CdS thin films doped with metal-organic salts using chemical bath deposition

CdS thin films doped with metal-organic salts were grown on glass substrates at 90 °C by the chemical bath deposition technique. Metal-organic salts such as zinc acetate, chromium acetylacetonate, ammonium fluoride, aluminum nitrate, tin acetate and indium acetate were used. The chemical bath was prepared with cadmium acetate, ammonium acetate, thiourea and ammonium hydroxide. In the case of un-doped films, the S/Cd ratio was varied by changing the thiourea in the range 1-12. The best optical, structural and electrical properties were found for S/Cd = 2. The doped films were prepared by always keeping the ratio S/Cd constant at 2. The band gap (E_g) of doped and un-doped films was evaluated from transmittance spectra, where films with lower sulfur concentration exhibited higher E_g. X-ray analysis showed that both un-doped and doped films were polycrystalline with preferential orientation along the (111) direction and with the zincblende structure in all cases. The dark electrical results showed that CdS doped with Zn (1 at.%) exhibited the lowest resistivity values of 10 Ω cm.     

Optical and structural properties of chemically deposited CdS thin films on polyethylene naphthalate substrates

CdS thin films were deposited on polyethylene naphthalate substrates by means of the chemical bath deposition technique in an ammonia-free cadmium-sodium citrate system. Three sets of CdS films were grown in precursor solutions with different contents of Cd and thiourea maintaining constant the concentration ratios [Cd]/[thiourea] and [Cd]/[sodium citrate] at 0.2 and 0.1 M/M, respectively. The concentrations of cadmium in the reaction solutions were 0.01, 7.5 × 10⁻³ and 6.8 × 10⁻³ M, respectively. The three sets of CdS films were homogeneous, hard, specularly reflecting, yellowish and adhered very well to the plastic substrates, quite similar to those deposited on glass substrates. The structural and optical properties of the CdS films were determined from X-ray diffraction, optical transmission and reflection spectroscopy and atomic force microscopy measurements. We found that the properties of the films depend on both the amount of Cd in the growth solutions and on the deposition time. The increasing of Cd concentration in the reaction solution yield to thicker CdS films with smaller grain size, shorter lattice constant, and higher energy band gap. The energy band gap of the CdS films varied in the range 2.42-2.54 eV depending on the precursor solution. The properties of the films were analyzed in terms of the growth mechanisms during the chemical deposition of CdS layers.     

Structural and optical properties of CdS thin films grown by chemical bath deposition

Cubic cadmium sulphide (CdS) thin films with (111) preferential orientation were prepared by chemical bath deposition (CBD) technique, using the reaction between NH₄OH, CdSO₄ and CS(NH₂)₂. The films properties have been investigated as a function of bath temperature and deposition time. Structural properties of the obtained films were studied by X-ray diffraction analysis. The structural parameters such as crystallite size have been evaluated. The transmission spectra, recorded in the UV visible range reveal a relatively high transmission coefficient (70%) in the obtained films. The transmittance data analysis indicates that the optical band gap is closely related to the deposition conditions, a direct band gap ranging from 2.0 eV to 2.34 eV was deduced. The electrical characterization shows that CdS films' dark conductivities can be controlled either by the deposition time or the bath temperature.     

Structural, electrical and optical studies of SILAR deposited cadmium oxide thin films: Annealing effect

Successive ionic layer adsorption and reaction (SILAR) method has been successfully employed for the deposition of cadmium oxide (CdO) thin films. The films were annealed at 623 K for 2 h in an air and changes in the structural, electrical and optical properties were studied. From the X-ray diffraction patterns, it was found that after annealing, H₂O vapors from as-deposited Cd(O₂)_0.88(OH)_0.24 were removed and pure cubic cadmium oxide was obtained. The as-deposited film consists of nanocrystalline grains of average diameter about 20-30 nm with uniform coverage of the substrate surface, whereas for the annealed film randomly oriented morphology with slight increase in the crystallite size has been observed. The electrical resistivity showed the semiconducting nature with room temperature electrical resistivity decreased from 10⁻² to 10⁻³ Ω cm after annealing. The decrease in the band gap energy from 3.3 to 2.7 eV was observed after the annealing.     

