Phase transformation and quantum confinement effect in CdSe/Se multilayer thin films prepared by physical vapour deposition

CdSe/Se multilayer (ML) thin films with different thickness ratios of Se and CdSe sublayers were prepared by using a thermal evaporation method. Prepared samples were annealed at temperature 300 K. From X-ray diffraction (XRD) studies, samples prepared at room temperature showed a (100) plane of CdSe with wurtzite structure, whereas the annealed samples confirmed the cubic structure. Stress created in ML systems was calculated from XRD data and found that it increases with decreasing particle size. The energy band gap value of a CdSe/Se ML thin film is shifted to a value higher than that of the bulk CdSe (1.74 eV) semiconductor. This is due to decrease in the crystallite size smaller than the Bohr exciton diameter of CdSe (11.2 nm). Crystallite sizes (≈5 nm) were calculated from UV–VIS data with the predictions of an effective mass approximation model. The photoluminescence peak of the ML samples is split into two bands having nearest values due to the emissions from spin–orbit split-up of the excited energy state.     

Thermally induced effects on structural and electrical properties of selenium-rich Cd-Se thin films

The effect of annealing in nitrogen atmosphere on structural and electrical properties of selenium rich CdSe (SR-CdSe) thin films deposited by thermal evaporation onto glass substrates were studied. X-ray diffraction (XRD) patterns showed that the as-prepared films were amorphous, whereas the annealed films were polycrystalline. Analyzing XRD patterns reveals the coexistence of both Se and CdSe crystalline phases which exhibits a hexagonal structure. The microstructure parameters (crystallite size, microstrain and dislocation density) were calculated for annealed films.Temperature dependence (300–500 K) of d.c. conductivity was studied for as-prepared and annealed thin films. The experimental results indicate that the electrical conduction taking place through thermally activated process. At higher temperatures, electrical conduction for as-prepared film is taking place in the extended states while localized states conduction in the band tails is most likely to take place for annealed films. Regarding the lower temperature range, conduction by hopping in the localized states near the Fermi level is found to be dominant. Thus, conductivity data in this range was analyzed using Mott's variable range hopping conduction, where Mott's parameters were calculated for SR-CdSe thin films.     

TiO2/CdSe多层膜结构的制备及光电化学性能研究

采用电化学方法在导电的ITO/TiO₂ 薄膜上沉积了棕红色CdSe薄膜, 并制得TiO₂/CdSe多层膜体系,研究了多层膜的微结构和光电化学性能. 实验表明, CdSe薄膜沿着(111)方向择优生长, 多层膜结构的厚度和紫外-可见光吸收强度随着沉积层数的增加而增加. 通过测定多层膜电极的光电化学性能表明, 二层膜体系的开路电压和短路电流密度最大,光电化学性能最好.     

An approach to MgCl2 activation on CdSe thin films for solar cells

The energy demand of the world is rapidly increasing and to cater this, there is a need to explore new renewable energy resources. CdSe thin film solar cells may be promising alternative to the CdTe solar cells which are extensively studied and used in solar cell technology. The pre/post deposition chlorine based treatments (viz. CdCl₂, MgCl₂, NH₄Cl) are the important steps to enhance the performance of Cd-based thin film solar cells. Therefore, a study on MgCl₂ activation treatment to CdSe thin films for solar cell applications as absorber layer is undertaken. Different physical properties of e-beam evaporated CdSe films (thickness 550 nm) grown on glass and ITO substrates are investigated and found to be strongly dependent on the post-chlorine treatment. The films have cubic zinc-blende structure and phase transformation from cubic (111) to hexagonal (002) is achieved with the MgCl₂ treatment while the optical band gap is reduced. I-V characteristics reveal the linear relation between voltage and current as well as the surface roughness is varied with treatment and improved homogeneity. The deposition of CdSe thin films is confirmed by elemental analysis where Cd and Se were found to be rich with treatment. The investigated results suggest that CdSe thin films treated by MgCl₂ and annealed at 320 °C may be a viable alternative absorber layer to the Cd-based solar cells.     

The preparation and evaluation of graded multilayer ta-C films deposited by FCVA method

In this study, a series of graded multilayer ta-C films were investigated by varying their sublayer thickness ratios, in which each film sublayer was prepared at different substrate bias by filtered cathode vacuum arc (FCVA) method. The experimental results show that the graded multilayer film structure can effectively decrease the internal stress level of deposited ta-C film, and meanwhile the graded multilayer ta-C films still have high sp³ fractions. The applied substrate bias voltage and sublayer thickness ratio can apparently influence the microstructure characteristics and internal stress of the graded multilayer ta-C films. The graded multilayer ta-C film has larger sp³ fraction when applying a larger negative substrate bias voltage and having a thicker outer sublayer during the film deposition process. However, the internal stress in the as-deposited film also increases with larger thickness of the outer sublayer, and the optimal ratio of sublayer thicknesses is 1:1:1:1 for graded ta-C film with four sublayers.     

