Formation of cadmium sulfide (CdS) nanofilm on a Cd(OH)2/SiO2 precursor layer

Dense thin nanostructured films of cadmium sulfide CdS obtained by chemical deposition from aqueous solutions are strongly bound to a substrate due to the formation of cadmium hydroxide Cd(OH)₂ in the system. By X-ray reflectometry and grazing incidence diffraction it is found that at the beginning of the deposition a dense Cd(OH)₂/SiO₂ layer is produced on the surface of a silicon or glass substrate. This layer is formed through the atomic-layer adsorption of crystalline 1–3 nm thick Cd(OH)₂ film by the oxygencontaining substrate surface. During sulfidation of this cadmium-containing substrate layer, a surface nucleation layer of CdS/Cd(OH)₂/SiO₂ forms, which provides the growth, denseness, and strong adhesion to the substrate of nanostructured CdS film with a disordered structure. According to the obtained experimental data, a “hydroxide scheme” of film deposition is confirmed and refined, and the stages of CdS nanofilm formation are determined.     

Study of the first nucleation steps of thin films by XPS inelastic peak shape analysis

The initial steps in the formation of thin films have been investigated by analysis of the peak shape (both inelastic background and elastic contributions) of X‐ray photoelectron spectra. Surface coverage and averaged height of the deposited particles have been estimated for several overlayers (nanometre range) after successive deposition cycles. This study has permitted the assessment of the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of an XPS spectrometer. To check the performance of the method, several materials (i.e. cerium oxide, vanadium oxide and cadmium sulfide) have been deposited on different substrates using a variety of preparation procedures (i.e. thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition). It is shown that the first deposited nuclei of the films are usually formed by three‐dimensional particles whose heights and degree of surface coverage depend on the chemical characteristics of the growing thin film and substrate materials, as well as the deposition procedure. It is concluded that XPS peak shape analysis can be satisfactorily used as a general method to characterize morphologically the first nanometric moieties that nucleate a thin film. Copyright © 2006 John Wiley & Sons, Ltd.     

Features of the Formation of Thin Films of Supersaturated Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>S Solid Solutions by Chemical Bath Deposition

Thin nanostructured films of lead sulfide-based Cd_xPb_1–xS solid solutions, strongly supersaturated with respect to the substituting component, were prepared by hydrochemical deposition from ammonia-citrate, ethylenediamine-citrate, and ethylenediamine reaction mixtures onto glass-ceramic substrates. The structure, composition, and morphology of the resulting films were examined. An interesting feature of the synthesis was revealed, a distinct correlation between the linear dimensions of the crystallites constituting the films and the cadmium sulfide content therein: the higher cadmium sulfide content, the smaller were the crystallites.     

Fabrication of CdS films with superhydrophobicity by the microwave assisted chemical bath deposition

A simple method of microwave assisted chemical bath deposition (MA-CBD) was adopted to fabricate cadmium sulfide (CdS) thin films. The superhydrophobic surface with a water contact angle (CA) of 151 degrees was obtained. Via a scanning electron microscopy (SEM) observation, the film was proved having a porous micro/nano-binary structure which can change the property of the surface and highly enhance the hydrophobicity of the film. A possible mechanism was suggested to describe the growth of the porous structure, in which the microwave heating takes an important role in the formation of two distinct characteristic dimensions of CdS precipitates, the growth of CdS sheets in micro-scale and sphere particles in nano-scale. The superhydrophobic films may provide novel platforms for photovoltaic, sensor, microfluidic and other device applications.     