Preparation of II–VI and IV–VI semiconductor films for solar cells by the isovalent substitution technique with a CBD-made substrate

II–VI and IV–VI semiconductor films for solar cell applications, namely, CdTe, CdS, CdSe, PbS, PbSe and PbTe, can be prepared in a two-stage deposition process. In this work we illustrate the two-stage process to obtain PbTe and CdSe films from precursor oxide or hydroxide films deposited by chemical bath deposition (CBD). At the first stage, plumbonacrite Pb₁₀(CO₃)₆O(OH)₆ or cadmium oxide/hydroxide CdO₂/Cd(O₂)_0.88(OH)_0.24 films were deposited onto a glass substrate by CBD, using an ammonia-free low-temperature process in an alkaline aqueous solution with corresponding ion sources. Then, at the second stage, the obtained film was placed in a chemical vapor deposition (CVD) Hot Wall reactor with gas transportation, where it acted as a substrate in the reaction of isovalent substitution of Te or Se for the nonmetallic film component, thus forming PbTe and CdSe films. A nitrogen flux of 0.25 L/min was used as the transporting gas. The source temperature was adjusted between boiling (Tb) and melting point (Tm) to control the flux gas of the source. The substrate temperature was adjusted to improve film quality. Structural and optical investigation of the films proved their high quality, which determines the possibility of using them as solar cell elements, in particular, in multijunction cells.     

Structural and optical properties of nanocrystalline CdS thin films prepared using microwave-assisted chemical bath deposition

Cadmium sulfide (CdS) nanocrystalline thin films were prepared using the microwave-assisted chemical bath deposition method onto glass substrates at 80 °C. Aqueous solutions of either cadmium chloride or cadmium acetate and thiourea were used as sources of Cd²⁺ and S²⁻ ions, respectively. Two sets of samples with different concentrations were prepared. A microwave oven was used as a heating source to synthesize the nanocrystalline CdS thin films. The prepared thin films had a good adhesion with no pinholes. These films were examined for their structural and surface morphologies by X-ray diffraction (XRD), scanning electron microscopy, and atomic force microscopy. The optical properties were investigated using UV-vis spectrophotometer, photoluminescence, and Raman spectroscopy. Particle size values obtained from XRD were compared with these calculated using effective mass models. The values of optical band gaps according to optical transmission measurements decreased as the ion source molar concentration increased.     

化学水浴沉积时间对CdS薄膜性质的影响

采用CBD法在醋酸镉溶液体系中制备CdS半导体薄膜,通过XRD、XRF、SEM和光学透过率谱等测试手段研究了沉积时间对CdS薄膜沉积过程和性质的影响.结果表明,随着沉积时间的增加,薄膜增厚;S/Cd原子比增加,但都为富Cd的CdS薄膜;XRD研究表明,薄膜结构由立方、六方混合相向立方相转变,(111)方向成为择优生长方向;SEM研究表明,随沉积时间增加,薄膜变致密,薄膜表面出现的白色附着颗粒增多,尺寸增大;沉积时间对薄膜的光学性质也有很大的影响,随着沉积时间的增加薄膜透过率减小,而禁带宽度值增大.     

Study of annealing-induced changes in CdS thin films using X-ray diffraction and Raman spectroscopy

We have investigated as grown and annealed (300 °C, 400 °C and 500 °C) thin films of CdS grown on GaAs (001) by chemical bath deposition. X-ray diffraction (XRD) shows that the as grown CdS film is polycrystalline and predominantly cubic. A residual compressive stress of the order of 1.45% in the as grown film relaxes on annealing the film at 300 °C. Furthermore, CdS film undergoes a structural phase transition from the metastable cubic phase to the stable hexagonal phase, when, annealed at 500 °C. This is accompanied by significant improvement in crystalline quality of the film. Line shape analysis of the asymmetry of the longitudinal optical phonon shows a disorder-activated mode, which correlates well with the crystalline quality estimated from XRD and photoluminescence measurements. The additional features observed in the Raman spectra ∼ 254 cm^− 1 and 309 cm^− 1 are investigated using temperature dependent Raman spectroscopy and identified as superposition of transverse optical: E₁ (TO) and E₂ phonons at q = 0 and combination mode (two zone-edge E₂ phonons) respectively.     

