CdS薄膜的化学沉积法制备及其特性的研究

用化学沉积方法在沉积温度为90 ℃下制备了CdS薄膜。研究了直接退火处理和涂敷CdCl₂甲醇饱和溶液后退火处理对CdS薄膜的影响。利用X射线衍射、扫描电子显微镜对薄膜的晶体结构、表面形貌进行了研究,发现没有任何处理的CdS薄膜没有明显的晶型;直接退火处理促进了CdS立方相的结晶,晶粒没有增大且生长出许多细小的晶粒;涂敷CdCl₂甲醇饱和溶液后退火处理不仅极大地促进了CdS六角相的结晶,而且晶粒增粗增大,表面更加光滑。用吸收光谱研究了薄膜的光学特性,发现退火使薄膜的禁带宽度变窄,涂敷CdCl₂甲醇溶液后退火处理使吸收边变陡和带尾变小。表明涂敷CdCl₂甲醇溶液退火处理明显改善CdS薄膜的结晶质量和光学性质。     

化学水浴法和磁控溅射法制备硫化镉薄膜的性能研究

以氯化铵、氯化镉、氢氧化钾和硫脲为反应物采用化学水浴法制备了硫化镉薄膜,为了作对比研究,采用射频磁控溅射以硫化镉为靶材,氩气为溅射气体,制备了硫化镉薄膜。采用X射线衍射、扫描电子显微镜和紫外-可见光光谱仪分别表征了硫化镉薄膜的结构、形貌和光学吸收特性。结果表明,采用以上两种方法制备的硫化镉均具有(002)择优取向,溅射法制备的硫化镉薄膜较致密,薄膜表面较光滑,平均晶粒尺寸在20～30nm;水浴法制备的硫化镉薄膜颗粒尺寸较小,缺陷较多。除了在短波段溅射所得硫化镉薄膜的透过率略差于水浴法所得硫化镉薄膜之外,溅射法制备的硫化镉薄膜的性能整体上优于水浴法制备的薄膜。两种方法制备的硫化镉薄膜的能隙在2.3～2.5eV。     

UV-illuminated chemical bath deposition of CdS buffer layer for CIGSSe solar cells

In this paper, we compare the performance of Cu(In,Ga)(S,Se)₂ (CIGSSe) thin film solar cells with a CdS buffer layer grown by chemical bath deposition (CBD) with UV irradiation of 365 nm or 254 nm at an output power of 8 W. The effects of UV light irradiation on the CBD-CdS thin film deposition mechanism were investigated through chemical and electro-optical studies. UV light irradiation during the solution process promotes the hydrolysis of thiourea, thereby inhibiting the formation of the intermediate products being developed on the reaction pathways and decreasing the solution pH. Therefore, the efficiency of the CdS/CIGSSe solar cells was improved because of the increased elemental ratio of S/(S + O) in the CdS thin film. This very simple and effective approach can be used to control the S/O ratio of the CdS thin film fabricated by the CBD process without artificially controlling the process temperature, solution pH or concentration.     

Structural, optical and photoelectrochemical characterization of CdS nanowire synthesized by chemical bath deposition and wet chemical etching

Nanocrystalline thin films of CdS have been grown onto flexible plastic and titanium substrates by a simple and environmentally benign chemical bath deposition (CBD) method at room temperature. The films consist of clusters of CdS nanoparticles. The clusters of CdS nanoparticles in the films were successfully converted into nanowire (NW) networks using chemical etching process. The possible mechanism of the etching phenomenon is discussed. These films were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-vis spectrophotometry techniques, respectively. Photoelectrochemical (PEC) investigations were carried out using cell configuration as n-CdS/(1 M NaOH + 1 M Na₂S + 1 M S)/C. The film of nanowires was found to be hexagonal in structure with the preferential orientation along the (0 0 2) plane. The nanowires have widths in the range of 50-150 nm and have lengths of the order of a few micrometers. Optical studies reveal that the CdS nanowires have value of band gap 2.48 eV, whereas it is 2.58 eV for nanoparticles of CdS. Finally, we report on the ideality of junction improvement of PEC cells when CdS nanoparticles photoelectrode converted into nanowires photoelectrode.     