Synthesis and optical properties of cadmium sulfide in perfluorosulfonic membrane

Synthesis of nano-dimensional particles of cadmium sulfide in the pores of perfluorosulfonic membrane by means of the ion-exchange fixation of Cd²⁺ cations and the subsequent treating with gaseous hydrogen sulfide is carried out. As a result of gradual “step-by-step” accumulation of the guest substance monotonous downfield shift of the absorption bands in the visible spectrum is observed. In the luminescence spectra a set of bands is registered characterizing the dimensional distribution of small X-ray amorphous particles. Contrary to that one-step capsulation of cadmium sulfide by means of sulfidation of membrane with the content of Cd²⁺ ions close to the saturated state provides the formation of nano-dimensional particles of cubic structure. Their absorption band is maximally close in its position to that of the bulk CdS, and in the luminescence spectrum characteristic long-wave radiation with λ_max 670 nm dominates. Optical properties of cadmium sulfide and their dimensional specific features are described considering the population of (Cd-S)-antibonding orbitals resulting from photoexcitation.     

The synthesis of nucleus-shell Cd(OH)<Subscript>2</Subscript>/CdS structures by chemical precipitation from aqueous solutions

The region of stable coexistence of Cd(OH)₂ and CdS as a function of pH and the concentration of the complex-forming agent (ammonia) was determined by thermodynamic analysis with the purpose of the preparation of Cd(OH)₂ cadmium hydroxide particles surrounded by cadmium sulfide CdS shells. In this region, powders were obtained by chemical precipitation during various precipitation times from aqueous solutions. X-ray diffraction was used to track the growth of the CdS nanophase of a disordered structure and hexagonal Cd(OH)₂ phase consumption with time. It was found by complexonometry that part of cadmium formed insoluble structures as a result of the formation of continuous nanosized CdS shells on single crystalline Cd(OH)₂ particles. A comparative analysis of the experimental data was used to determine the kinetics of formation of nucleus-shell Cd(OH)₂/CdS particles in the system.     

Chemical Composition and Structure of Thin Films Produced by Chemical Vapor Deposition

This paper reports results from studies of the chemical composition and structure of semiconducting, dielectric, and metallic films produced from molecular precursors by the chemical vapor deposition method. A study was made of films of zinc sulfides, mixed copper, cadmium, and zinc sulfides, boron nitride, carbonitride, silicon carbonitride, and iridium films. It is shown that the use of metal compounds with different ligands (zinc and manganese) enables production of zinc sulfide films in which manganese ions are uniformly incorporated into the zinc sulfide crystal lattice to substitute zinc at the lattice sites. For the films of simple and mixed cadmium, copper, and zinc sulfides, the film structure depends on the type of substrate. The thin layers of mixed cadmium and zinc sulfides are asubstitution solution with a hexagonal structure. The thin layers of boron nitride produced from borazine exhibit a nanocrystalline structure and are a mixture of cubic and hexagonal phases. Composite layers were produced from alkylamine boranes and their mixtures with ammonia. Depending on synthesis conditions, the layers are mixtures of hexagonal boron nitride, carbide, and carbonitride or pure boron nitride. Using silyl derivatives of asymmetric dimethylhydrazine containing Si—N and C—N bonds in the starting molecule, we produced silicon carbonitride films whose crystal habit belongs to a tetragonal structure with lattice parameters a = 9.6 and c = 6.4 . The iridium films obtained by thermal decomposition of iridium trisacetylacetonate(III) on quartz substrates in the presence of hydrogen have a polycrystalline structure with crystallite sizes of 50 to 500 . A method for determining grainsize composition was proposed, and grain shapes for the iridium films were analyzed. The influence of substrate temperature on the internal microstructure and growth of the iridium films is demonstrated. At the iridium–substrate interface, a transition layer forms, whose composition depends on the substrate material and deposition conditions.     

