CdS thin films growth by ammonia free chemical bath deposition technique

Cadmium Sulfide CdS thin films were deposited by chemical bath deposition technique using ethanolamine as complexing agent instead of commonly used ammonia to avoid its toxicity and volatility during film preparation. In order to investigate the film growth mechanism samples were prepared with different deposition times. A set of substrates were dropped in the same bath and each 30 minutes a sample is withdrawn from the bath, by this way all the obtained films were grown in the same condition. The films structure was analyzed by X rays diffraction. In early stage of growth the obtained films are amorphous, with increasing the deposition time, the films exhibits a pure hexagonal structure with (101) preferential orientation. The film surface morphology was studied by atomic force microscopy. From these observations we concluded that the early growth stage starts in the 3D Volmer-Weber mode, followed by a transition to the Stransky-Krastanov mode with increasing deposition time. The critical thickness of this transition is 120 nm. CdS quantum dots were formed at end of the film growth. The optical transmittance characterization in the UV-Visible range shows that the prepared films have a high transparency ranging from 60 to 80% for photons having wavelength greater than 600 nm.     

Effect of complexing agent on growth process and properties of nanostructured Bi2S3 thin films deposited by chemical bath deposition method

Nanostructured Bi₂S₃ thin films have been prepared onto amorphous glass substrates by chemical bath deposition method at room temperature using bismuth nitrate and sodium thiosulphate as cationic and anionic precursors with EDTA as complexing agent in aqueous medium. The X-ray diffraction study reveals that the films deposited without the complexing agent are amorphous in nature and becomes nanocrystalline in the presence of EDTA. The resistivity for the films prepared from EDTA complexed bath is decreased due to the improvement in grain structure. The decrease in optical bandgap and activation energy is observed as the thickness of the film varies from 45 to 211 nm on account of the variation of the volume of complexing agent in reaction bath. Studies reveal that the growth mechanism of Bi₂S₃ gets affected in the presence of complexing agent EDTA and shows impact on structural, electrical and optical properties.     

Effect of complexing agents: investigations on structural,morphological, topographical and optical analysis of copper iron sulphide thin films deposited by chemical bath deposition method

Copper iron sulphide (FeCuS₂) thin films deposited by chemical bath deposition method using ferrous sulphate and copper sulphate as cationic sources and sodium sulphide as anionic source with complexing agents, EDTA and Leishman stain were reported. The structural, optical and morphological studies were carried out using X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV–Visible spectroscopy techniques. The X-ray spectrum reveals that the films are polycrystalline nature and also showed the deposition of cubic phases at room temperature. The SEM images for prepared films have clear morphology influenced by the complexing agents used in deposition process. The result of AFM studies shown that the particles in the film have grain size around ~?60–70 nm and also have almost similar thickness. Based on the optical absorbance spectra the FeCuS₂ film exhibited a high absorbance in the visible region. The absorption edge shifted toward lower wavelength with varying complexing agents. The band gap value obtained was found to be 3.57–3.85 eV. From these results, it is indicated that the prepared films are suitable candidate for solar cell applications.     

磁控溅射法制备的CdS:Al薄膜的性质研究

采用Al和CdS双靶共溅射的方法, 调控Al和CdS源的沉积速率, 制备出不同Al掺杂浓度的CdS:Al薄膜。通过XRD、SEM、AFM、紫外-可见透射光谱分析、常温霍尔测试对CdS: Al薄膜的结构、形貌、光学和电学性质进行表征。XRD结果表明, 不同Al掺杂浓度的CdS:Al薄膜均为六方纤锌矿结构的多晶薄膜, 并且在(002)方向择优生长。SEM和AFM结果表明, CdS:Al薄膜的表面均匀致密, 表面粗糙度随着Al掺杂浓度的增加略有增加。紫外-可见透射光谱分析表明, CdS:Al薄膜禁带宽度在2.42~2.46 eV 之间, 随着Al掺杂浓度的增加而略微减小。常温霍尔测试结果证明, 掺Al对CdS薄膜的电学性质影响显著, 掺Al原子浓度3.8%以上的CdS薄膜, 载流子浓度增加了3个数量级, 电阻率下降了3个数量级。掺Al后的CdS薄膜n型更强, 有利于与CdTe形成更强的内建场, 从而提高太阳电池效率。用溅射方法制备的CdS:Al薄膜的性质适合用作CdTe薄膜太阳电池的窗口层。     

Structure, surface morphology, composition and optical properties of dip coated CdS films

Cadmium sulphide is a promising semiconductor material. In the photovoltaic solar cells it can be used as a window material. In this paper the preparation of CdS film by chemical bath deposition and its solid state properties by taking XRD, SEM, XPS and optical properties has been reported. The XRD and SEM analyses of as deposited and annealed at 400°C clearly indicate the polycrystalline hexagonal phase of the film with (002) orientation. The surfaces are uniform. The XPS measurements indicate the ratio of Cd/S in both the films to be equal to 1·1 at the surface and bulk. It is observed that the thickness of the film depends upon the deposition duration and 5 min deposited films are good for device applications.     