磁控溅射制备极紫外高反射率多层膜应力研究

为制备硼边附近6.7 nm波长的极紫外高反射率多层膜反射镜,研究了Mo_2C/B_4C,Mo/B_4C周期多层膜,重点解决薄膜应力难题。采用直流磁控溅射技术制备了膜层厚度为30 nm的Mo,Mo_2C,B_4C,单层膜,周期厚度为3.5 nm,30对的Mo_2C/B_4C,Mo/B_4C周期多层膜。利用台阶仪测试了镀膜前后基底面形,计算并比较了不同薄膜样品的应力值。结果表明Mo_2C/B_4C多层膜压应力要远小于Mo/B_4C多层膜,且成膜质量与Mo/B_4C相当。因此Mo_2C/B_4C是应用于6.7 nm反射镜较好的多层膜材料组合。     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO₂纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO₂的沉积时间及SiO₂的沉积时间一定而改变薄膜厚度时，多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明：具有纳米层状结构的Au/SiO₂多层薄膜在560 nm波长附近有明显的表面等离子共振吸收峰，吸收峰的强度随Au颗粒的浓度增加而增强，在Au颗粒浓度相同的情况下，复合薄膜 关键词： 2纳米复合薄膜')" href="#">Au/SiO₂纳米复合薄膜 多靶磁控溅射 吸收光谱 有效介质理论     

Effect of thickness on the structural,optical and electrical properties of thermally evaporated PbI2 thin films

This work describes the physical properties of lead iodide (PbI₂) thin films with different thicknesses that were deposited on ultrasonically cleaned glass substrates using a thermal evaporation technique at 5×10^-6 torr. The initial material was purified by the zone refining technique under an atmosphere of argon gas. XRD analysis of the material demonstrates that the thin films were preferably oriented along the (001) direction. The size of the crystallites was calculated from the Scherer relation and found to be in the range of ～5–10 nm, with higher values being observed for increasing film thicknesses. The optical energy band gaps were evaluated and determined to belong to direct transitions. Because the band gap increased with decreasing film thickness, a systematic blue shift was observed. The surface morphologies of PbI₂ films exhibited a clear increase in grain size with increasing film thickness. The photoluminescence and dc conductivity of the thin films are also discussed.     

Preliminary investigations on the antibacterial activity of zinc oxide nanostructures

We have fabricated electroactive multilayer thin films containing ferritin protein cages. The multilayer thin films were prepared on a solid substrate by the alternate electrostatic adsorption of (apo)ferritin and poly(N-isopropylacrylamide-co-2-carboxyisopropylacrylamide) (NIPAAm-co-CIPAAm) in pH 3.5 acetate buffer solution. The assembly process was monitored using a quartz crystal microbalance. The (apo)ferritin/poly(NIPAAm-co-CIPAAm) multilayer thin films were then cross-linked using a water-soluble carbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide. The cross-linked films were stable under a variety of conditions. The surface morphology and thickness of the multilayer thin films were characterized by atomic force microscopy, and the ferritin iron cores were observed by scanning electron microscopy to confirm the assembly mechanism. Cyclic voltammetry measurements showed different electrochemical properties for the cross-linked ferritin and apoferritin multilayer thin films, and the effect of stability of the multilayer film on its electrochemical properties was also examined. Our method for constructing multilayer films containing protein cages is expected to be useful in building more complex functional inorganic nanostructures.     

CdSe quantum dot formation induced by amorphous Se

The mechanism allowing the transition from a two-dimensional strained layer of CdSe on ZnSe to self-assembled islands induced by the use of amorphous selenium is still not fully understood. For a better understanding, atomic force microscopy and transmission electron microscopy studies were performed on CdSe films with a thickness close to that for quantum dot formation. Below this thickness, the sample surface results in undulations along the [1 1 0] crystal direction, while few quantum dots are situated in the wave valleys. Plan view transmission electron microscopy studies reveal a strong anisotropy of the islands and show that the Se desorption conditions are crucial.     

