Structural and optical properties of nanocrystalline lead sulfide thin films prepared by microwave-assisted chemical bath deposition

Nanocrystalline PbS thin films have been successfully deposited on glass substrate from lead nitrate (Pb²⁺ ions) and thiourea (S^2? ions) precursors using MACB technique. The effects of molar concentration (0.02, 0.05, 0.075 and 0.1 M) on the structure and microstructure evolution were studied using X-ray diffraction (XRD), scanning electron microscopy, and atomic force microscopy. The optical properties were investigated using UV–vis spectrophotometer. Crystal size values obtained from XRD were compared with these calculated using atomic force microscopy (AFM). The values of optical band gaps were found to decrease as the ion source molar concentration increase.     

Investigation on growth of In2S3 thin films by chemical bath deposition

Indium sulfide (In₂S₃) thin films were prepared by chemical bath deposition using the mixed aqueous solutions of indium chloride, thioacetamide and citric acid, in which citric acid was used as the complexing agent. The films were investigated by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), the surface roughness automatic tester and UV–visible transmission spectra, respectively. The XRD results indicate that the as-deposited films at pH 1 and 2 are composed of β-In₂S₃ phase, which crystallize in cubic structure. The SEM images show that the surface morphologies of In₂S₃ films change from nanospheres to network-like morphologies with increase in growth time. Film thicknesses linearly increase with time and reach to balance stability finally. The ion-by-ion growth mechanism is proposed.     

Preparation and characterization of ZnS thin films prepared by chemical bath deposition

Zinc sulfide thin films were prepared by chemical bath deposition technique using zinc sulfate (ZnSO₄·7H₂O) and thiourea [SC(NH₂)₂] as sources of Zn²⁺ and S^2– ions, and ammonia (NH₃) and hydrazine hydrate (N₂H₄) as complexing agents. The structural, stoichiometric proportion, morphology and optical properties of the ZnS thin films were investigated as a function of thiourea and ammonia concentrations using X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM) and UV-visible spectrophotometry measurements. The deposition mechanism is discussed. The results reveal that the ZnS films exhibit poor crystallinity. The ammonia concentration had an obvious effect on the surface morphology, optical properties and deposition mechanism. The S/Zn atomic ratio and optical bandgap of the ZnS thin films first increased and then decreased with increasing ammonia or thiourea concentration.     

Cadmium recovery and recycling from chemical bath deposition of CdS thin layers

Cadmium sulfide thin layers for polycrystalline solar cells are produced by chemical bath deposition (CBD). This process generates wastes containing mainly ammonia and cadmium. We have implemented and described in a previous paper a process to recover 90% of ammonia and to confine cadmium as a cake which is a mixture of cadmium sulfide and cadmium cyanamide. The present paper concerns cadmium recycling to the CBD step. The cake is first dissolved in a moderate sulfuric acid solution 0.2–0.5 mol/l mixed with hydrogen peroxide (about 1 mol/l). This last component must be used in large excess (molar ratio H₂O₂/Cd ≥ 5) and must be completely removed from the solution before recycling or cadmium electrowinning. Hydrogen peroxide decomposition is electrochemically catalyzed by platinized platinum immersed into the solution. The resulting solution contains cadmium sulfate 0.2 mol/l, sodium and ammonium sulfate. One can either recycle it as a chemical bath, or recover the cadmium content by electrowinning; in this case the residual concentration of hydrogen peroxide is electrochemically reduced at the beginning of cadmium electrolysis. The raffinate solution is recycled into the stripping reactor. The pure cadmium metal recovered may be dissolved in a dilute sulfuric acid solution by means of internal electrolysis with two electrodes: a platinized platinum grid as cathode and the cadmium metal as anode. According to the mass of cadmium dissolved it is possible to obtain a concentrated solution of pure cadmium sulfate. The global process recovers at least 99.999% of cadmium and generates only solid sulfur and a liquid effluent containing traces of cadmium (< 10 μg/l). Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis and characterization of CdSe nanocrystalline thin films deposited by chemical bath deposition