Improved growth of solution‐deposited thin films on polycrystalline Cu(In,Ga)Se2

CdS and Zn(O,S) grown by chemical bath deposition (CBD) are well established buffer materials for Cu(In,Ga)Se₂ (CIGS) solar cells. As recently reported, a non‐contiguous coverage of CBD buffers on CIGS grains with {112} surfaces can be detected, which was explained in terms of low surface energies of the {112} facets, leading to deteriorated wetting of the chemical solution on the CIGS surface. In the present contribution, we report on the effect of air annealing of CIGS thin films prior to the CBD of CdS and Zn(O,S) layers. In contrast to the growth on the as‐grown CIGS layers, these buffer lay‐ ers grow densely on the annealed CIGS layer, even on grains with {112} surfaces. We explain the different growth behavior by increased surface energies of CIGS grains due to the annealing step, i.e., due to oxidation of the CIGS surface. Reference solar cells were processed and completed by i‐ZnO/ZnO:Al layers for CdS and by (Zn,Mg)O/ZnO:Al for Zn(O,S) buffers. For solar cells with both, CdS and Zn(O,S) buffers, air‐annealed CIGS films with improved buffer coverage resulted in higher power‐conversion efficiencies, as compared with the devices containing as‐grown CIGS layers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Modifying Quantum Well States of Pb Thin Films via Interface Engineering

We demonstrate the importance of interface modification on improving electron confinement by preparing Pb quantum islands on Si（111） substrates with two different surface reconstructions, i.e., Si（111）-7 ×7 and Si（111）- Root3×Root3-Pb （hereafter, 7 ×7 and R3）. Characterization with scanning tunneling microscopy/spectroscopy shows that growing Pb films directly on a 7 × 7 surface will generate many interface defects, which makes the lifetime of quantum well states （QWSs） strongly dependent on surface locations. On the other hand, QWSs in Pb films on an R3 surface are well defined with small variations in linewidth on different surface locations and are much sharper than those on the 7 × 7 surface. We show that the enhancement in quantum confinement is primarily due to the reduced electron-defect scattering at the interface.     

AFM, XPS and RBS studies of the growth process of CdS thin films on ITO/glass substrates deposited using an ammonia-free chemical process

This paper deals with a detailed study of the growth stages of CdS thin films on ITO/glass substrates by chemical bath deposition (CBD). The chemical and morphological characterization was done through X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS), and atomic force microscopy (AFM) techniques. On the other hand, optical transmission and X-ray diffraction (XRD) measurements were performed in order to study the optical and structural properties of the films. The time, the chemistry, and morphology of the different stages that form the growth process by CBD were identified through these results. Furthermore, clear evidence was obtained of the formation of Cd(OH)₂ as the first chemical species adhered to the substrate surface which forms the first nucleation centers for a good CdS formation and growth. On the other hand, the ITO coating caused growth stages to occur earlier than in just glass substrates, with which we can obtain a determined thickness in a shorter deposition time. We were able to prove that CBD is a good technique for the manufacture of thin films of semiconductor materials, since the CdS film does not have any impurities. Completely formed films were transparent, uniform, with good adherence to the substrate, of a polycrystalline nature with a hexagonal structure. These results indicate that films obtained by CBD are good candidates to be applied in different optoelectronic devices.     

Photoluminescence studies on nanostructured cadmium sulfide thin films prepared by chemical bath deposition method and annealed at different temperatures

Nanostructured cadmium sulfide (CdS) thin films have been prepared by chemical bath deposition (CBD) method and after post deposition annealing of the thin films at different temperatures, photoluminescence (PL) property has been studied. The effects of various photoexcitation wavelengths on the PL behaviour of different annealed films of CdS were studied by recording the PL spectra. The intensity of PL, the profile of the PL spectra and the effects of photoexcitation wavelength depend drastically on the temperature of the post deposition annealing of the thin films. The XRD patterns of the films show the presence of both the hexagonal and cubic phases (mixed phases). The emission peak arises from the surface defects of the CdS nanocrystalline thin films. Significant modification in the surface morphology of the CdS films upon annealing has been observed from the FESEM images. The morphology of the thin films is expected to influence the PL behaviour of the CdS thin films. The quantum size effect and size dependant PL have been observed.     