Properties of Cu2ZnSn(SxSe1−x)4 thin films prepared by one-step sulfo-selenization of alloyed metal precursors

The pentenary system, Cu₂ZnSn(S_xSe_1−x)₄ (CZTSSe), is a promising alternative for thin film solar cells. In this study, CZTSSe thin films were prepared using a two-stage process involving the thermal diffusion of sulfur (S) and selenium (Se) vapors into sputtered metallic precursors at approximately 450 °C. The effects of the sulfur content on the composition, structure, optical and electrical characteristics of the CZTSSe thin films were investigated. The films showed a kesterite structure with a predominant (112) orientation. X-ray diffraction and Raman spectroscopy confirmed the formation of a single phase CZTSSe compound. The band gap was dependent on the sulfur content and was calculated to be 1.25 eV, 1.33 eV and 1.40 eV for CZTSSe films with a S/(S + Se) ratio of 0.3, 0.5 and 0.7, respectively. All films exhibited p-type semiconductor properties.     

ZnS薄膜参数对有机/无机复合发光器件特性的影响

半导体量子点(QDs)具有发光效率高和发光波长可调等特点。采用胶体CdSe QDs作电致发光器件的有源材料,TPD(N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine)作空穴传输层,ZnS作电子传输层,研究了有机/无机复合发光器件ITO/TPD/CdSe QDs/ZnS/Ag的电致发光特性。TPD和CdSe QDs薄膜采用旋涂方法、ZnS薄膜采用磁控溅射方法沉积,器件表面平整。CdSe QDs的光致发光和电致发光谱峰位波长均位于～580 nm,属于量子点的带边激子发光。我们与以前的ITO/ZnS/CdSe QDs/ZnS/Ag发光器件结构进行了对比,发现新的器件结构的电致发光谱没有观察到QDs表面态的发光,而且新器件的发光强度是ITO/ZnS/CdSe QDs/ZnS/Ag结构的～10倍。发光效率的提高归因于碰撞激发与载流子注入两种发光机制并存的结果：一方面电子经过ZnS 层加速后,碰撞激发CdSe QDs发光;另一方面,空穴从TPD层注入CdSe QDs 与QDs中激发的电子复合发光。我们进一步研究了ZnS电子加速层厚度对发光特性的影响,选择ZnS薄膜的厚度分别是80,120 和160 nm,发现随着ZnS层厚度增大,器件启亮电压升高,EL强度增大,但是击穿电压降低。EL峰位随着ZnS厚度的减小发生明显蓝移,对上述实验现象进行了机理解释。     

Laser radiation effects on optical and structural properties of nanostructure CdSe thin film

Cadmium selenide (CdSe) thin films were deposited on a glass substrate using the thermal evaporation method at room temperature. The changes in the optical properties (optical band gap and absorption coefficient) after irradiation by TEA N₂ laser at different energies were measured in the wavelength range 190–800 nm using a spectrophotometer. It was found that the optical band gap is decreased after irradiating the thin films. The samples were characterized using X-ray diffraction (XRD), and the grain size of the CdSe thin film was calculated from XRD data, which was found to be 41.47 nm as-deposited. It was also found that grain size increases with laser exposure. The samples were characterized using a scanning electron microscope and it was found that big clusters were formed after irradiation by TEA N₂ laser.     

碲化铅/硫化锌红外多层滤光片的光谱漂移研究

采用碲化铅和硫化锌作为镀膜材料,研制了空间红外光学系统使用的红外多层带通滤光片。本文首次利用导纳轨迹图解技术,当在空间低温条件下使用时,对由碲化铅的折射率变化引起的光谱漂移机理进行了研究。根据多层膜各膜层间存在的光学厚度的补偿效应,建立了光谱漂移模型。并对设计的滤光片采用对分法计算了它在低温条件下波长的漂移量,计算结果与研制出的滤光片实测结果吻合很好。并成功地将研究结果应用于滤光片的设计,对原设计结果进行了准确的修正,使得最终研制的滤光片在低温下完全满足使用要求。     

Low temperature synthesis of cubic CdSe, HgSe and (CdHg)Se thin films and their characterization

A low temperature synthesis of CdSe, HgSe and Cd_0.5Hg_0.5Se alloy thin films in cubic modification under similar set of conditions is presented. The method is based on chemical reaction of complexed cadmium sulphate, mercuric nitrate or mixtures of both with sodium selenosulphate in aqueous ammonical medium at 5 °C. The films were characterized by using XRD, Optical absorption, Electrical measurements AAS and EDAX techniques. The films were found to be uniform, well adherent, dark red, nearly stoichiometric and polycrystalline in cubic form without trace of any hexagonallity. The growth of film was found to occurs by ion by ion by ion nucleation. CdSe, HgSe and (CdHg)Se films showed optical band gaps at 1.75 eV, 0.81 eV and 1.34 eV respectively. The electrical conductivity of (CdHg)Se alloy was found to be of the order of 10⁻² (Θcm)⁻¹. The rate of increase of conductivity with temperature was found to reduce with the inclusion of mercury. Thermoelectric study indicated the presence of n-type conduction mechanism for all the films. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