Cadmium selenide (CdSe) nanocrystalline thin films were prepared by chemical bath deposition (CBD) using ammonia and triethanolamine (TEA) as complexing agents, cadmium chloride and sodium selenosulphate as the sources of Cd²⁺ and Se^2? ions, respectively. The structural and optical properties of CdSe nanocrystalline thin films were investigated as a function of the sodium selenosulphate concentrations or ammonia concentrations in precursors using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) measurements, transmission electron microscopy (TEM) and UV–visible spectrophotometer measurements. The results reveal that the CdSe thin films are in the pure cubic phase, which composed of a large number of uniform spherical particles. Each spherical particle contains many nanocrystals 3–10 nm in crystallite size. An increase in both the average diameter of the spherical particles and the crystallite size of the nanocrystals occurs with an increase in ammonia concentrations. The Se/Cd atom ratios of CdSe thin films firstly increase and then decrease with an increase in ammonia concentration or sodium selenosulphate concentration. The optical band gap of CdSe thin films decrease with an increase in ammonia concentrations. The kinetics and reaction mechanism of the CdSe nanocrystalline thin films during deposition are discussed.     

Effect of deposition time on lead selenide thermoelectric thin films prepared by chemical bath deposition technique

A series of lead selenide (PbSe) films was deposited at constant bath temperature with various deposition time (3–5 h) using simple chemical bath deposition techniques, to study the effect of deposition time on its structural and thermoelectric properties. The as-deposited film was analyzed through X-ray diffraction, SEM, Energy dispersive X-ray analysis, Raman spectroscopy and Seebeck coefficient measurement. The improvement of crystallinity of the PbSe films was studied using X-ray diffraction and Raman scattering. The structural parameters, such as the lattice constant (a), crystallite size (D), dislocation density (δ) and microstrain (ε) were evaluated from the XRD spectra. Average crystallite size was calculated from Scherrer׳s formula and it was found to be increased from 19.65 to 23.97 nm as the deposition time was varied from 3 h to 5 h. The dislocation density and microstrain were found to vary inversely with the crystallite size, whereas the lattice constant increases with an increase in crystallite size. SEM images show that the morphology of particles strongly depends on the deposition time. The possible growth mechanism for the variation in the morphology is discussed. The thermoelectric measurements have shown n-type conductivity in “as deposited films” and the magnitude of Seebeck coefficient is found to be increasing with an increase in deposition time.     

SnS thin films deposited by chemical bath deposition, dip coating and SILAR techniques

The SnS thin films were synthesized by chemical bath deposition (CBD), dip coating and successive ionic layer adsorption and reaction (SILAR) techniques. In them, the CBD thin films were deposited at two temperatures: ambient and 70 ℃. The energy dispersive analysis of X-rays (EDAX), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and optical spectroscopy techniques were used to characterize the thin films. The electrical transport properties studies on the as-deposited thin films were done by measuring the I-V characteristics, DC electrical resistivity variation with temperature and the room temperature Hall effect. The obtained results are deliberated in this paper.     

Characterization and antibacterial capabilities of nanocrystalline CdS thin films prepared by chemical bath deposition