电子束蒸发制备CdS多晶薄膜及性质研究

采用电子束蒸发工艺在普通玻璃衬底上制备了硫化镉(CdS)多晶薄膜,研究了不同衬底温度对薄膜结构、表面形貌及光透过率的影响.测试结果显示:(1)不同衬底温度下沉积的CdS薄膜均呈现了〈002〉晶向的高度优势生长,属于六方相结构.随着衬底温度的升高,还逐渐出现了〈103〉、〈004〉、〈105〉等六方晶向;(2)CdS多晶薄膜表面连续,致密性好,且晶粒大小随着衬底温度的升高而增大;(3)低温下制备CdS薄膜吸收谱有较宽的吸收边,随着衬底温度的升高,吸收曲线趋于陡直.制备样品在550nm波段后的平均透过率都超过70%,符合作为CdTe太阳电池的窗口层.     

Comparison of CdS thin films prepared by different techniques for applications in solar cells as window materials

CdS thin films as window materials for solar cells have been prepared by three procedures; chemical bath deposition, electrodeposition in an aqueous medium at 80 °C and electrodeposition in a non-aqueous medium at 170 °C. As deposited films along with those obtained after annealing in air at 400 °C for 15 min were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), scanning electron microscopy (SEM), optical absorption spectra and photoelectrochemical spectroscopy (PEC) techniques under identical experimental conditions. X-ray diffraction data indicate the formation of hexagonal CdS as the predominent phase, but the SEM studies show that their textures are widely dependent on the conditions employed. GDOES profiling indicates the incorporation of Na and Si into CdS films prepared by all three techniques. Annealing of chemical bath deposited films causes a red shift of the absorbance edge and also a shift in the maxima of the photocurrent action spectra towards the low energy side. However, this effect was comparatively negligible for the samples prepared by the other two techniques. PEC studies indicate that CdS materials grown by all three techniques are all n-type. All studies indicate that the films grown at 170 °C using non-aqueous solutions are of better crystallinity and of improved electrical properties. © 1998 Kluwer Academic Publishers     

The effect of sulfur concentration on the properties of chemical bath deposited CdS thin films

We study the structural, surface morphology and optical properties of chemical bath deposited (CBD) cadmium sulfide (CdS) thin films under the effect of variation of S/Cd ratio. CdS thin films have been successfully deposited by CBD technique with solutions containing S/Cd ionic concentration ratio of 5.0, 2.5, 1.0, 0.5 and 0.25. Single phase CdS, with a hexagonal structure, is observed for the concentration of S/Cd = 5.0, 2.5, 1.0 and 0.5 films while for the ratio of 0.25, the films exhibited a partially amorphous nature. These have been confirmed by X-ray diffraction (XRD), transmission and scanning electron microscopy (TEM and SEM) analyses. The band gaps of the films obtained by transmission and photoacoustic spectra are found to be in the range of 2.40 to 3.26 eV. The large variation of band gaps of the films with composition is discussed by employing quantum size effect phenomena. The transition levels of CdS are also studied using photoacoustic spectroscopy.     

Effect of dehydration rate on non-hydrolytic TiO2 thin film processing: Structure,optical and photocatalytic performance studies

The influence of complexing agent diethanolamine (DEA) on the rate of dehydration due to hydrolysis in titania thin films prepared by non-aqua sol–gel process was investigated. The formation of complex with titanium precursor controls the rate of hydrolysis over wide range of temperature. The rate of hydrolysis with respect to complex formation and firing temperate was studied by using thermogravimetry and differential thermal analysis (TG–DTA). The role of complexing agent in the crystallization of anatase and phase transformation to rutile was studied by X-ray diffraction (XRD). Effect of complexing agent on the optical transmittance in the visible range was monitored by ultraviolet–visible absorption spectroscopy. Photocatalytic performance of the titania films was measured using methylene blue (MB) as the model contaminant. Mechanical characteristics such as hardness and adhesion of the film were rated by using scratch tests as per ASTM standards.     

