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.     

Fabrication of bismuth telluride nanoparticles using a chemical synthetic process and their thermoelectric evaluations

Bismuth telluride nanoparticles for thermoelectric applications were successfully prepared via a water-based chemical reaction. In this process, we used both a complexing agent (ethylenediaminetetraacetic acid) and a reducing agent (ascorbic acid) to stabilize the bismuth precursor (Bi(NO₃)₃) in water and to favor the reaction with the reduced source of tellurium. The resulting powder was confirmed to range in size below ca. 100 nm with the crystalline structure corresponding to the rhmobohedral Bi₂Te₃. We sintered the nanocrystalline powder via a spark plasma sintering process, thus we obtained the sintered body composed of nano-sized grains. Then, we measured some important transport properties (electrical resistivity, Seebeck coefficient, and thermal conductivity) of the sintered body to calculate its thermoelectric performance, the figure of merit. Finally, we discussed the effect of the nanostructure in the sintered body on the thermal conductivity.     

Electrodeposition of silver telluride thin films from non-aqueous baths

We describe a method for preparation of crystalline silver telluride films by cathodic deposition from dimethyl sulfoxide (DMSO) solutions containing 0.1 M NaNO₃, 5.0 mM AgNO₃ and 3.5-7.0 mM TeCl₄. X-ray diffraction data indicated that the deposited silver telluride films could be adjusted from Ag excess and stoichiometric monoclinic Ag₂Te to hexagonal Ag₇Te₄ by increasing the concentration of TeCl₄ in the electrolyte or lowering the deposition potential. The Ag₂Te film is gray and the Ag₇Te₄ film is dark blue-gray and mirror like adhered strongly to the substrates. Scanning electron microscopy images show that Ag₂Te films were formed with globular grains with average diameters of more than 1 μm. In contrast, Ag₇Te₄ film consists of triangles characteristic of a (1 1 1) single-crystal with a hexagonal structure in average sizes of about 0.4 μm. The X-ray photoelectron spectra (XPS) indicated that the binding energies deviation of Te3d in Ag₇Te₄ is less than that in Ag₂Te, which is consistent with the apparent valences of Te in Ag₂Te and Ag₇Te₄. Finally, the cathodic deposition reactions were studied by cyclic voltammetry.     

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.     

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 and characterization of Bi2Se3 thin films by electrochemical atomic layer epitaxy (ECALE)

Bismuth selenide thin films were grown on Pt substrate via the route of electrochemical atomic layer epitaxy (ECALE) in this work for the first time. The electrochemical behaviors of Bi and Se on bare Pt, Se on Bi-covered Pt, and Bi on Se-covered Pt were studied by cyclic voltammetry and coulometry. A steady deposition of Bi₂Se₃ could be attained after negatively stepped adjusting of underpotential deposition (UPD) potentials of Bi and Se on Pt in the first 40 deposition cycles. X-ray diffraction (XRD) analysis indicated that the films were single phase Bi₂Se₃ compound with orthorhombic structure, and the 2:3 stoichiometric ratio of Bi to Se was verified by EDX quantitative analysis. The optical band gap of the as-deposited Bi₂Se₃ film was determined as 0.35 eV by Fourier transform infrared spectroscopy (FTIR), which is consistent with that of bulk Bi₂Se₃ compound.     

Electrodeposition and characterization of manganese–bismuth system from chloride based acidic bath

In this work, Mn–Bi system has been successfully electrodeposited on Cu/Si substrates from aqueous ammonium chloride containing electrolyte. A thermodynamic study of the electrolysis bath highlights the possible formation of manganese complexes and bismuth complexes The mechanism process involving Mn and Bi electrodeposition is investigated by cyclic voltammetry. Mn–Bi films can be grown under potentiostatic control. The physico-chemical, morphological and structural characterizations of the deposits were carried out by scanning electron microscopy (SEM) and X-rays analysis (XRD). The results reveal a granular surface quality and a heterogeneous chemical composition of the films. The energy dispersive spectroscopy (EDS) analysis reveals the presence of manganese and bismuth peaks whose relative intensities vary according to the imposed potential and the position on the sample. The X-rays diffraction analysis showed three different crystalline phases: α-manganese (body centred cubic system), γ-manganese (body centred tetragonal system) and bismuth (rhombohedral system).     

