired-structured deposits with a preferential orientation at (1 1 0) in acidic and basic (in the presence of ethylenediaminetetraacetic acid (EDTA)) medium, respectively. The results show that the nucleation and growth mechanism follows 3D mode in acidic solutions and 2D mode in basic solution containing EDTA additive. The optical characterization performed by reflection absorption Fourier transform infrared (RA-FTIR) spectroscopy showed that the band gap energy of Bi₂Te₃ nanostructures depends on the thickness, size, and shape of the nanostructures and the band gap increases as the deposition time decreases. Moreover, the quantum confinement is strengthened in the wire-like deposits relative to the film-like deposits. Energy dispersive X-ray spectroscopy (EDS) analysis demonstrated that Bi₂Te₃ nanostructures were always in 2:3 stoichiometry, and they were made up of only pure Bi and Te.     

Investigations on the electrodeposition behaviors of Bi0.5Sb1.5Te3 thin film from nitric acid baths

The electrochemical reduction process of Bi³⁺, HTeO₂⁺, Sb^III and their mixtures in nitric acid medium was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The reduction products electrodeposited at various potentials were examined using X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). The results show that cathodic process in the nitric acid solution containing Bi³⁺, HTeO₂⁺ and Sb^III involves the following reduction reactions in different polarizing potential ranges: In low polarizing potential ranges, Te⁰ is formed firstly on the electrode surface through the electrochemical reduction of HTeO₂⁺; with the negative shift of the cathodic polarizing potential, the reduction reaction of Bi³⁺ with Te⁰ to form Bi₂Te₃ takes place; when the cathodic polarizing potential is negative enough, Bi³⁺ and Sb^III react with Te⁰ to form Bi_0.5Sb_1.5Te₃. The results indicate that Bi_0.5Sb_1.5Te₃ films can be fabricated by controlling the electrodepositing potential in a proper high potential ranges.     

The underpotential deposition of Bi2Te3−ySey thin films by an electrochemical co-deposition method

Bi₂Te_3−ySe_y thin films were grown on Au(1 1 1) substrates using an electrochemical co-deposition method at 25 °C. The appropriate co-deposition potentials based on the underpotential deposition (upd) potentials of Bi, Te and Se have been determined by the cyclic voltammetric studies. The films were grown from an electrolyte of 2.5 mM Bi(NO₃)₃, 2 mM TeO₂, and 0.3 mM SeO₂ in 0.1 M HNO₃ at a potential of −0.02 V vs. Ag|AgCl (3 M NaCl). X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were employed to characterize the thin films. XRD and EDS results revealed that the films are single phase with approximate composition of Bi₂Te_2.7Se_0.3. SEM studies showed that the films are homogeneous and have micronsized granular crystallites.     

Comparison of AlPO4- and Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode materials for Li-ion battery

Electrochemical and thermal properties of Co₃(PO₄)₂- and AlPO₄-coated LiNi_0.8Co_0.2O₂ cathode materials were compared. AlPO₄-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 170.8 mAh g⁻¹ and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g⁻¹. Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 177.6 mAh g⁻¹ and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co₃(PO₄)₂ coating. The Co₃(PO₄)₂ coating material could react with LiOH and Li₂CO₃ impurities during annealing to form an olivine Li_xCoPO₄ phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni⁴⁺ ions compared to the AlPO₄-coated cathode. Differential scanning calorimetry results showed Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO₄-coated sample.     

High performance electrode for electrochemical oxygen generator cell based on solid electrolyte ion transport membrane

A double-layer composite electrode based on Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ + Sm_0.2Ce_0.8O_1.9 (BSCF + SDC) and BSCF + SDC + Ag was investigated to be a promising cathode and also anode for the electrochemical oxygen generator based on samaria doped ceria electrolyte. The Ag particles in the second layer were not only the current collector but also the improver for the oxygen adsorption at the electrode. a.c. impedance results indicated that the electrode polarization resistance, as low as 0.0058 Ω cm² was reached at 800 °C under air. In oxygen generator cell performance test, the electrode resistance dropped to half of the value at zero current density under an applied current density of 2.34 A cm⁻² at 700 °C, and on the same conditions the oxygen generator cell was continual working for more than 900 min with a Faradic efficiency of ∼100%.     

Dielectric and ferroelectric properties of Ba0.8Sr0.2Ti1−5x/4NbxO3 ceramics

Ba_0.8Sr_0.2Ti_1−5x/4Nb_xO₃ ceramics, x = 0, 0.01, 0.05, 0.10, were fabricated by conventional solid-state reaction. With increasing niobium content the ferroelectric phase transition temperature decreases linearly, and the dispersivity of the transition increases. Niobium B-site decreases transition temperature more pronounced than Sr²⁺ at A-site. The heterovalent substitution of Nb⁵⁺ in low content causes local defect dipole, while more substitutions introduce disorder to disturb the long-range dipole correlation. Ba_0.8Sr_0.2Ti_1−0.5/4Nb_0.1O₃ ceramic shows weak ferroelectric loop at room temperature far from its transition temperature, 153 K.     