Investigation of CdS and CdTe thin films and influence of CdCl2 on CdTe/CdS structure

CdTe/CdS heterojunction solar cell structure has been fabricated using simple, easy and low-cost methods. To fabricate this structure, CdS and CdTe thin films are deposited onto FTO-coated conducting glass substrates by chemical bath deposition (CBD) and electrodeposition method, respectively. The optimized growth conditions are chosen for both CdS and CdTe films by investigating the optical, structural and morphological properties of both the as-deposited and annealed films. Optical measurement showed that CdS films have higher transmittance and lower absorbance, and CdTe films have lower transmittance and higher absorbance in the near infrared region. The band gap of CdS films is estimated to lie in the range 2.29–2.41 eV and that of CdTe films is in the range 1.53–1.55 eV. X-ray diffraction (XRD) study reveals that CdS and CdTe films are polycrystalline with preferential orientation of (1 1 1) plane. Scanning electron microscopy (SEM) study reveals that both films are smooth, void-free and uniformly distributed over the surface of the substrate. Fabricated CdTe/CdS structure showed the anticipated rectifying behaviour, and the rectifying behaviour is observed to improve due to CdCl₂ treatment.     

ZnS overlayer on in situ chemical bath deposited CdS quantum dot-assembled TiO2 films for quantum dot-sensitized solar cells

ZnS overlayers were deposited on the CdS quantum dot (QD)-assembled TiO₂ films, where the CdS QDs were grown on the TiO₂ by repeated cycles of the in situ chemical bath deposition (CBD). With increasing the CdS CBD cycles, the CdS QD-assembled TiO₂ films were transformed from the TiO₂ film partially covered by small CdS QDs (Type I) to that fully covered by large CdS QDs (Type II). The ZnS overlayers significantly improved the overall energy conversion efficiency of both Types I and II. The ZnS overlayers can act as the intermediate layer and energy barrier at the interfaces. However, the dominant effects of the ZnS overlayers were different for the Types I and II. For Type I, ZnS overlayer dominantly acted as the intermediate layer between the exposed TiO₂ surface and the electrolyte, leading to the suppressed recombination rate for the TiO₂/electrolyte and the significantly enhanced charge-collection efficiency. On the contrary, for Type II, it dominantly acted as the efficient energy barrier at the interface between the CdS QDs and the electrolyte, leading to the hindered recombination rate from the large CdS QDs to the electrolyte and thus enhanced electron injection efficiency.     

Photoluminescence in gradient recrystallization grown CdTe

Photoluminescence properties of Gradient Recrystallization Grown (GREG) polycrystalline CdTe films are reported and compared to other thin film semiconductors as e.g. Chemical Bath Deposited (CBD) CdS, and Spray Pyrolyzed (SP) CdTe films. In spite of similarities, it is suggested not to interpret the results found for GREG CdTe and CBD CdS in terms of recombination at defect sites in intergranular regions, as was recently proposed for spray pyrolyzed CdTe films, but of recombination due to defect sites located in single microcrystallites.     

Optimisation of the CBD CdS deposition parameters for ZnO/CdS/CuGaSe2/Mo solar cells

We present an optimisation of our recipe for the CdS chemical bath deposition process as applied to solar cells based on polycrystalline CuGaSe₂ (CGSe) absorber layers prepared in two stages by physical vapour deposition. We investigate the influence of the ammonia (NH₃) and the thiourea (H₂NCSNH₂) concentration, both being constituents of the chemical bath deposition (CBD) solution, at a deposition temperature of 80 °C on the microstructural and optical properties of CdS layers and on ZnO/CdS/CuGaSe₂/Mo device parameters. The composition of the CdS layers and their thickness were determined using X-ray Fluorescence Analysis. Transmission and reflection measurements performed at 300 K were used for the calculation of absorption and optical band gap energy (E_g). The E_g values of the films varied from 2.41 to 2.46 eV depending on deposition conditions. Cubic phase of the as-grown layers was identified by X-ray diffraction analysis. An improvement in the investigated solar cells efficiency was achieved when the ammonia concentration was increased and the thiourea concentration was reduced, compared to the previously used standard HMI recipe. The influence of the CBD CdS preparation recipe on the ZnO/CdS/CuGaSe₂/Mo electrical and photoelectrical properties is discussed.     