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.     

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.     

Electrodeposition of bismuth from nitric acid electrolyte

The electrodeposition of Bi from acidic nitrate solution was examined. Bismuth deposition was determined to be quasi-reversible on Au, with a current efficiency of 100%, based on integration of deposition and stripping voltammetric waves. No interference from nitrate reduction was found on Bi and Au, whereas nitrate reduction occurred on W and Cu electrodes. Analysis of current-time transients clearly shows nucleation on Au to be instantaneous. Field emission SEM revealed nodular deposits with moderate surface roughness. Nodule size varied from 1 to 5 μm depending on deposition potential and deposit thickness. X-ray diffraction (XRD) patterns for all deposits were indexed to rhombohedral bismuth. The deposits showed fairly strong (0 1 2) crystallographic texture at high deposition overpotentials.     

Electrodeposition of nanocrystalline CdSe thin films from dimethyl sulfoxide solution: Nucleation and growth mechanism, structural and optical studies

Cadmium selenide (CdSe) nanocrystalline semiconductor thin films have been synthesized by electrodeposition at controlled potential based in the electrochemical reduction process of molecular selenium in dimethyl sulfoxide (DMSO) solution. The nucleation and growth mechanism of this process has been studied. The XRD pattern shows a characteristic polycrystalline hexagonal wurtzite structure with a slight (1 0 1 0) crystallographic preferred orientation. The crystallite size of nanocrystalline CdSe thin films can be simply controlled by the electrodeposition potential. A quantum size effect is deduced from the correlation between the band gap energy and the crystallite size.     

Cyclic voltammetry study of electrodeposition of Cu(In,Ga)Se2 thin films

The electrodeposition of Cu(In,Ga)Se₂ has been investigated by cyclic voltammetry (CV) in a DMF-aqueous solution that contained citrate as a complexing agent. The effects of the citrate ion on the reduction potentials of Cu²⁺, In³⁺, Ga³⁺ and H₂SeO₃ were examined for a unitary system. Furthermore, a cyclic voltammetry study was performed in a ternary Cu-In-Se system, a quaternary Cu-In-Ga-Se system, and binary Cu-Se, In-Se and Ga-Se systems. The insertion of In and Ga into the solid phase may proceed by an underpotential deposition mechanism, which involves two different routes: In³⁺ and Ga³⁺ reduction by a surface-induced effect from Cu₃Se₂ and/or reaction with H₂Se.     

Morphology-controlled synthesis and characterization of bismuth sulfide crystallites via a hydrothermal method

Bismuth sulfide (Bi₂S₃) crystallites with various morphologies have been successfully synthesized via a hydrothermal process assisted by KOH mineralizer. X-ray diffraction (XRD) and scanning electron microscopy (SEM) indicated that the mineralizer played a key role in the crystallization and morphology-controlled synthesis of Bi₂S₃ crystallites. The room temperature photoluminescence spectra (PL) showed that uniform rod-shape morphology resulted in better luminescence.     

The effect of Bi2O3 compensation during thermal treatment on the crystalline and electrical characteristics of bismuth titanate thin films

Bismuth titanate thin films are deposited on ITO/glass substrates by rf magnetron sputtering at room temperature using a Bi₄Ti₃O₁₂ ceramic target. The deposited Bi₄Ti₃O₁₂ films are annealed in a conventional furnace in ambient air for 10 min at temperatures ranging from 550 to 640 °C. One specimen is annealed in a crucible containing additional Bi₂O₃ compensation powder, while the other specimen is annealed in ambient air. XRD analysis shows that the crystal phases of films annealed with Bi₂O₃ powder are better than those of films annealed without Bi₂O₃ powder. Furthermore, the EDS results reveal that the bismuth weight percentage of the former is higher than that of the latter. SIMS analysis shows that the bismuth decreases near the surface of Bi₄Ti₃O₁₂ film annealed without Bi₂O₃ powder, but reveals a stable distribution throughout the film annealed with Bi₂O₃ powder. These results imply that bismuth is readily evaporated during the thermal treatment process, particularly from the region near the film surface. Finally, the dielectric and polarization properties of the thin films annealed with Bi₂O₃ powder are found to be superior to those of the films annealed in ambient air.     

