Effect of four different zinc salts and annealing treatment on growth,structural, mechanical and optical properties of nanocrystalline ZnS thin films by chemical bath deposition

ZnS thin films were deposited from four different zinc salts on glass substrates by chemical bath deposition method. Different anions of zinc salts affect the deposition mechanism and growth rate, which influence the properties of the films significantly. The ZnS thin film deposited from ZnSO₄ is smoother, thicker, more homogeneous and compact, nearly stoichiometric, comparing with the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂, and ZnCl₂. The scratch test of bonding force between ZnS film and substrate shows that the ZnS film deposited from ZnSO₄ has the most excellent adhesion with the substrate. The presence of SO₄²⁻ promotes heterogeneous ZnS thin film growth via ions by ions deposition, and the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂ are formed via clusters by clusters deposition. XRD and HRTEM results show that cubic ZnS films are obtained after single deposition, and the grain size of ZnS thin film deposited from ZnSO₄ for 2.5 h is 10 nm. The average transmission of all films is greater than 85% in the wavelength ranging from 600 to 1100 nm, and the transmission of films deposited from ZnSO₄ or Zn(NO₃)₂ for 1.5, 2 and 2.5 h is greater than 85% in the wavelength varying from 340 to 600 nm, which can enhance the blue response. The band gaps of all ZnS thin films are in the range of 3.88–3.99 eV. After annealing treatment, the mechanical and optical properties of the ZnS thin film deposited from ZnSO₄ are improved significantly.     

Optimising conditions for the growth of nanocrystalline ZnS thin films from acidic chemical baths

The growth of nanocrystalline zinc sulfide thin films onto glass substrates by chemical bath deposition has been optimized at acidic pH. Powder X-ray diffraction (p-XRD) confirms the deposition of sphalerite, the cubic phase of ZnS. The crystallite size calculated by Scherrer equation was found to be 4.0 nm. Scanning Electron Microscopy (SEM) show clusters of spherical nanoparticles uniformly distributed over the surface of the glass substrates. Energy Dispersive X-ray (EDX) analysis of the deposited thin films show the zinc to sulfur ratio close to 1:1. The observed band gap (3.78 eV) of the deposited thin films is higher than that reported for cubic phase of bulk ZnS (3.54 eV) as expected due to nano-size crystallites. Binding energies calculated by X-ray Photoelectron Spectroscopy (XPS) confirm the material as ZnS and the photoluminescence measurements show the blue shift in emission maximum.     

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.     

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.     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

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.     

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.     

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.     

Comparative studies on the structural,morphological, optical,and electrical properties of nanocrystalline PbS thin films grown by chemical bath deposition using two different bath compositions

High-quality lead sulfide (PbS) thin films were synthesized by chemical bath deposition from two baths with different compositions. One of them (bath-І) contained an aqueous solution of lead acetate, thiourea, sodium hydroxide, and the second (bath-ІІ) had additional triethanolamine. The introduction of triethanolamine reduced the grain size and increased the optical band gap of the PbS nanoparticles. The structure, morphology, and optical properties of the obtained films were investigated and compared with respect to the deposition time. X-ray diffraction data were used to obtain the crystallite size, lattice constant, and strain of the films. Atomic force microscopy results show that the roughness and rms-surface slope of the samples obtained from bath-I (PbS-I) were higher than those of bath-II (PbS-II) samples. PbS thin films with high reflectance (~61%) in the near-infrared region, which is important in our solar system, were obtained. The band gap, extinction coefficient, and refractive index of the samples were calculated. Furthermore, Raman analysis was performed and electrical properties of the samples were studied.     

Investigation of characteristics of ZnO:Ga nanocrystalline thin films with varying dopant content

In this study, undoped and Ga doped ZnO thin films were synthesized by the sol–gel spin coating technique. The effect of Ga contribution on the structural, morphological and optical properties of the ZnO thin films was examined. XRD results showed that all films had a hexagonal wurtzite crystal structure with polycrystalline nature. The intensity of the (002) peak changed with the variable Ga content. The scanning electron microscopy (SEM) results revealed that the surface morphology of the ZnO thin films was affected by Ga content. Moreover, it consisted of nanorods as a result of the increased function of the Ga content. Additionally, the presence of Ga contributions was evaluated by energy dispersive x-ray (EDX) measurements. Although the transparency and the optical band gap of the ZnO thin films increased with Ga contribution, Urbach energy values decreased from 221 meV to 98 meV. In addition, these steepness parameters increased with the increased Ga content from 0% to 6%. The correlation between structural and optical properties was investigated and significant consistency was found.     

Synthesis of mackinawite FeS thin films from acidic chemical baths

The growth of monophasic iron sulfide thin films onto glass substrates has been achieved by chemical bath deposition at acidic values of pH. Powder X-ray diffraction (p-XRD) confirms the deposition of tetragonal FeS (mackinawite) with preferred orientation along (001) plane. The crystallite size estimated by Scherrer equation was found to be 14 nm. Scanning electron microscopy (SEM) shows the formation of nanoflakes as base layer and nanoflowers as top layer. Energy Dispersive X-ray (EDX) analysis of the deposited iron sulfide thin films shows the iron to sulfur ratio close to 1:1 confirming the deposition of FeS. UV–vis absorption spectroscopy showed a blueshift due to the nanosize crystallites FeS with a band gap of 1.87 eV.     