Antibacterial capabilities of nanocrystalline cadmium sulfide (CdS) thin films have been developed against Gram-positive and Gram-negative bacteria in dark and sunlight at 60 °C. For this purpose, a strain of Gram-positive Staphylococcus aureus, and two strains of Gram-negative bacteria (Pseudomonas aeruginosa, and Escherichia coli) were used. The nanocrystalline CdS thin films have been prepared using a chemical bath deposition (CBD) method at different thicknesses (50, 80 and 100 nm). The different deposition parameters including the speed of rotation of substrate, temperature of chemical bath, pH of solution and time of the deposition were optimized. The Polyvinylpyrrollidone (PVP) was successfully used as capping agent in order to stop the agglomeration in the CdS thin films. It was found that, CdS thin films have remarkable antibacterial activity in dark and sunlight and it could be applied as antimicrobial agent in medical field. In order to confirm the crystalline structure of CdS thin films, the polycrystalline nature of the deposited CdS thin films with hexagonal structure was obtained. Furthermore, the structural parameters including lattice parameters, cell volume, the space group, average grain size, dislocation density and the strain have been calculated. The topography and surface roughness of the CdS thin films have been studied before and after the bacteriostatic effect using Scanning Electron Microscopy (SEM). Furthermore, the compositions of nanocrystalline CdS thin films have been evaluated using Energy Dispersive X-ray emission (EDX) and a Transmission Electron Microscope (TEM). Based on the optical measurements in the range of 300–2500 nm, the band gap energy of the prepared CdS thin films was found to be 2.4 eV.     

Characterization of nanocrystalline PbS thin films prepared using microwave-assisted chemical bath deposition

Nanocrystalline lead sulfide (PbS) thin films were synthesized on glass substrates using microwave-assisted chemical bath deposition (CBD) method. Various deposition periods of time ranging from 30 to 120 min were used. Results demonstrated that the thickness of the thin films increased with longer deposition time. X-ray diffraction (XRD) measurement revealed that all thin films have cubic rock salt (NaCl) type structure. The surface morphology studied using scanning electron microscopy (SEM) showed that the films have uniform surface morphology over the entire substrate and were of good quality. AFM images confirm that the films have a smooth surface with good adherence to the substrate, a narrow particle size distribution, and that the surface roughness increased with increasing deposition time. Energy gap E_g decreases as the deposition time increases. Electrical measurements revealed that all films were p-type and that the conductivity decreased as the deposition time increased.     

Effects of annealing on nanocrystalline Bi2S3 thin films prepared by chemical bath deposition

Nanocrystalline Bi₂S₃ thin films are deposited on tin chloride treated glass substrate from the solution containing bismuth nitrate, triethanolamine (TEA) and thioacetamide (TAM) at a bath temperature 318 K. The prepared films are subsequently annealed at different temperatures for studying the effect of thermal treatment on the structural, surface morphology, optical and electrical properties of the films. The X-ray diffraction studies affirmed that the deposited films are orthorhombic structures with average crystallites size of 14 nm to 28 nm. The scanning electron microscopy (SEM) images revealed that the films comprise of grains of spherical shape of unequal size. It is also observed that the small particles aggregate together to form a larger cluster. The average grain sizes determined from the TEM images are smaller than the crystallites size obtained from the XRD studies. The optical band gap of the films has been estimated to be 2.24–2.05 eV for the as-prepared and annealed films, respectively. The electrical conductivity of the as prepared Bi₂S₃ films at room temperature is found to be in the order of 10⁻³ Ω⁻¹ m⁻¹.     

Effect of temperature on structural and optical properties of ZnS thin films by chemical bath deposition without stirring the reaction bath

ZnS thin films were deposited at different temperatures on glass substrates by chemical bath deposition method without stirring the deposition bath. With deposition temperature increasing from 50 °C to 90 °C, pH decreases rapidly, homogeneous precipitation of ZnS, instead of Zn(OH)₂ easily forms in the bath. It means that higher temperature is favorable for the formation of relatively high stoichiometric film, due to the lower concentration of OH⁻. The thickness of the films deposited at 90 °C is much higher than that of the films deposited at 50 °C and 70 °C. Combining the film thickness with the change of pH, the growth of film, especially deposited at 90 °C mainly comes from the fluctuation region of pH. At the same time, with the increase of deposition temperature, the obtained films are transparent, homogeneous, reflecting, compact, and tightly adherent. The ZnS films deposited for 1.5 h, 2 h and 2.5 h at 70 °C and 90 °C have the cubic structure only after single deposition. The average transmission of all films, especially the thicker films deposited at 90 °C, is greater than 90% for wavelength values in the visible region. Comparing with the condition of stirring, the structural and optical properties of films are improved significantly. The direct band gaps range from 3.93 to 4.06 eV.     