Sb2S3:C/CdS p-n junction by laser irradiation

In this paper, we report laser irradiated carbon doping of Sb₂S₃ thin films and formation of a p-n junction photovoltaic structure using these films. A very thin carbon layer was evaporated on to chemical bath deposited Sb₂S₃ thin films of approximately 0.5 μm in thickness. Sb₂S₃ thin films were prepared from a solution containing SbCl₃ and Na₂S₂O₃ at 27 °C for 5 h and the films obtained were highly resistive. These C/Sb₂S₃ thin films were irradiated by an expanded laser beam of diameter approximately 0.5 cm (5 W power, 532 nm Verdi laser), for 2 min at ambient atmosphere. Morphology and composition of these films were analyzed. These films showed p-type conductivity due to carbon diffusion (Sb₂ S₃:C) by the thermal energy generated by the absorption of laser radiation. In addition, these thin films were incorporated in a photovoltaic structure Ag/Sb₂S₃:C/CdS/ITO/Glass. For this, CdS thin film of 50 nm in thickness was deposited on a commercially available ITO coated glass substrate from a chemical bath containing CdCl₂, sodium citrate, NH₄OH and thiourea at 70 °C. On the CdS film, Sb₂S₃/C layers were deposited. This multilayer structure was subjected to the laser irradiation, C/Sb₂S₃ side facing the beam. The p-n junction formed by p-Sb₂S₃:C and n-type CdS showed V_oc = 500 mV and J_sc = 0.5 mA/cm² under illumination by a tungsten halogen lamp. This work opens up a new method to produce solar cell structures by laser assisted material processing.     

Bio-template route for facile fabrication of Cd(OH)2@yeast hybrid microspheres and their subsequent conversion to mesoporous CdO hollow microspheres

Cadmium oxide (CdO) microspheres with a porous hollow microstructure were prepared by a facile yeast mediated bio-template route. The yeast provides a solid scaffold for the deposition of cadmium hydroxide (Cd(OH)₂) from cadmium acetate and sodium hydroxide solutions to form the hybrid Cd(OH)₂@yeast precursor. Thermal conversions of this at above 500 °C in air have produced hollow CdO microspheres. The products were characterized by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), thermal gravimetric and differential thermal analysis (TGA-DTA), and Brunauer-Emmett-Teller (BET) surface analysis respectively. The obtained CdO microspheres have uniform size (length = 2.6 ± 0.4 μm; width = 2.0 ± 0.2 μm) and a well defined, continuous, mesoporous hollow microstructure. The shell is about 250-280 nm in thickness. The mechanism of formation of Cd(OH)₂@yeast precursor and its conversion to CdO hollow microspheres is discussed. In comparison with traditional template-directed method, the present strategy represents a general, economical and environmentally benign route for the formation of metal oxide hollow microspheres. These materials have potential applications in different fields such as encapsulation, drug delivery, efficient catalysis, battery materials and photonic crystals. The method presented can be extended to the synthesis of other inorganic hollow microstructures of different sizes and shapes by pre-selecting suitable bio-templates.     

Cadmium sulfide nanotubes thin films: Characterization and photoelectrochemical behavior

Monodisperse cadmium sulfide nanotubes (CdS NTs) with a diameter of 100 nm were synthesized on indium-doped tin oxide glass substrates using chemical bath deposition and self-sacrificial template technique. This CdS thin film was characterized by transmission electron microscope, scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis spectrophotometer. This film gave a short circuit photocurrent of 4.4 mA/cm², an open circuit photovoltage of 0.75 V, a fill factor of 0.49, and an overall conversion efficiency of 1.29% under a simulated solar illumination of 100 mW/cm². All these photoelectrochemical properties of the films were dependent on the microstructure of the nanotubes and the thickness of the film. A facile and efficient way to prepare CdS-based photoelectrodes for photoelectrochemical cells was provided in this report.     