Effect of potential on bismuth telluride thin film growth by electrochemical atomic layer epitaxy

In the present study, bismuth telluride compound thin film was grown by means of electrochemical atomic layer epitaxy (ECALE) with an automated thin layer flow cell deposition system. The dependence of the Bi and Te deposition potentials on Pt electrode was studied. Because developing a contact potential between the substrate and the growing semiconductor, the deposition potential adjustment is necessary for the first 30 or more cycles of each component. The dependence of the deposit as a function of the deposition potential adjustment slope has been investigated. The results show that an excess elemental Bi existed at a slope of −2 mV/p (p indicates per cycle), indicating that this is a lack of deposition at the potential. Single-phase Bi₂Te₃ compound could be obtained between −4 and −6 mV/p. Bi₂Te₃ and Bi₄Te₃ coexistence is observed at a slope of −10 mV/p. The EDS data indicates that the stoichiometry of compound is consistent with XRD result. SEM studies show that the deposits are inhomogeneous and have an micron sized particles morphology.     

Strategy for the syntheses of isolated fine silver nanoparticles and polypyrrole/silver nanocomposites on gold substrates

In this work, isolated fine silver nanoparticles and polypyrrole/silver nanocomposites with diameters of about 10 nm on gold substrates were first prepared by electrochemical methods. First, an Ag substrate was cycled in a deoxygenated aqueous solution containing 0.1 M HCl from −0.30 to +0.30 V versus Ag/AgCl at 5 mV/s with 30 scans. Subsequently the Ag working electrode was immediately replaced by an Au electrode and a cathodic overpotential of 0.2 V was applied under controlled sonication to synthesize Ag nanoparticles on the Au electrode. Then pyrrole monomers were encouragingly found to be polymerized on the deposited Ag nanoparticles. This polymerization is distinguishable from the known chemical or electrochemical one, due to the electrochemical activity of unreduced species of Ag_n⁺ clusters inside the nanoparticles. Also, this polymerization may be ascribed to the oxidizing agent of AuCl₄⁻, which is present on the Au electrode.     

Multiwall carbon nanotube supported poly(3,4-ethylenedioxythiophene)/manganese oxide nano-composite electrode for super-capacitors

MWCNT-PSS/PEDOT/MnO₂ nano-composite electrodes were fabricated by generating pseudo-capacitive poly(3,4-ethylenedioxythiophene) (PEDOT)/MnO₂ nano-structures on poly(styrene sulfonate) (PSS) dispersed multiwalled carbon nanotubes (MWCNTs). PSS dispersed MWCNTs (MWCNT-PSS) facilitated the growth of PEDOT and MnO₂ into nano-rods with large active surface area and good electrical conductivity. The ternary MWCNT-PSS/PEDOT/MnO₂ nano-composite electrode was studied for the application in super-capacitors, and exhibited excellent capacitive behavior between −0.2 V and 0.8 V (vs. saturated Ag/AgCl electrode) with high reversibility. Specific capacitance of the nano-composite electrode was found as high as 375 F g⁻¹. In contrast, specific capacitance of MWCNT-PSS/MnO₂ and MWCNT-PSS nano-composite electrodes is 175 F g⁻¹ and 15 F g⁻¹, respectively. Based on cyclic voltammetric studies and cycle-life tests, the MWCNT-PSS/PEDOT/MnO₂ nano-composite electrode gave a highly stable and reversible performance up to 2000 cycles. Our studies demonstrate that the synergistic combination of MWCNT-PSS, PEDOT and MnO₂ has advantages over the sum of the individual components.     

Nanosized α-LiFeO2 as electrochemical supercapacitor electrode in neutral sulfate electrolytes

In this work we have explored the electrochemical properties of two lithiated iron oxide powders for supercapacitor purposes. These samples mainly consisted of α-LiFeO₂ in nanosized or micrometric form. Electrolyte was an aqueous 0.5 M Li₂SO₄ solution and voltage range studied was between 0 and −0.7 V vs. a Ag/AgCl reference electrode. As expected, electrochemical performance was dependent on the particle size. When electrolyte was deaerated a stable capacitance of ≈50 F g⁻¹ is provided by the nanosized sample for several hundred cycles. Other sulfate based salts (Na₂SO₄, K₂SO₄, Cs₂SO₄) were investigated as electrolytes but only Li₂SO₄ leads to a stable capacitance upon cycling, probably due to lithium intercalation. An hybrid cell consisting of this sample and MnO₂ as negative and positive electrodes, respectively, delivered 0.3 F cm⁻² (10 F g⁻¹). Although these values are lower than reported for other aqueous hybrid cell, α-LiFeO₂/MnO₂ asymmetric capacitor is interesting from both, an economic and an environmental point of view.     