Synthesis of cadmium sulphide in pure and mixed Langmuir-Blodgett films of n -octadecylsuccinic acid

Cadmium sulphide (CdS) nanoparticles were grown by the reaction of sodium sulphide (Na₂S) with Langmuir-Blodgett (LB) films of cadmium salts ofn-octadecylsuccinic acid (ODSU) and with LB films of ODSU in mixtures of octadecylamine and octadecyl alcohol. The results indicate that heterogeneous nucleation and aggregation in the pure ODSU LB films due to processes like Ostwald ripening are destabilized by the presence of the long-chain amine and alcohol in mixed systems. CdS nanoparticles in the LB films were monitored by UV-visible absorption spectra, which allow an estimation of the size of the particles. The morphology, size and nature of the nanocrystallites formed depend on whether the sulphidation was done on the pure film or in the mixed films. It is seen that particles of size around 1.6 nm were formed in ODSU/octadecylalcohol and ODSU/ octadecylamine mixed LB films while in pure ODSU films the size was about 2.7 nm. These films showed typical needle-shaped structures, as observed by the optical microscopic technique. Mean size and morphology were confirmed by transmission and scanning electron microscopy, while selective area electron diffraction patterns showed six-fold symmetry and indicated that the CdS crystals grow epitaxially with respect to the monolayer. Further, the crystallisation enhanced in the mixed LB films showed a characteristic zinc oxide (Wurtzite) structure compared with the pure ODSU matrix.     

TiO2 photoanodes prepared by cathodic electrophoretic deposition in 2-propanol: effect of the electric field and deposition time

This paper evaluates the influence of electric field and deposition time applied on cathodic electrophoretic formation of TiO₂ films in organic medium (2-propanol). The film morphology was tracked by measuring the deposited mass and film thickness. The variation in film porosity was correlated with the apparition of surface states distribution in the cyclic voltammetric characterization in the dark, due to grain boundaries defects generated in the contact of the TiO₂ particles. The open-circuit voltage decay curves showed that there is no formation of deep energy states inside the band gap of the TiO₂. The photopotential of the films increased until a critical thickness but the photocurrents showed to be dependent on operational variables, due to the fact that anodic polarization in thin films increases the electric field generated by the illumination at the ITO/TiO₂ interface, favoring the transport of the photogenerated electrons to the rear contact.     

Fabrication of CdS Nanorods in PVP Fiber Matrices by Electrospinning

Summary: A controlled fabrication of rod‐like nanostructures of cadmium sulfide (CdS) incorporated into polymer fiber matrices has been developed by an electrospinning method. Here, poly(vinyl pyrrolidone) (PVP) was used as a polymer capping reagent, utilizing the interactions of cadmium ions with the carbonyl groups in the PVP molecules. The formation of CdS nanorods inside the PVP was carried out via the reaction of Cd²⁺ with H₂S. SEM images showed that the electrospun films of PVP/CdS are composed of fibers with a diameter between 100 and 900 nm. TEM proved that most of the CdS nanorods are incorporated in the PVP fibrous film. The diameter of the rod is about 50 nm and the length is from 100 to 300 nm.

TEM image of the CdS nanorods formed in the PVP fibrous film.     

Photochemical synthesis of cadmium sulfide nanoparticles

The formation of cadmium sulfide nanoparticles upon UV irradiation of aqueous solutions of cadmium thiosulfates was established on the basis of spectroscopic and macroscopic data. The yield and size of the cadmium sulfide nanoparticles depend on the ratio of cadmium to thiosulfate ions in solution, the concentration of the solution, and the irradiation duration. The cadmium sulfide nanoparticles with a diameter of 4 nm were obtained by the photolysis of solutions with a concentration of 10⁻³ mol L⁻¹ at the ratio S₂O₃ ²⁻: Cd²⁺ = 2: 1.     

Synthesis of nanocomposite, (CdxZn1-x)S by gamma-irradiation in an aqueous system

Gamma-irradiation has been applied to synthesize the nanocomposite semiconductor constituted of zinc and cadmium sulfide Cd_1-xZn_xS ultra fine particles at room temperature by utilizing homogeneous release of S^2– ions from the decomposition of sodium thiosulfate. The structure, morphology, size and optical properties of that compound have been studied by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and ultraviolet-visible spectrometer (UV-visible). The product obtained from irradiated solutions containing zinc ions, cadmium ions and the sulfur source has been characterized as a composite of (Cd_xZn_1-x)S, with spherical morphology and with a diameter of average size of about 5.3 nm. The possible mechanism of formation of the composite is proposed.The financial support of Shanghai Science and Technology Foundation through No. 0252nm 095 is gratefully acknowledged.The authors would thank the staff of Shanghai Applied Radiation Institute of Shanghai University for their valuable contributions.     