Development of low temperature approaches to device quality CdS: A modified geometry for solution growth of thin films and their characterisation

Cadmium sulphide thin films have been grown using a modified chemical bath deposition method with four innovative features: i) ethylenediamine was used as the complexing agent, enabling the use of low cadmium concentrations, ii) a rectangular bath geometry with heated glass plate walls was employed, iii) a low deposition temperature (30 °C) was used and iv) nitrogen gas was flowed over the substrate surface during growth. The latter two features eliminate the formation and adherence of gas bubbles on the substrate during growth, hence reducing pinhole formation. On inspection, films were found to be specularly reflective and homogeneous with no visible pinholes. Characterisation was performed by atomic force microscopy, grazing incidence X-ray diffraction, optical transmittance and photoluminescence spectroscopy. It was shown that films possessed a low surface roughness value of 5.2 nm, were highly crystalline, textured, had a grain size of 15 nm and a bandgap of 2.42 eV. Preliminary results from CdTe/CdS thin film photovoltaic devices demonstrate a notable efficiency of 9.8%.     

Optical studies on chemical bath deposited nanocrystalline CdS thin films

Nanocrystalline cadmium sulphide thin films were prepared by the chemical bath (CB) deposition using a mixed aqueous solution of cadmium chloride, thiourea, and ammonium chloride. The XRD patterns showed that the CdS films were of hexagonal phase with preferred (002) orientation. From ellipsometric measurements, the film thickness was found to be in order of 66 nm and the optical band gap was estimated to be 2.4 eV.     

Chemical bath deposition of CdS highly-textured, columnar films

Chemical bath deposition (CBD) is one of the most common techniques for depositing CdS films. While there have been many studies on these films, and considerable characterization of their morphologies, most of this characterization has been by either X-ray diffraction or plan-view electron microscopy. With the exception of epitaxial films deposited on single crystal substrates, there has been little characterization of the cross-sectional structure of CBD CdS films. We show how, using a CdSO₄ bath and ethylenediamine as complexant, dense, columnar films of predominantly cubic CdS can be very reproducibly obtained. The initial growth is disordered, but preferential growth perpendicular to the polar face results in highly textured growth. A similar, if somewhat less ordered, morphology is obtained from a commonly-used ammonia bath using CdCl₂ as the source of Cd. Although not explicitly recognized, chloride baths in the literature exhibited sharp X-ray diffraction peaks and this is now connected with the growth mode these baths have in common with ethylenediamine baths.     

Ammonia-free chemical bath deposition of nanocrystalline ZnS thin film buffer layer for solar cells

In this work, we prepared zinc sulfide thin films on glass substrates by ammonia-free chemical bath deposition method using thioacetamide as the sulfide source and Ethylene Diamine Tetra Acetic Acid disodium salt as the complexing agent in a solution of pH = 6.0. Thin films of ZnS with different thicknesses of 18–450 nm were prepared. The effect of film thickness and annealing temperature in atmospheric air, on optical properties, band gap energy and grain size of nanocrystals were studied. The X-ray diffraction analysis showed a cubic zinc blend structure and a diameter of about 2–5 nm for ZnS nanocrystals. The Fourier Transform Infrared spectrum of films revealed no peaks due to impurities. The as-deposited ZnS films had more than 70% transmittance in the visible region. The direct band gap of as-deposited films ranged from 3.68 to 3.78 eV and those of annealed films varied from 3.60 to 3.70 eV.     

Enhanced excitonic emission and visible luminescence of chemically synthesized ZnS:Co film phosphors

Undoped and Cobalt doped ZnS thin films have been synthesised using chemical bath deposition technique. The X-ray diffraction pattern revealed a hexagonal structure for all the films. An increase in Co/Zn molar ratio resulted in a decrease in the intensity of diffraction peak corresponding to (100) plane and increase in crystallite size of the samples. The transmittance of the samples in the visible region was found to improve on doping. The optical band gap was found to vary from 3.46 to 3.66 eV with the incorporation of cobalt ions. The scanning electron microscope images of the samples exhibit a denser and more compact morphology for the doped films as compared to the undoped film. Photoluminescence studies reveal that all samples exhibit rare excitonic or near band-edge luminescence along with emissions in the visible region. The luminescence efficiency of ZnS film is appreciably enhanced with increase in concentration of the dopant.     