Enhancement of the photochromic and thermochromic properties of molybdenum oxide thin films by a cadmium sulfide underlayer

We investigated the photochromic and thermochromic behavior of amorphous MoO₃ films prepared by thermal evaporation of MoO₃ powder on glass and glass/CdS substrates. We used the cadmium sulfide as a carrier charge injector to produce higher color center concentrations in the MoO₃ film. The semiconductor CdS (cadmium sulfide) film was synthesized using the chemical bath deposition technique. The glass/MoO₃ and glass/CdS/MoO₃ films were subjected to tungsten lamp (100 W) exposure times of 45 to 180 min to study the photochromic sensitivity of the films. To study the thermochromic properties, samples were thermally annealed at temperatures ranging from 100 to 250 °C during 2 h. X-ray diffraction studies show that the CdS films were polycrystalline, and the oxide films were amorphous. Optical absorption measurements showed the presence of an absorption band centered around 850 nm due to the formation of color centers. Concentrations of these were calculated using the Smakula equation. Results indicate that the addition of CdS films enhances the photochromic and thermochromic properties of MoO₃. Photochromism is more effective than thermochromism in generating color centers when using CdS as a charge carrier.     

Hydrothermal synthesis of β-nickel hydroxide nanocrystalline thin film and growth of oriented carbon nanofibers

Novel well-crystallized β-nickel hydroxide nanocrystalline thin films were successfully synthesized at low temperature on the quartz substrates by hydrothermal method, and the oriented carbon nanofibers (CNFs) were prepared by acetylene cracking at 750 °C on thin film as the catalyst precursor. High resolution transmission electron microscopy (HR-TEM) measurement shows that thin films were constructed mainly with hexagonal β-nickel hydroxide nanosheets. The average diameter of the nanosheets was about 80 nm and thickness about 15 nm. Hydrothermal temperature played an important role in the film growth process, influencing the morphologies and catalytic activity of the Ni catalysts. Ni thin films with high catalytic activity were obtained by reduction of these Ni(OH)₂ nanocrystalline thin films synthesized at 170 °C for 2 h in hydrothermal condition. The highest carbon yield was 1182%, and was significantly higher than the value of the catalyst precursor which was previously reported as the carbon yield (398%) for Ni catalysts. The morphology and growth mechanism of oriented CNFs were also studied finally.     

Multiple dip deposition of CdS films prepared by oscillating chemical bath

Highly oriented CdS thin films with thicknesses greater than 1 μm were deposited using the oscillating chemical bath deposition technique with multiple dips at 75 °C, and from 15 to 75 min as deposition times. Samples with different thicknesses were deposited by repeating the chemical deposition process one, two and three times. All CdS films present the α-greenockite hexagonal structure with (002) as the preferential orientation. Band-gap energy values ranged from 2.35 to 2.42 eV, being the smaller value for the two dip processes. Energy dispersion spectroscopy measurements show good stoichiometry of the CdS films with 4.3 at.% as the maximum Cd variation.     

Analysis of the early growth mechanisms during the chemical deposition of CdS thin films by spectroscopic ellipsometry

Chemically deposited CdS thin films were analyzed in this work by means of the spectroscopic ellipsometry technique. The CdS thin films were deposited from an ammonia-free process at short durations in order to obtain information about the layer microstructure and kinetic growth process. We found that the conditions of the ammonia-free reaction solution promote the ion-by-ion deposition process at the early growth stages yielding a compact, high refraction index and highly crystalline oriented CdS layers. Using a concentration of 1.82 mg/ml of cadmium in the reaction solution, the resulting films possess a double layer microstructure which consists of an inner compact layer and an external porous one. The inner layer is developed during the first 15 min of deposition time and it reaches a thickness around of 80 nm. After this time and on this inner layer of CdS, it grows an external porous layer whose thickness increases with the deposition time. The formation of the CdS compact layer at the early stages is related with the ion-by-ion growth mechanism. The subsequent CdS porous layer is formed during the cluster-by-cluster growth stage at longer deposition times. By reducing the cadmium concentration in reaction solution down to 0.76 mg/ml, maintaining constant molar ratio concentrations of Cd/complexing and Cd/thiourea, the chemically deposited CdS films develop only the inner compact layer with a thickness of about 80 nm after 35 min of deposition time.     