Effect of deposition temperature on structural,optical properties and configuration of CdSe nanocrystalline thin films deposited by chemical bath deposition

CdSe nanoparticle thin films were deposited on glass substrates by the chemical bath deposition (CBD) method at low deposition temperature ranging from room temperature up to 50 °C while the pH of the bath was kept constant at 12.1. The structural and morphological variation were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) technique. The energy band gap and optical properties were characterized by the absorbance spectra. Rutherford backscattering spectroscopy (RBS) analysis reveals the excess of Cd rather than Se in depth profile along the thin film thickness. The prepared CdSe nanoparticles have cubic structure and by increasing the temperature the deposited films become continues, homogeneous and tightly adherent. The results also revealed that by increasing the deposition temperature from room temperature up to 50 °C, the band gap decreases from 3.52 eV up to 1.84 eV.     

Growth mechanisms and their effects on the opto-electrical properties of CdS thin films prepared by chemical bath deposition

Chemically deposited CdS exhibits high sensitivity in the opto-electrical performance to the growth mechanisms. Hence it is of a great interest to study the effects of growth mechanisms on the opto-electrical performance in such films. Studies were carried out by the means of spectroscopic ellipsometry, and coupled with structural, optical, and electrical characterization. A range of bath temperatures (55 °C–95  °C) were used as the means to alter the growth mechanisms. Ion-by-ion process dominated deposition at lower bath temperatures throughout the length of the deposition. This mechanism produced films composed of single phase cubic crystals with corresponding opto-electrical properties inherent to such structures. Complex formations at higher bath temperatures supplement the sole ion-by-ion mechanisms with the cluster-by-cluster mechanism. This results in a mixed cubic/hexagonal structure, and deviation from stoichiometry. As a result, carrier concentrations and mobility increased nearly eight and four fold respectively. Resistivity decreased more than four times from 33.2 to 7.5 Ω cm. A noticeable decrease of, ~0.2 was observed in the refractive index and an increase of ~0.07 eV in the band gap is also reported. Nuclear magnetic resonance analysis confirms deviation from stoichiometry in the cluster-by-cluster mechanisms, resulting in interstitially trapped Cd⁺² and S⁻² ions. The trapped ions act as donors in the film enhancing its electrical performance.     

Optical properties of chemical bath deposited CdS thin films

CdS thin films have been prepared by chemical bath deposition. As-deposited films are cubic and show a sulfur deficiency. From the transmittance and reflectance data analysis direct band gaps (E_g) ranging from 2.180 to 2.448 eV have been obtained. Air and vacuum annealed samples show a decrease in the band gap. The refractive index (n) lies in the range 1.61–2.34. A dependence of band gap on composition has been observed and the possible reasons are discussed.     

Characterization of CdSe thin films deposited by chemical bath solutions containing triethanolamine

Cadmium selenide (CdSe) thin films were prepared by chemical bath deposition on glass substrates at different temperatures beginning at room temperature (25 °C) upto 80 °C from an aqueous alkaline medium using a precursor solution containing cadmium acetate, 2,2′,2′′-nitrilotriethanol (triethanolamine), ammonia and sodium selenosulphate. The pH of bath was kept constant around 10.50±0.10. Energy dispersive analysis of X-rays confirmed that the films are nearly stoichiometric in composition. The structural and surface morphological properties have been studied by X-ray diffraction, Scanning electron microscopy and Atomic force microscope techniques. X-ray diffraction study reveals a cubic structure with preferential orientation along (111) direction. The dependency of structural parameters such as crystallite size, strain and dislocation density with different bath temperatures for CdSe thin films are calculated. X-ray peak broadening was used to evaluate the crystallite size and lattice strain by the Williamson–Hall plots. Optical properties are studied by photoluminescence spectra which shows blue shift in peak position and reduction in luminescence intensity were observed for films deposited at different bath temperatures.     