Electrodeposition of ZnSe

The conditions of the electrodeposition of a thin film of polycrystalline ZnSe phase on copper substrate from aqueous baths were studied. The electrochemical behavior of Zn²⁺ and H₂SeO₃ species was investigated using cyclic voltammetry. Thin films were deposited potentiostatically on copper substrate and the influence of deposition parameters such as deposition potential, H₂SeO₃ and ZnSO₄ concentration, and temperature of bath on the crystallinity and on the chemical composition of the film is discussed. The ZnSe layers were characterized by X-ray diffraction, X-ray energy dispersive spectroscopy and scanning electron microscopy.     

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.     

Preparation and characterization of Bi2Se3 nanowires by electrodeposition

The electrodeposition of Bi₂Se₃ nanowires on an anodic aluminum oxide template was investigated by cyclic voltammetry in a tartaric acid aqueous solution. The electrochemical behavior of the Bi₂Se₃ nanowires in the electrolytic solution was also investigated using cyclic voltammetry, and the underpotential deposition mechanism of the Bi₂Se₃ nanowires was determined. According to the cyclic voltammetric curves, −0.20 V vs. SCE (saturated calomel electrode) was chosen as the deposition potential of the Bi₂Se₃ nanowires. The ratio of Bi to Se is nearly 2:3, verified by energy-dispersive X-ray spectroscopy and with the addition of surfactant. X-ray diffraction, scanning electron microscopy, selected-area electron diffraction and high-resolution transmission electron microscopy indicate that annealing can improve the crystallinity and chemical composition of Bi₂Se₃ nanowires. Surfactant can also improve the surface morphology and composition of the Bi₂Se₃ nanowires.     

Self-propagation high-temperature synthesis of bismuth titanate

A series of 20 experiments on the powder production of the ferroelectric Bi₄Ti₃O₁₂ (BIT) has been performed through self-propagating high-temperature synthesis (SHS), exploring urea (CO(NH₂)₂) and the polysaccharide ((C₆H₁₀O₅)_n) as fuels. Different experimental conditions such as annealing temperatures, stoichiometric ratios and the use of TiO₂ and TiCl₂ as titanium sources were investigated. The percentage of BIT crystalline phase present in each sample prepared was calculated from X-ray diffraction. The platelike morphology of the powders produced by SHS was the same as that observed in the reference sample synthesized by solid-state reaction. Some of the proposed routes were shown to be very advantageous, providing BIT with particle sizes smaller than 1 μm in few minutes of reaction plus 30 min of annealing, while the solid-state route takes approximately 150 h to achieve similar results.     

Electrodeposition of Lu-Ni alloy thin films

The electrodeposition of Lu-Ni alloy thin films from Lu(III) and Ni(II) solutions was studied in a nonaqueous dimethysulfoxide (DMSO). Different substrates have been used (platinum and copper), and the effect of them on the electrochemical behavior of the studied ions is shown. The obtained Lu-Ni alloy thin films were subjected to scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction analysis (XRD). The lutetium content in Lu-Ni alloy thin films increases as the potential was made more cathodic, reaching a maximum value of 28.77 at.%, and then decreases. The films were amorphous. After heat treatment of crystallization at 520 °C for 1 h, the alloy phase of Lu-Ni can be found in XRD patterns.     

Facile preparation of Bi nanoparticles by novel cathodic dispersion of bulk bismuth electrodes

A novel electrochemical approach has been developed to prepare clean bismuth nanoparticles (NPs) with a bulk Bi electrode in a 0.5 mol dm⁻³ NaOH solution under highly cathodic polarization of −8 V versus a saturated mercurous sulfate electrode, requiring no any precursor ions and organic protective agents. The bulk Bi electrode can be facilely dispersed into Bi NPs at the condition of intensive hydrogen evolution. This cathodic dispersion of the bulk Bi electrode involves the formation and decomposition of unstable bismuth hydrides and the aggregation of atomic bismuth from the decomposition. Moreover, Bi₂O₃ NPs have also been achieved by heating the precursor Bi NPs. Field-emission scanning electron microscopy, transmission electron microscope and X-ray diffraction were used to characterize these NPs. The as-prepared Bi NPs mainly existed in rhombohedral phase.