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.     

CdS纳米薄膜的水浴法制备与表征

CdS是一种直接能隙半导体，其带隙约为2．42eV，是一种良好的太阳能电池窗口层材料和过渡层材料。化学水浴法沉积CdS薄膜具有工艺简单，成本低廉，成膜均匀、致密以及可大面积生产等优点。本文通过对化学水浴法沉积CdS薄膜的研究，阐述了CdS膜的生成和生长过程及其机理，并不断优化此方法中的各种工艺参数，得到了适合做铜铟镓硒薄膜太阳能电池过渡层的CdS薄膜，并对该薄膜的形貌、结构和性能进行了分析。     

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.     

Optical properties of chemical bath deposited CdS thin films

CdS thin films have been prepared by chemical bath deposition. As-deposited films are cubic and show a sulfur deficiency. From the transmittance and reflectance data analysis direct band gaps (E_g) ranging from 2.180 to 2.448 eV have been obtained. Air and vacuum annealed samples show a decrease in the band gap. The refractive index (n) lies in the range 1.61–2.34. A dependence of band gap on composition has been observed and the possible reasons are discussed.     

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.     

CIGS薄膜太阳能电池缓冲层CdS薄膜的制备研究

目前CdS材料的制备方法有很多种,但是最常用的是化学水浴法。本文研究了浓度、反应溶液pH值、温度、沉积时间对CdS缓冲层薄膜的影响,对CIGS薄膜太阳能电池缓冲层CdS薄膜的制备方法进行了论述。     

Modification of the dark and photoconductivity and the optical transmittance of solution-grown CdS thin films

Very interesting behaviour is shown by chemically deposited CdS thin films for optoelectronic applications after air and vacuum (10^?5 Torr) annealing. Vacuum annealing of samples at about 100°C caused the dark conductivity to improve by five orders of magnitude. The dark and photoconductivity of air-annealed (at around 200°C) samples increased by seven and two orders of magnitude respectively. Air-annealed (at 350°C for about 2 min) samples exhibited a very quick photoresponse (<2 s for two decades of photocurrent decay) with σ_p/σ_d ≈ 10⁵ for a bias of 10 V, which may be exploited for photodetector applications. Air or vacuum annealing of samples for a minimum of 10–15 min caused the optical transmittance above the band edge to increase by 10%–15% and annealing the sample at 200°C caused the absorption edge to shift towards the longer-wavelength region compared with the as-prepared and 100 and 350°C annealed films.     

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.     

太阳电池中CdS薄膜的制备及其性能的研究

分别采用化学池沉积(CBD)和真空蒸发法,在三种衬底(玻片、ITO玻片、SnO2玻片)上沉积CdS薄膜,并利用扫描电镜(SEM)、透射光谱、X射线衍射(XRD)等方法对沉积膜进行了测试分析,同时阐述了两种不同方法下CdS膜的生长沉积机制。     

Chemical bath deposition of nanocrystalline ZnS thin films: Influence of pH on the reaction solution

Zinc sulfide (ZnS) thin films were deposited onto glass substrates using chemical bath deposition technique (CBD). The deposition were carried out in a bath solution with pH ranged from 9 to 11. X-ray diffraction (XRD) and atomic force microscopy (AFM) were used to characterize the films structure and morphology respectively. The amorphous structure of as-deposited films is converted to a nanocrystalline one after a thermal annealing at 550 °C. The deposited ZnS films exhibit a high optical transmission in the UV–visible range (≥80%). They have a direct band gap. Using a solution with pH equal to 10 yields to films with larger optical band gap, smoother surface and lower electrical conductivity.     

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.     

溶液PH值对CdS薄膜结构特性的影响

采用化学水浴沉积(CBD)工艺在玻璃衬底上制 备CdS薄膜,研究溶液PH值对CdS 薄膜结构特性的影响。薄膜的厚度、组份、晶相结构和表观形貌分别由台阶仪、X射线荧光 光谱(XRF)、X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)来表征。溶液的 PH值为11.26、 11.37和11.48时,CdS薄膜的晶相以六方相为主,薄膜的厚度先增大后减小; PH值为11.62、11.66时,薄膜的晶相以立方相为主,薄 膜的厚度进一步减小。同时,随着溶液PH值 增大,CdS薄膜的晶格常数也逐渐增大。两种晶相的CdS薄膜缓冲层与CIGS薄膜分别构成异 质 对形成异质结时的晶格失配分别为32.297%和1.419%,界面态密度分别为2.792×10¹⁴和8.507×10¹²,因此高效CIGS薄 膜太阳电池更需要立方相的CdS薄膜。     

ZnCdS films for solar cell and photodetector applications deposited by In Situ chemical doping of CdS with Zn

ZnCdS films were formed by in situ chemical doping of CdS with Zn in a chemical bath. The X-ray diffraction (XRD) patterns of CdS films after Zn doping showed a more disordered nature, consisting of reflections from Zn_0.049Cd_0.951S (JCPDS 40-834) as well as CdS greenockite (hexagonal, JCPDS 41-1049) and hawleyite (cubic, JCPDS 10-0454) phases. A comparison of the optical transmittance spectra for undoped and Zn-doped films showed that the cut-off wavelength was modified after Zn doping, indicating the presence of impurity states in the band gap. Zn-doped films showed an increase in dark conductivity after annealing at about 200°C. These films exhibit promising characteristics for application in solar cell and photodetector structures.     