CdSe thin films: morphological, optoelectronic and photoelectrochemical studies

Polycrystalline cadmium selenide (CdSe) thin films have been synthesized at room temperature by using chemical bath deposition method. The synthesized films were characterized by using X-ray diffraction (XRD), optical absorbance, electrical conductivity, scanning electron microscope, energy dispersive X-ray analysis, photoluminescence and photoelectrochemical (PEC) techniques. The film of 0.84 μm thickness, deposited on glass substrate showed uniform spherical morphology with an optical band gap of 1.99 eV. The XRD analysis confirmed presence of cubic structure. Scanning electron micrograph shows a typical spherical ball like morphology with large surface area, which is useful for absorption of large solar radiation. The conductivity measurements showed n type semiconducting nature of the film. A PEC cell device fabricated using ‘as deposited’ CdSe film as anode showed a stable conversion efficiency of 0.7 %.     

薄膜太阳电池缓冲层硫化镉的制备

采用操作简单的化学水浴法(CBD)在普通载玻片上制备了太阳能电池用缓冲层硫化镉薄膜。通过改变反应温度、溶液p H值和退火温度等实验条件,探讨了硫化镉薄膜的最佳制备工艺条件,并利用X射线衍射仪、紫外-可见-分光光度计和电化学工作站对生成的薄膜样品进行了表征。结果表明,制备均匀性好、致密、覆盖度好的硫化镉薄膜的最佳实验条件如下:反应温度为70℃,溶液p H值为10,且后续在350℃温度下进行热处理1 h。此条件下得到的硫化隔薄膜的可见光透过率较高,具有明显的光电导现象;通过计算,最优实验条件下获得薄膜的禁带宽度为2.3 5 e V,与理论值2.42 e V很接近。     

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.     

CdS annealing treatments in various atmospheres and effects on performances of CdTe/CdS solar cells

In this work, a systematic research on CdS annealing treatments under various atmospheres had been done to understand their effects on CdS/CdTe solar cells. CdS films were prepared by a standard CBD method and annealed under various atmospheres, including Ar, Ar+H₂, O₂, Ar+S and Ar+CdCl₂. Morphological, structural, optical and chemical properties were investigated using Atom force microscope (AFM), X-ray diffraction (XRD), UV–VIS spectroscopy and X-ray photoelectron spectroscopy (XPS). Annealing treatments enhanced modifications of morphology, structure and electrical properties of CdS films. AFM showed different surface morphologies and roughnesses of CdS films annealed under various atmospheres. XRD indicated the transition of CdS films from metastable cubic structure to stable hexagonal structure after annealing treatment, especially annealed in Ar+CdCl₂. From XPS analysis, Fermi levels of CdS films shifted closer to conduction band after annealing under O₂ and Ar+CdCl₂, while the levels shifted away from conduction band under Ar+H₂ and Ar+S. The relationships between those modifications by annealing treatments and effects on the performance of solar cells were discussed. Solar cell based on CdS annealed with Ar+CdCl₂ had the best performance due to the high n-doping of CdS layer introduced by annealing process.     

ZnO-CdS core-shell quantum dots sensitized solar cell: influence of crystalline and amorphous CdS structures in photovoltaic performance

ZnO nanoparticles (NPs) coated with amorphous and crystalline CdS quantum dots (QDs) were successfully synthesized through chemical bath deposition (CBD) process. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) have been utilized to characterize the samples morphology and structural properties. The conduction band of CdS QDs is much higher than the ZnO conduction band facilitates electron transfer process through cascade system. The thickness and crystallinity of the CdS QDs coated on ZnO NPs critically controls the electron diffusion length and photovoltaic performance of the solar cell. The red shift from 506 to 524 nm, increased optical absorption in the UV-visible range and electron diffusion length limited by the thickness of the amorphous/crystalline CdS QDs coated on ZnO NPs film, influences the performance of the QDs sensitized solar cell (QDSSCs) under one sun illumination intensity (AM 1.5, 100 mW/cm2). The results discuss the CBD process controlled growth of CdS QDs on ZnO NPs and its influence on the photovoltaic performance of QDSSCs.     

A new approach towards the growth of cadmium sulphide thin film by CBD method and its characterization

Cadmium sulphide thin films were deposited by the chemical bath deposition method using tartaric acid as a complexing agent and annealed at different temperature in nitrogen atmosphere and characterized. The crystallographic structure and the crystallite size were studied by the X-ray diffraction (XRD) pattern. Transmittance of the deposited film is significantly higher in the visible region. The optical band-gap of deposited film is 2.4 eV and it decreases with increase in annealing temperature. Temperature dependence of resistivity confirmed the semiconducting behaviour of the film. Scanning electron micrographs (SEM) showed the presence of grain particles of size < 1 μm. X-ray photoelectron spectroscopy (XPS) studies supported the composition of cadmium sulphide thin film determined by EMPA and also indicated the presence of carbon and oxygen as impurity in the film.