具有高阻抗本征SnO2过渡层的CdS/CdTe多晶薄膜太阳电池

采用超声喷雾热解法制备了具有高阻抗的本征SnO₂透明导电膜，将其运用在CdS层减薄了的CdS/CdTe多晶薄膜太阳电池中，对减薄后的CdS薄膜进行了XRD,AFM图谱分析，并对电池进行了光、暗I-V，光谱响应和C-V测试.结果表明，在高阻膜上沉积的减薄CdS薄膜(111)取向更明显，但易形成微孔.引入高阻层后，能消除CdS微孔形成的微小漏电通道，有效保护p-n结，改善了电池的并联电阻、填充因子和短波响应，使载流子浓度增加，暗饱和电流密度减小，从而电池性能得到改善，电池转换效率增加了14.4%. 关键词： CdTe电池 过渡层 效率     

Spectroscopic analysis of CIGS2/CdS thin film solar cell heterojunctions on stainless steel foil

This paper presents a spectroscopic analysis of the interface between a CuIn_1−xGa_xS₂ (CIGS2) absorber and a CdS buffer layer on stainless steel foil by Auger electron spectroscopy (AES), inverse photoemission spectroscopy (IPES) and photoelectron spectroscopy (PES) such as X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). By combining these spectroscopic techniques, detailed information about the electronic and chemical properties of the CIGS2 surface and the CdS/CIGS2 interface can be obtained. The gallium concentration in CIGS2 films was found to increase continuously towards the Mo back contact. XPS analysis showed the presence of KCO₃ on the surface of CdS, deposited on etched and un-oxidized samples indicating diffusion of potassium. No potassium was observed on oxidized as well as samples having thicker CdS (50 nm) indicating the effectiveness of oxidation and chemical bath deposition (CBD) process in cleaning the sample surface effectively. In addition, investigation of the electronic level alignment at the interface has been carried out by combining PES and IPES. Conduction band offset of −0.45 (±0.15) eV and a valence band offset of −1.06 (±0.15) eV were measured. These unfavorable conditions limit efficiency of CIGS2 thin film solar cells.     

TEM and XPS studies on CdS/CIGS interfaces

Copper indium gallium selenide (CIGS) was deposited by metallic precursors sputtering and subsequently submitted to a selenization process. The upper CdS layers were deposited by chemical bath deposition (CBD) technique. The CdS/CIGS interfaces were investigated by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). As checked by XPS analysis, the CIGS surface exhibited a hydroxide-terminated CdSe layer when treated with Cd Partial Electrolyte solution (Cd PE). Its thickness was roughly estimated to several nanometers. A 100 nm thick CdS layer was deposited onto CIGS surface. The TEM images revealed a clear and sharp interface between CdS and CIGS. XPS analysis showed a CIGS surface covered by a pinhole free and homogeneous CdS layer. XPS depth profile measurement of the CdS/CIGS interface did not evidence elemental inter-diffusion between the CIGS and CdS layers, in very good agreement with TEM observations.     

Effects of annealing in nitrogen atmosphere and HCl-etching on the photoluminescence spectra of spray-deposited CdS:In thin films

The aim of this work is to find the effect of processing on the photoluminescence (PL) of spray-deposited CdS:In thin films. So the PL spectra of the as-deposited, annealed and HCl-etched CdS:In thin films prepared by the spray pyrolysis (SP) technique were recorded at T = 23 K. The yellow and red bands were observed in the spectrum of the as-deposited film beside bands with weaker intensity in the infrared region. The PL signal was weakened by annealing in nitrogen atmosphere at T = 400 °C and HCl-etching. A deconvolution peak fit was established to find the effects of these treatments on the different bands. The spectrum of the as-deposited film was deconvoluted to 12 peaks, which were reduced to 6 peaks after both treatments. It was found that both treatments have approximately the same effects on the PL spectra; that is they removed most of the peaks and shoulders in the red and infrared regions and attenuated most of the peaks in the yellow region. Some peaks were blue-shifted after annealing which was explained by the growth of nanocrystallites due to the thermal stress that results from the different expansion coefficients of the film and the substrate. These changes were accompanied by a phase change from the mixed (cubic and hexagonal) phase to the hexagonal phase as shown in the X-ray diffractograms.     