The relationship between refractive index-energy gap and the film thickness effect on the characteristic parameters of CdSe thin films

CdSe thin films were deposited on glass substrates using Successive Ionic Layer Adsorption and Reaction (SILAR) method at room temperature and ambient pressure. The relationship between refractive index and energy bandgap was investigated. The film thickness effect on the structural, morphological, optical and electrical properties of CdSe thin films was investigated. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that all the films exhibit polycrystalline nature with hexagonal structure and are covered well with glass substrates. The crystalline and surface properties of the films improved with increasing film thickness. The optical absorption studies revealed that the films are found to be a direct allowed transition. The energy bandgap values were changed from 1.93 to 1.87 eV depending on the film thickness. The electron effective mass (m_e^?/m_o), refractive index (n), optical static and high frequency dielectric constant (ε_o, ε_∞) values were calculated by using the energy bandgap values as a function of the film thickness. The resistivity of the films changed between 10⁶ and 10² Ω-cm with increasing film thickness at room temperature.     

Effect of the amorphous thin layer on the surface growth of amorphous/crystalline binary multilayer films

The effect of the amorphous thin layer on the surface growth of amorphous/crystalline binary multilayer films has been studied by using a continuum model. It is shown that both the surface roughness and the growth exponent of amorphous/crystalline binary multilayer films decrease with increasing thickness ratio between amorphous and crystalline layers. Our simulations have also revealed, in contrast to the monotonous rise in surface roughness observed in single-layer films grown on flat substrates, the surface growth of a multilayer film consists of two processes: interface smoothing and roughening, namely the film roughness decreases during the growth of amorphous thin layers but increases monotonously during the growth of crystalline thin layers. The observed interface smoothing and roughening can be obviously influenced by the change in the thickness ratio between amorphous and crystalline layers. The rise in thickness ratio between amorphous and crystalline layers enhances the interface smoothing effect but lowers the interface roughening effect and consequently shows a marked smoothing effect on the surface roughness.     

Determination of Thickness and Optical Constants of ZnO Thin Films Prepared by Filtered Cathode Vacuum Arc Deposition

ZnO thin films are prepared on glass substrates by filtered cathode vacuum arc （FCVA） deposition technique. A new method is demonstrated to extract the refractive index, thickness and optical band gap of ZnO thin films from the transmission spectrum alone. The refractive index is calculated from the extremes of the interference fingers. The transmission spectrum is divided into two terms, non-interference term and interference effect term. The thickness of thin films is calculated by simulating the interference term, and the non-interference term is used to calculate optical band gap with the gained thickness. The results are compared with measurements by using an ellipsometry and a scanning electron microscope.     

A correlation for crystallite size of undoped ZnO thin film with the band gap energy – precursor molarity – substrate temperature

Transparent conducting undoped zinc oxide thin films were deposited on glass substrate by ultrasonic spray and spray pyrolysis techniques. The thin films were deposited at different substrate temperatures ranging between 300 and 450 °C with various precursor molarities. The correlation between the structural and optical properties suggests that the crystallites sizes of the films are predominantly influenced by the band gap energy of the thin films. The data of the correlation is suspected of involving some experimental measurement errors and therefore discarded in the development of the present correlation. The coefficient of correction is equal to 0.01, indicating high quality representation of data based on Eq. (1). The correlation also indicates that the crystallites sizes of the films are predominantly influenced by the band gap energy and the precursor molarity of the thin films. The model proposed of undoped ZnO thin film with substrate temperature was investigated.     

非晶态Se薄膜的自发晶化研究

利用真空热蒸镀的方法制备了非晶Se薄膜,测试了稳定的非晶Se薄膜,不稳定的非晶Se薄膜和初始自发晶化的非晶Se薄膜的透射率光谱和拉曼光谱,对透射率光谱曲线进行了拟合,计算了薄膜的厚度和折射率随波长的变化关系。在自我晶化过程中,Se薄膜折射率逐渐增大;随波长增大,折射率则减小,初始自发晶体的Se薄膜中,出现标志Se8环和链的结构,不完整的环和链结构在自发晶化过程中得到了增强。