Synthesis of nanocomposite, (CdxZn1-x)S by gamma-irradiation in an aqueous system

Gamma-irradiation has been applied to synthesize the nanocomposite semiconductor constituted of zinc and cadmium sulfide Cd_1-xZn_xS ultra fine particles at room temperature by utilizing homogeneous release of S^2– ions from the decomposition of sodium thiosulfate. The structure, morphology, size and optical properties of that compound have been studied by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and ultraviolet-visible spectrometer (UV-visible). The product obtained from irradiated solutions containing zinc ions, cadmium ions and the sulfur source has been characterized as a composite of (Cd_xZn_1-x)S, with spherical morphology and with a diameter of average size of about 5.3 nm. The possible mechanism of formation of the composite is proposed.The financial support of Shanghai Science and Technology Foundation through No. 0252nm 095 is gratefully acknowledged.The authors would thank the staff of Shanghai Applied Radiation Institute of Shanghai University for their valuable contributions.     

Growth of semiconducting iron sulfide thin films by chemical vapor deposition from air-stable single-source metal organic precursor for photovoltaic application

Semiconducting nanostructured iron sulfide thin films were prepared by aerosol chemical vapor deposition at 673 and 723?K from newly synthesized iron complex of dithiocarbo-1,2,3,4-tetrahydroquinoline [Fe(S₂CNC₉H₁₀)₂]. The degree of film surface roughness was determined by atomic force microscopy. The nature of the deposited thin films formed was determined by a combination of EDX analysis and glancing angle X-ray diffraction.     

Growth mechanism of Nb-doped TiO<Subscript>2</Subscript> sol–gel multilayer films characterized by SEM and focus/defocus TEM

TiO₂ and Nb-doped TiO₂ films were prepared by sol–gel processing, their microstructure was adjusted by varying the number of subsequent coating-firing cycles that resulted in final total film thickness of ~100 nm. When only few subsequent coatings are stacked (large single layer thickness) granular polycrystalline microstructures are observed. Doping with Nb reduces the crystallite size compared to the respective pure anatase films. When the single layer thickness is reduced, the film growth is successively dominated by the nucleation of subsequent films on the underlying crystalline material resulting in a columnar dense film structure. The multilayer architecture of such films can be demonstrated by defocus TEM imaging even if crystalline columns exceed single film boundaries. Results indicate that Nb is homogeneously incorporated into the anatase lattice by substitution of Ti, nevertheless the electric conductivity after H₂ post annealing is significantly lower than reported for analogous films prepared by magneton sputtering or pulsed laser deposition.     

Chemical bath deposition of thin nanocrystalline tin(II) sulfide films with thioacetamide

Nanocrystalline tin(II) sulfide layers 100–650 nm thick were prepared by hydrochemical deposition on glass–ceramic supports from a citrate system at 323?343 K using thioacetamide as chalcogenizing agent. These films are of interest for the development of thin-film solar radiation converters based on the multicomponent compound Cu₂ZnSnS₄ of kesterite structure, prepared using a cost-saving process. Examination by scanning electron microscopy shows that tin(II) sulfide layers are formed from spherical nanocrystallites of 20–40 nm size. X-ray diffraction analysis shows that they crystallize in the orthorhombic system with the unit cell parameters a = 4.276, b = 11.243, and c = 3.986 Å. Analysis by X-ray photoelectron spectroscopy revealed the presence of up to 44.86 at. % oxygen in the surface layer of the film. This oxygen is mainly present in surface contaminants and is also incorporated in SnO present on the surface.     