Observations on the influence of pH control on the properties of chemically deposited CdS films in an ammonia-free system

In this work we report on the properties of chemically deposited CdS thin films in an ammonia-free cadmium-sodium citrate system. We studied the influence on the properties of the films of the pH control of the reaction solution. For this, we deposited two types of CdS films employing two different types of reaction solutions. The only difference between both reaction solutions was the addition of a pH buffer in one of them in order to control its pH throughout the deposition process. Several sets of CdS films were deposited from growth solutions with different contents of Cd to determine also the influence of this parameter on the properties of the films. The CdS films were studied by X-ray diffraction, optical transmission and reflection spectroscopy and scanning electron microscopy measurements. We found that the properties of the films depend both on the amount of Cd in the growth solutions and on their pH control. The increase in Cd in the reaction solution yields to films with shorter lattice constant and then higher energy band gap. On the other hand, the pH control of the reaction produces higher deposition rate, larger final thickness and higher energy band gaps in the CdS films.     

Adsorption of 7-ethynyl-2,4,9-trithia-tricyclo[3.3.1.1]decane on ultra-thin CdS films

The adsorption mechanism for the new compound, 7-ethynyl-2,4,9-trithia-tricyclo[3.3.1.1^3,7]decane (7ETTD), on ultra-thin films (∼3 nm) of CdS is investigated. Multiple reflection absorption IR spectroscopy, in conjunction with inelastic electron tunneling spectroscopy, indicates that this compound forms a self-assembled monolayer adsorbed on the CdS surface via each molecule’s trithia-adamantane anchor. Conductance-voltage data are recorded for tunnel junctions of the type Al/CdS/7ETTD/Pb over a temperature range of 4 K to room temperature and they indicate that the presence of the 7ETTD layer on the CdS dramatically modifies the conductance-voltage behavior of the junctions. These measurements show that different conduction mechanisms, including tunneling and possibly hopping, are responsible for charge transfer through the junctions depending on current, temperature, and voltage. WKB fits to the data are used to determine barrier parameters (height and width) for Al/CdS/Pb junctions with and without adsorbed 7ETTD layers on the CdS. Analysis of the fits shows that tunneling occurs at low bias (less than ∼0.2 V) but, at higher bias voltages, modification of the barrier parameters alone is insufficient to account for the observed conductance changes. A frontier orbital model is invoked which does offer a plausible explanation for these conductance changes. The model assumes bias-dependent coupling between HOMO and LUMO states of the adsorbed 7ETTD and the surface states on the CdS. The present work suggests that, because of the marked effect on the conductance of CdS ultra-thin films, 7ETTD and other similar compounds may be candidates for use in molecular electronic device fabrication.     

Photoelectric properties of pure and aluminium doped CdS films

Photoelectric properties of pure and Al doped vacuum deposited CdS films have been studied to explore the possibility of their application in photoactivated liquid crystal light valves. The effect of heat treatment in oxygen atmosphere, rate of deposition and the extent of Al doping, etc. on the resistivity, photo-response spectral characteristics, rise and decay time of photo-current, etc. have been investigated. It has been found that in contrast to pure CdS films, the properties of Al-doped films significantly depend on both the rate of deposition and the extent of Al doping. The dark resistivity in all cases was found to increase with heat treatment in oxygen. Unlike pure CdS films, Al doped films show photo-conductivity which is enhanced by heat treatment. Al doped films deposited at higher rates show better photo response even at lower light levels. At various light levels the rise and decay time of Al-doped films were found to be fairly constant and lower than that for pure CdS films. All these properties have been explained in terms of the presence of trapping levels due to doping. These trapping levels are also indicated by TSC, optical absorption and EPR studies.     

A novel preparation method and investigation of sprayed CdS films

The main reason for the low photovoltaic efficiency of Cu₂S/CdS cells, in which the CdS film is deposited by solution spraying, is the very small average dimensions of the crystalline grains. The difficulty in depositing films with transverse dimensions of crystalline grains larger than 1 m is due to the fast decrease of substrate temperature during the spraying deposition of the CdS film. We have since arranged an experimental set-up able to maintain the surface temperature of the substrate constant. In this way it is possible to control the parameters which affect the deposition and to obtain a high degree of reproducibility of morphological properties. Average grain sizes of more than 1 m are obtained. We have investigated the crystalline grain sizes and the film thickness as a function of the deposition temperature and the spraying rate.Work supported by Ministero Pubblica Istruzione and Centro Regionale Ricerche Nucleari e Struttura della materia