Surfactant assisted chemical bath deposition based synthesis of 1-D nanostructured CuO thin films from alkaline baths

Nanostructured CuO thin films were prepared by a simple chemical bath deposition method in the absence and presence of different surfactants. The obtained structures were characterised on the basis of x-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy and UV–Vis spectral absorption. XRD and Raman studies pointed to the formation of a pure phase of monoclinic CuO. SEM studies revealed 1-D nanostructures of different orientations and aspect ratios. The presence of surfactants produced more uniform and oriented nanostructures. The samples were absorbing in the UV–Vis region demonstrating their potential application in photothermal systems. All the samples showed photocatalytic activity against methylene blue with different degradation efficiencies.     

Filament-activated chemical vapour deposition of nitride thin films

We have applied the novel method of hot filament-activated chemical vapour deposition (HFCVD) for low-temperature deposition of a variety of nitride thin films. In this paper the results from our recent work on aluminium, silicon and titanium nitride have been reviewed. In the HFCVD method a hot tungsten filament (1500–1850°C) was utilised to decompose ammonia in order to deposit nitride films at low substrate temperatures and high rates. The substrate temperatures ranged from 245 to 600°C. The film properties were characterised by a number of analytical and optical methods. The effect of various deposition conditions on film properties was studied. All the films obtained were of high chemical purity and had very low or no detectable tungsten contamination from the filament metal.     

Self-catalyzed chemical vapor deposition method for the growth of device-quality metal thin films

Deposition of metals and alloys was demonstrated using thermal chemical vapor deposition starting from commercially available precursors in the absence of molecular hydrogen. The adopted chemical strategy relies solely on the selective reactivity of alcohols with metal complexes at deposition temperature. In this report, particular interest was given to the growth of nickel and silver. This process allows the optimization of the growth of single hcp and fcc phases of nickel starting from Ni(acac)₂, whereas several silver precursors allow the deposition of the fcc crystalline structure of silver. Steady growth kinetics, without incubation time, was noticed for all investigated precursors. The electrical conductivity of hcp-Ni, fcc-Ni and fcc-Ag shows the typical decay to the bulk value with increased film thickness, and the temperature resistivity coefficients are similar to the corresponding bulk material.     

Growth of chromium-doped alumina thin films by metal-organic chemical vapour deposition

Amorphous thin films of chromium-doped alumina were grown from Al(OⁱPr)₃ (ⁱPr, Isopropyl) and Cr(CO)₆ on silicon and quartz substrates by chemical vapour deposition at 673 K. The films were annealed at 1223 and 1473 K to form chromium-doped γ-Al₂O₃ and γ-Al₂O₃respectively. The lattice constant a of the γ-Al₂O₃thin films enlarged with increasing Cr Concentration. The lattice constant a (=b) of the α-Al₂O₃ thin films increased while the lattice constant c decreased with increasing Cr concentration. UV-visible spectra of the annealed films showed maximum absorptions near 380, 500 and 690 nm.     

Electrochemical deposition and characterisation of CdTe thin films from an ethylene-glycol-based bath

CdTe films were deposited on Ni and conducting glass (SnO₂) substrates from an ethylene-glycol-based bath by galvanostatic and potentiostatic methods. The film composition and electrical properties depend on parameters such as working electrode potential current density, deposition temperature, substrate type and post-deposition treatments. It is possible to improve the grain size and stoichiometry of the film by post-deposition heat treatment in air. The conductivity type was determined from the photocurrent-working electrode potential behaviour of the film. Dark capacitance measurements in a 0.5 M H₂SO₄ solution at 10 kHz showed a linear behaviour, from which the flatband potential V_fb= −0.365 V vs. a saturated calomel electrode (SCE) and the doping density N_D = 1.35 × 10¹⁸ cm⁻³ were determined. © 1997 John Wiley & Sons, Ltd.