Chemical modification of carbon-coated anodic alumina films and their application to membrane filter

An anodic aluminum oxide film that has uniform and straight nanochannels was exposed to propylene at 800°C, resulting in uniform carbon deposition on the inner-surface of the channels as well as the external surface of the film. The carbon-coated aluminum oxide film was then chemically modified by either fluorination or HNO₃ treatment. The change in channel structure due to the carbon deposition and the subsequent chemical modification was analyzed. Gas permeation behavior through these films was examined by using He and N₂. Furthermore, the films were applied to pervaporation separation of water/ethanol mixture and it was found that water preferentially permeated the fluorinated film. The present study demonstrated that even a membrane whose pore size is as large as 24 nm exhibits selectivity in pervaporation.     

Properties of nanocrystalline electrodeposited CoFeP alloy with low phosphorus content

CoFe and low phosphorus containing (<4 at.%) CoFeP alloy films were electrodeposited from NaH₂PO₂ containing solutions at pH 4 on copper substrates under galvanostatic conditions. At the low phosphorus composition, nanocrystalline CoFeP alloy films are formed. The structure, composition and morphology of the thin films were studied using X-ray diffraction, energy dispersive spectroscopy and atomic force microscopy. The magnetic properties of the film were studied using superconducting quantum interference device magnetometer. The thin film performance features were explained on the basis of microstructural features developed during deposition. Whereas the electrodeposited CoFe alloy thin film exhibited mixed hcp and fcc phase structure in the absence of phosphorus, the low phosphorus containing thin film exhibited an increasing mixed bcc and hcp phase structure as its phosphorus content increases, showing modification in the grain size morphology and magnetic properties. In addition to applied current, the amount of P co-deposited in CoFeP alloy depends on the concentration of NaH₂PO₂ source in the bath. Qualitative analysis of the Tafel slope of CoFe and CoFeP deposition suggests that the presence of P in the CoFe deposit does not affect the mechanism of anomalous deposition of Co and Fe, thereby suggesting that CoFeP deposition is anomalous.     

Electrochemical properties of composite films based on poly-3,4-ethylenedioxythiophene with inclusions of metallic palladium

The electrochemical behavior of composite Pd-PEDOT films is studied. These films are obtained by chemical deposition of Pd particles in the polymeric matrix of PEDOT (poly-3,4-ethylenedioxythiophene). Characteristics of the films are determined by means of cyclic voltammetry, faradaic impedance, microgravimetry, and energy-dispersive x-ray fluorescence analysis. Impedance spectra of composite Pd-PEDOT films, compared to the original PEDOT film, reveal a new response at potentials of −0.3 and −0.4 V in the form of a distinct semicircle, which results from processes in the electrochemical sorption-desorption of hydrogen. Weight gain during the chemical deposition of palladium in the polymer structure is estimated by mircrogravimetry. It is shown that the mass of palladium loaded in the film depends on the time of synthesis and the initial concentration of palladium ions in solution. The size of the actual surface and the average radius of dispersed palladium particles in the film are also estimated.     

Investigation of surface topography, morphology and structure of amorphous carbon films by AFM and TEM

Morphology and structure of amorphous carbon films deposited with a pulsed arc source (LASER-ARC) have been studied using microscopical methods (SEM, TEM and AFM), electron diffraction and spectroscopical investigation (EELS). The parameters of the arc source and the deposition conditions (substrate temperature) influence morphology and structure of deposited amorphous carbon films. Especially the incorporation and growth of particles, embedded in the film have been investigated. By particle analysis using an optical microscope a majority of particles that is smaller than 500 nm has been determined. The morphology has been also demonstrated similar by AFM and TEM images. Their number and size of particles is strongly influenced by the deposition temperature. The structure of amorphous film is characterized by the EELS-spectra, but the particle structure was not detectable.