Vibrational modes in ZnAl2S4 and CdIn2S4 crystals

Infrared reflectivity spectra and Raman scattering of the ZnAl₂S₄ and CdIn₂S₄ crystals have been investigated. Reflectivity spectra contours were calculated and phonon parameters and dielectric constants were determined. Effective charges for the Zn, Cd, In and S ions of these materials were determined.     

Growth mechanism and characterisation of chemically grown Sb doped Bi2Se3 thin films

The synthesis of combinatorial Bi_2−xSb_xSe₃ thin films by arrested precipitation technique (APT) using triethanolamine-bismuth, triethanolamine-antimony and sodium selenosulphite as sources of Bi³⁺, Sb³⁺ and Se²⁻, respectively is investigated on commercial glass substrates. The growth mechanism of film formation, composition and surface morphology of the as deposited films were studied as a function of preparative parameters and bath composition. The films were monophasic, polycrystalline and covered the surface of the substrate completely. Energy dispersive X-ray analysis gave coherent elemental composition indicating single phase BiSbSe₃ was made. The good results obtained for Bi_2−xSb_xSe₃ thin films revealed that arrested precipitation technique is best suited for the deposition of large area thin films on conducting/nonconducting substrates to produce materials for device applications.     

Photoelectrochemical properties of electrochemically deposited CdIn2S4 thin films

Thin films of CdIn₂S₄ have been deposited on to stainless steel and fluorine-doped tin oxide (FTO)-coated glass substrates from aqueous acidic bath using an electrodeposition technique. Ethylene diamine tetra-acetic acid (EDTA) disodium salt is used as complexing agent to obtain good-quality deposits by controlling the rate of the reaction. The different preparative parameters like concentration of bath, deposition time, bath temperature, pH of the bath have been optimized by the photoelectrochemical (PEC) technique in order to get good-quality photosensitive material. Different techniques have been used to characterize CdIn₂S₄ thin films. Optical absorption shows the presence of direct transition with band gap energy 2.17 eV. The X-ray diffraction (XRD) analysis of the as-deposited and annealed films showed the presence of polycrystalline nature. Energy-dispersive analysis by X-ray (EDAX) study for the sample deposited at optimized preparative parameters shows that the In-to-Cd ratio is almost 2 and S-to-Cd ratio is almost 4. Scanning electron microscopy (SEM) for samples deposited at optimized preparative parameters reveals that spherical grains are uniformly distributed over the surface of the substrate indicates the well-defined growth of polycrystalline CdIn₂S₄ thin film. PEC characterization of the films is carried out by studying photoresponse, spectral response and photovoltaic output characteristics. The fill factor (ff) and power conversion efficiency (η) of the cell are 69 and 2.94%, respectively.     

Effect of different oxidizing gases on the in-situ growth of YBa2Cu3O7−δ films by pulsed laser deposition

The effectiveness of oxygen (O₂), nitrous oxide (N₂O), and nitrogen dioxide (NO₂) as oxidizing agents during in-situ growth of YBa₂Cu₃O_7−δ (YBCO) films on (100) SrTiO₃ substrates by pulsed laser deposition has been studied as a function of deposition temperature (700–800°C), and laser wavelength (193,248 and 355 nm), for a wide range of oxidizer gas pressure (0.1–200 mTorr). In general, the superconducting transition temperature of the films has been found to increase with increasing oxidant pressure, with zero-resistance temperature ≈90 K only obtained in films prepared in a relatively high pressure (150–200 mTorr) of oxidizer gas. At lower pressures, the transition temperature while being depressed is quite sensitive to the nature of the oxidant, the laser wavelength and the deposition temperature. Nevertheless, independent of the oxygen source or other growth parameters, an almost linear decrease in transition temperature with a corresponding increase in the c-axis lattice parameter has been observed for all the film. YBCO films have also been deposited in a low pressure background (≤ 1 mTorr) using a combination of atomic oxygen and pulsed molecular oxygen. The results are discussed in terms of the oxygen requirement for kinetic and thermodynamic stability of YBCO during growth of the film by pulsed laser deposition.     

Synthesis and physical behaviour of In2S3 films

In₂S₃ layers have been grown by close-spaced evaporation of pre-synthesized In₂S₃ powder from its constituent elements. The layers were deposited on glass substrates at temperatures in the range, 200–350 °C. The effect of substrate temperature on composition, structure, morphology, electrical and optical properties of the as-grown indium sulfide films has been studied. The synthesized powder exhibited cubic structure with a grain size of 63.92 nm and S/In ratio of 1.01. The films grown at 200 °C were amorphous in nature while its crystallinity increased with the increase of substrate temperature to 300 °C. The films exhibited pure tetragonal β-In₂S₃ phase at the substrate temperature of 350 °C. The surface morphological analysis revealed that the films grown at 300 °C had an average roughness of 1.43 nm. These films showed a S/In ratio of 0.98 and a lower electrical resistivity of 1.28 × 10³ Ω cm. The optical band gap was found to be direct and the layers grown at 300 °C showed a higher optical transmittance of 78% and an energy band gap of 2.49 eV.     