CdS薄膜的真空热蒸发制备及在CIGS薄膜太阳电池中的应用

采用真空热蒸发(VTE)的方法制备了CdS多晶薄膜,研究了不同衬底温度对其微观结构与光电性能的影响。结果显示,不同衬底温度下制备的CdS薄膜均属于六方相多晶结构且具有(002)择优取向;随着衬底温度的升高,(002)特征衍射峰强度增加,半高宽变小,相应薄膜结晶度增大;由CdS薄膜的透射光谱可知,在500~1 000nm波段平均透过率均超过80%,光学带隙随着衬底温度的升高而增大(2.44~2.56eV),表明真空热蒸发方法制备的CdS薄膜可以作为CIGS薄膜太阳电池的缓冲层。将真空热蒸发法制备CdS薄膜与磁控溅射法制备CIGS薄膜太阳电池相结合,在同一真空室内得到了CIGS薄膜太阳电池器件,为CIGS薄膜太阳电池的工业化推广提供了新途径。     

CdS/TiO_2纳米棒阵列复合电极制备及性能研究

染料敏化太阳电池以其良好的电池性能、简单的制作工艺、廉价的制作成本等优点越来越受到人们的关注。尝试用水热合成法在透明导电玻璃FTO(SnO2∶F)衬底上一步制备出高度有序的TiO2单晶纳米棒阵列,使用扫描电子显微镜SEM及X射线衍射仪(XRD)等对其进行表征分析。用制备的样品作为光阳极封装电池并对其进行电池性能的测试。用化学浴沉积(CBD)方法对制备的样品进行CdS表面修饰,通过测量其紫外-可见吸收光谱及明暗场的电流-电压特性曲线等考察电池性能随硫化镉修饰次数的变化规律。     

Influence of the indium nominal concentration in the formation of CuInS2 films grown by CBD

Copper indium disulfide (CuInS₂) thin films were prepared by chemical bath deposition in an acid medium on glass substrates. CuInS₂ films were grown using CuSO₄, InCl₃ and C₂H₅NS as copper, indium and sulfur sources, respectively. The CuSO₄ and C₂H₅NS concentrations remained constant, while the InCl₃ concentration was varied from 0.002 M to 0.025 M. The structural analysis show that initially the films have a mixture of CuS and CuInS₂ phases, when the indium nominal concentration increases the formation of CuInS₂ ternary compound was promoted until the final formation of a CuInS₂ film. The morphological study shows that the surface of CuInS₂ films is constituted by nanotubes. The structural and compositional analysis show that for 0.025 M InCl₃ concentration CuInS₂ films were obtained.     

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.     

Hot plasma chemical vapor deposition of GaN on GaAs(100) substrate

GaN films have been deposited on GaAs(lOO) substrates by a novel growth technique, hot plasma chemical vapor deposition. A radio frequency N plasma source with high power, up to 5 kW, provides an abundance of nitrogen atoms during growth. In addition, strong ultraviolet emissions from the hot plasma irradiate onto the substrate and promote the dissociation of triethylgallium, this results in growth of GaN at very low temperature (even at room temperature). In this paper, we describe the characteristics of hot nitrogen plasma and present the results of the low temperature growth of GaN. In addition, we have investigated the effects of the nitridation of GaAs substrates. Reflection high energy electron diffraction indicates the formation of a surface cubic nitrided layer on the pretreated GaAs. The GaN films grown on fully nitrided GaAs(l00) substrates are of dominantly cubic structures.     

衬底偏压对HWCVD制备纳米晶硅薄膜结晶性的影响

通过在热丝化学气相沉积(HWCVD)制备纳米晶硅 薄膜过程中施加衬底偏压,研 究衬底偏压对HWCVD制备纳米晶硅薄膜结晶性能的影响。利用拉曼(Raman)光谱,X射线 衍射(XRD)和扫描电子显微镜(SEM)对所制备的纳米晶硅薄膜的结构性能进行分析。结果表 明,与未施加衬底偏压的薄膜相比,当衬底偏压为－300V时,薄膜 的晶化率由42.2%升高至 46.2%;当衬底偏压升高至－600V时,晶化率 又降至40.6%;未施加衬底偏压与施加－300V 偏压的纳米晶硅薄膜表面由长约200nm、宽约100nm的晶粒构成,－600V衬底偏压的薄 膜表面晶粒尺寸明显变小,并且出现大量非常细小的晶粒。分析产生上述现象的原因,主要 与 高温热丝发射电子、电子在电场作用下加速运动并与反应气体、基团碰撞发生能量传递有关 。