Growth of thin CdS films on glass substrates via reaction of thiourea with cadmium acetate in aqueous solution

Thin CdS films have been produced by chemical surface deposition from aqueous solutions of cadmium acetate, Cd(CH₃COO)₂. We have studied the morphology and optical properties of the CdS films and calculated the mechanical stress induced by the difference in linear thermal expansion coefficient between the film and substrate materials.     

An in-situ chemical reaction deposition of nanosized wurtzite CdS thin films

Nanocrystalline CdS thin films were deposited on glass substrates by an ammonia-free in-situ chemical reaction synthesis technique using cadmium cationic precursor solid films as reaction source and sodium sulfide based solutions as anionic reaction medium. Effects of ethanolamine addition to the cadmium cationic precursor solid films, deposition cycle numbers and annealing treatments in Ar atmosphere on structure, morphology, chemical composition and optical properties of the resultant films were investigated by X-ray diffraction, field emission scanning electron microscope, energy dispersive X-ray analysis and UV-Vis spectra measurements. The results show that CdS thin films deposited by the in-situ chemical reaction synthesis have wurtzite structure with (002) plane preferential orientation and crystallite size is in the range of 16 nm-19 nm. The growth of film thickness is almost constant with deposition cycle numbers and about 96 nm per cycle.     

Effect of CdCl2 annealing treatment on thin CdS films prepared by chemical bath deposition

In order to study the CdS recrystallization mechanism, a comparative study was carried out on thin films prepared by chemical bath deposition. The CdS films were annealed in air with or without a CdCl₂ coating layer. In-situ Raman spectra obtained during the annealing showed that both the air- and the CdCl₂-annealing did not cause rearrangement of the neighboring atoms in the CdS clusters below ~ 300 °C. CdS thin film was partially oxidated to CdO and CdSO₄ on the cluster surface when annealed in air. The oxides and the sulfur stoichiometric deficiency prevented the clusters to coalesce at higher temperatures. Coating thin CdS film with a thin CdCl₂ layer protected it from oxidation during annealing in air and promoted formation of Cl_S and V_Cd point defects in CdS. The anti-oxidation was attributed to the incorporation of a significant amount of Cl into CdS to form the Cl_S, which prevented the oxygen in-diffusion and chemical bonding during the annealing. The anti-oxidation at the CdS nano-crystalline surface and the point defects formed in the CdS promoted coalescence of the neighboring clusters without the need of long-range redistribution of the atoms. Large CdS grains with good crystalline quality formed through recrystallization during the CdCl₂ heat treatment, which provided the solid basis for the subsequent CdTe growth and high efficient CdS/CdTe solar cell fabrication.     

Mechanism for CdS electrodeposition from fused salt

Electrodeposition of CdS on a graphite substrate from LiCl-KCl eutectic melt containing CdCl₂ and Na₂SO₃ has been examined. It has been found that the cathodic deposition of CdS onto a graphite substrate occurs in competition with the formation of CdS particles by homogeneous precipitation in the bath. We have proposed as a deposition mechanism that the underpotential deposition of cadmium occurs under the influence of some sulphur species. We have also found that crystals of solid solution of CdS-CdSe are electrodeposited by adding selenium powder in the bath.     

Comparison of the optical and structural properties of nickel oxide-based thin films obtained by chemical bath and sputtering

Nickel oxide thin films were prepared using chemical bath deposition and reactive magnetron dc-sputtering. Through the chemical route, Ni(OH)₂ films were deposited with a nano-porous structure providing large specific surface area. Subsequent annealing at 300 °C transformed the films into NiO. These films showed high absorption in the visible range and low crystallinity due to Ni vacancies. Annealing at higher temperatures removes Ni vacancies improving transmittance and crystallinity. Sputtered films were obtained in Ar + O₂ and Ar + H₂ + O₂ atmospheres at different flux ratios. During deposition in the former atmosphere, substrate temperature was 300 °C producing dense polycrystalline films with excellent optical properties. In the hydrogen containing atmosphere, the substrate was at room temperature and polycrystalline films with a dark-yellowish color and expanded lattice were obtained.