Photoanodic response of iron oxide electrode in aqueous solution and its application to Pb removal under visible light irradiation

The iron oxide electrode was prepared from thermal oxidation of iron at 600 °C for 3 h in air atmosphere. This electrode with the structure of Fe₃O₄ and α-Fe₂O₃ showed the response of photoanodic current to the light with wavelength shorter than 600 nm. The band gap energy of this electrode was 1.99 eV. The onset potential of distinct steady photocurrent and also the flatband potential were 0.80 and 0.09 V vs. Ag/AgCl, respectively, in 0.1 M HNO₃ aqueous solution. The cell consisting of the iron oxide photoanode in HNO₃-Pb(NO₃)₂ and the graphite cathode in H₂SO₄-Ce(SO₄)₂ caused the PbO₂ deposit on the surface of the former electrode due to visible light irradiation without application of voltage. By holding the potential of this electrode at more positive value than 0.90 V, the photoanodic removal rate of Pb²⁺ in HNO₃-Pb(NO₃)₂ solution was higher than that observed when Ce⁴⁺ was used as electron acceptor.     

Preparation and characterization of reticular SSC cathode films by electrostatic spray deposition

Sm_0.5Sr_0.5CoO_3−δ (SSC) cathode films were deposited on CGO (Gd_0.1Ce_0.9O_1.95) electrolyte substrates by electrostatic spray deposition to prepare SSC/CGO/SSC symmetrical cells. Deposition parameters were changed systematically to examine their effects on film microstructure and electrode performance. A set of deposition parameters including a 0.01 M precursor solution containing metal nitrates in a mixture solvent of de-ionized water (0.6 vol%), ethanol (1.5 vol%) and diethyl butyl carbitol (97.9 vol%), a flow rate of 6 ml/h for precursor solution, a deposition temperature of 350 °C and an imposed electric field of 10 kV/3 cm was identified for preparation of films with a highly porous reticular structure. The superior performance of a reticular SSC electrode was evidenced by its low interfacial resistances of 0.275 and 0.018 Ω cm² measured in 500 and 700 °C, respectively. These values were one-half to one order of magnitude smaller than that of the screen-printed or slurry-painted electrodes.     

Characterization of electrodeposited CuInSe2 (CIS) film

CuInSe₂ thin film was grown by one-step cathodic electrodeposition on Pt-coated glass using amperometry mode (fixed potential), in a three-electrode potentiostatic system containing the precursor solutions, 10 mM CuSO₄, 50 mM InSO₄, 30 mM SeO₂, and 0.1 M K₂SO₄ as a supporting electrolyte, at a pH of 1.5 (±0.1) adjusted with 0.1 M H₂SO₄. The structure, chemical composition, morphology, optical properties, and uniformity of the electrodeposited CuInSe₂ film were characterized by X-ray diffraction (XRD), electron probe micro analysis (EPMA), UV-vis-NIR spectrophotometry, field-emission scanning electron microscopy (FE-SEM), and Auger electron spectroscopy (AES), respectively. Several experiments were conducted in which the deposition voltage and post-annealing conditions were varied. As the applied deposition voltage was increased from −0.6 V to −0.7 V versus Ag/AgCl, a CuInSe₂ thin film with a chalcopyrite structure came to be predominantly formed, in accordance with the chemical composition, while the formation of the binary compounds (CuO and Cu_xSe) which influence the degradation of the performance in the application of CIS-based solar cells, rapidly decreased. The optimum conditions consisted of an annealing temperature of about 350 °C for 30 min under nitrogen ambient. At this temperature, a CuInSe₂ thin film, in the form of ternary compound, is formed with the required conditions, namely good crystallinity, good stoichiometry, a suitable bandgap, and depth uniformity.     

Supercapacitive properties of a nanowire-structured MnO2 electrode in the gel electrolyte containing silica

Nanowire-structured MnO₂ active materials were prepared by a chemical precipitation method and their supercapacitive properties for use in the electrodes of supercapacitors were investigated by means of cyclic voltammetry in an aqueous gel electrolytes consisting of 1 M Na₂SO₄ and fumed silica (SiO₂). The MnO₂ electrode showed a maximum specific capacitance of 151 F g⁻¹ after 1000 cycles at 100 mV s⁻¹ when using the gel electrolyte containing 3 wt.% of SiO₂, which is higher than 121 F g⁻¹ obtained when using the 1 M Na₂SO₄ liquid electrolyte alone.