Electrospray deposition and characterization of cobalt oxide thin films

Cobalt oxide thin films were fabricated by means of electrospray deposition. The obtained films were characterized by Raman spectroscopy, X-ray diffraction and Scanning electron microscopy. The solution that was used gave the Co₃O₄ phase at different growth temperatures. The best granular surfaces were obtained at 250 °C as verified by all characterization techniques, while flaky surfaces were obtained at higher temperatures. The surface morphology is mostly granular except for high temperatures where the cobalt oxide is formed as flakes instead of grains.     

Spray deposition and characterization of zirconium-oxide thin films

Zirconium oxide films were prepared by the pyrosol process using zirconium acetylacetonate as source material onto clear fused quartz and (100) silicon at substrate temperatures ranging from 300°C to 575°C. X-ray diffraction (XRD) measurements show that samples prepared at substrate temperatures lower than 425°C are amorphous. Films deposited at higher temperatures and short deposition times show a cubic crystalline structure. However, for long deposition times, the samples show monoclinic crystalline structure. A similar phase transformation is observed on samples deposited at short time if they are annealed at high temperature. The cubic and monoclinic phases of the corresponding samples were confirmed by infrared (IR) and Raman spectroscopy, respectively. The ZrO₂ films with cubic phase show an almost stoichiometric chemical composition and refractive index values of the order of 2.1 with an energy band gap of 5.47 eV. The current-density electric-field characteristics of metal-oxide semiconductor (MOS) structures show a small ledge from 2 MV/cm to 4.5 MV/cm, indicating current injection and charge trapping. For higher electric fields, the current is associated with oxygen ion diffusion through the zirconium oxide film. The dielectric breakdown is observed at 6 MV/cm, which is a value higher than those observed in the monoclinic and tetragonal phases.     

Effect of annealing on physical properties of CBD synthesized nanocrystalline FeSe thin films

Nanocrystalline FeSe thin films were successfully prepared by solution growth method using ferric chloride and sodium selenosulphate as cationic and anionic precursors along with complexing agent oxalic acid. The thickness dependent physical properties of FeSe thin films prepared by varying deposition time are discussed. The FeSe films of thickness 161 nm were further annealed to investigate its impact on physical properties. The X-ray diffraction studies showed that, as deposited FeSe films are nano crystalline in nature and their crystallinity increases with thickness as well as with annealing temperature. The morphological studies showed that FeSe exhibits granular surface with channel like features at higher thickness. The electrical resistivity and thermo-emf measurements confirmed that, FeSe films are semiconducting in nature with P-type conductivity. The activation and band gap energies of FeSe films are found dependent on film thickness as well as on annealing temperature.     

Thickness dependent physical properties of chemically deposited nanocrystalline MgSe thin films deposited at room temperature by solution growth method

Chemical bath deposition method has been employed to deposit nanocrystalline magnesium selenide thin films of thickness 104–292 nm onto glass substrates at room temperature. The deposition bath consists of magnesium chloride, triethanolamine (TEA) and selenium dioxide. The as deposited films were characterized by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM), optical absorption, electrical resistivity and thermo-emf measurements. The X-ray diffraction (XRD) studies revealed that the crystallinity of the magnesium selenide thin film increases with thickness. SEM studies reveal that MgSe films exhibit uniform distribution of round shaped grains over the entire substrate surface.The optical band-gap and electrical resistivity of MgSe film decrease as the film thickness increases. Such type of dependence is attributed to the quantum size effect that is observed in nanocrystalline semiconductors.The thermo-emf measurement confirms its p-type conductivity.     

硫化法制备ZnS薄膜的结构和光学性能研究

采用直流反应磁控溅射法,在玻璃衬底上沉积了ZnO薄膜,然后在H2S气氛和500℃温度下退火制备了六方ZnS薄膜。利用X射线衍射仪(XRD)、UV-VIS分光光度计、扫描电子显微镜(SEM)对样品进行了表征。结果表明:ZnO经0.5 h硫化就能全部生成ZnS,适当提高硫化时间可改善ZnS的结晶性,但硫化时间超过2 h后,结晶性会有所降低;所有制得ZnS薄膜都沿c轴择优生长,其晶粒明显比ZnO更大。此外,这些ZnS薄膜在500~1 100nm波长范围内的光透过率均高达约75%,带隙为3.65~3.70 eV。     

衬底温度对纳米晶SnO_2薄膜结晶特性的影响

阐述了金属氧化物SnO2纳米薄膜研究的发展情况及其应用前景,介绍了采用磁控溅射技术,使用混合气体Ar和O2,在衬底温度为150～400℃的耐热玻璃基片上制备了纳米晶SnO2∶Sb透明导电薄膜。通过测定x射线衍射谱,表明薄膜择优取向为[110]和[211]方向,SnO2∶Sb薄膜的结晶特性随衬底温度变化。     

Facile deposition of ZnO:Cu films: Structural and optical characterization

Sol–gel technology has been applied for preparation of ZnO:Cu films. The proposed facile approach allows obtaining a wide variety of copper doped zinc oxide systems, revealing different structural and optical behaviors. The work presents structural and optical studies depending on Cu concentration and thermal treatments in the range of 500–800 °C. The structural analysis is performed by X-Ray diffraction (XRD). It reveals that small Cu addition enhances the film crystallization. Increasing copper concentration results in deterioration of ZnO:Cu crystallization. XRD study manifests no Cu oxide phases in ZnO:Cu film structure for lower Cu additions. For a specific higher copper concentration, an appearance of a small fraction of copper oxide is detected. Vibrational properties have been characterized by FTIR spectroscopy. The effect of the copper introduction into ZnO reveals a slight change of optical properties compared to ZnO films for certain Cu ratios. ZnO:Cu films with higher copper contents manifest different optical behaviors with very high transparency in spectral visible range.