Effect of deposited temperatures of the buffer layer on the band offset of CZTS/In_2S_3 heterostructure and its solar cell performance

The effect of the deposition temperature of the buffer layer In_2S_3 on the band alignment of CZTS/In_2S_3 heterostructures and the solar cell performance have been investigated.The In_2S_3 films are prepared by thermal evaporation method at temperatures of 30,100,150,and 200 ℃,respectively.By using x-ray photoelectron spectroscopy(XPS),the valence band offsets(VBO) are determined to be-0.28 ±0.1,-0.28 ±0.1,-0.34 ±0.1,and-0.42 ±0.1 eV for the CZTS/In_2S_3heterostructures deposited at 30,100,150,and 200 ℃,respectively,and the corresponding conduction band offsets(CBO)are found to be 0.3 ±0.1,0.41 ±0.1,0.22±0.1,and 0.01 ±0.1 eV,respectively.The XPS study also reveals that interdiffusion of In and Cu occurs at the interface of the heterostructures,which is especially serious at 200 ℃ leading to large amount of interface defects or the formation of CuInS_2 phase at the interface.The CZTS solar cell with the buffer layer In_2S_3 deposited at 150 ℃ shows the best performance due to the proper CBO value at the heterostructure interface and the improved crystal quality of In_2S_3 film induced by the appropriate deposition temperature.The device prepared at 100 ℃presents the poorest performance owing to too high a value of CBO.It is demonstrated that the deposition temperature is a crucial parameter to control the quality of the solar cells.     

Superconducting Nd1.85Ce0.15CuO4 films grown by the pulsed electron deposition technique

Nd_1.85Ce_0.15CuO_4−δ superconducting thin films were prepared on (1 0 0) SrTiO₃ substrates by pulsed electron deposition technique without reducing atmosphere. Oxygen content is finely controlled by high temperature vacuum annealing, and optimal superconductivity has been obtained. The deposition conditions of the film are discussed in details. Higher deposition temperature and lower gas pressure result in the loss of copper and the appearance of the foreign phase Ce_0.5Nd_0.5O_1.75. High quality Nd_1.85Ce_0.15CuO_4−δ epitaxial films are deposited at 840–870 °C in the mixed gas with a ratio of O₂:Ar = 1:3.     

Deposition and characterization of carbon nitride films from hexamethylenetetramine/N2 by microwave plasma-enhanced chemical vapor deposition

Carbon nitride thin films were deposited on Si(1 0 0) substrate by microwave plasma-enhanced chemical vapor deposition (PECVD). Hexamethylenetetramine (HMTA) was used as carbon and nitrogen source while N₂ gas was used as both nitrogen source and carrier gas. The sp³-bonded C---N structure in HMTA was considered significantly in the precursor selection. X-ray diffraction analysis indicated that the film was a mixture of crystalline - and β-C₃N₄ as well as graphitic-C₃N₄ and β-Si₃N₄ which were not easily distinguished. Raman spectroscopy also suggested the existence of - and β-C₃N₄ in the films. X-ray photoelectron spectroscopy study indicated the presence of sp²- and sp³-bonded C---N structures in the films while sp³C---N bonding structure predominated to the sp² C---N bonding structure in the bulk composition of the films. N was also found to be bound to Si atoms in the films. The product was, therefore, described as CN_x:Si, where x depends on the film depth, with some evidences of crystalline C₃N₄ formation.     

Improved initial epitaxial growth of superconducting YBa2Cu3O7 thin films on Y–ZrO2 substrates with a La1.85Sr0.15CuO4 buffer layer

Epitaxial thin films of YBa₂Cu₃O₇ (YBCO) have been deposited on Y–ZrO₂ (YSZ) substrates by means of the pulse laser deposition technique. It has been found that the initial epitaxy of YBCO thin films grown on YSZ can be significantly improved by using La_1.85Sr_0.15CuO₄ (LSCO) as a buffer layer. X-ray diffraction measurements show that the epitaxial YBCO films have single in-plane orientation with YBCO [100]LSCO [100] and LSCO [100]YSZ [110]. The real-time resistance measurements reveal that with LSCO buffer layers the initial formation of the YBCO ultra-thin films changes from the island growth to the layer-by-layer growth.     

Optical characterization of amorphous Ga50Se45S5 films

The transmission spectra of thermally evaporated Ga₅₀Se₄₅S₅ films were measured over the wavelength range 300–900 nm. A simple method, suggested by Swanepoel, was used for the determination of the optical constants and thickness of the films. Increasing the thickness of the film beyond 450 nm does not affect the optical constants. The dependence of the absorption coefficient on the photon energy (hν) at the edge of the absorption band is well described by the relation hν=β(hν−E_opt)² with an optical gap equals 2.4 eV. A good fit of the experimental points with Tauc relation indicates that non-direct transition is the most probable mechanism responsible for the photon absorption inside the investigated film.     

Formation of Ca-doped YBa2Cu4O8 phase in thin films

Ca-doped YBa₂Cu₄O₈ (124) thin films are prepared on (100) SrTiO₃ substrates by annealing the amorphous films deposited using a pulsed laser deposition technique. The X-ray diffraction measurements show that the Ca-doped YBa₂Cu₄O₈ phase is formed by annealing below 800°C at a oxygen pressure of 1 atm. The 124 films have c-axis orientation normal to the substrates. As the Ca content increases, the proportion of the 123 impurity phase in the samples increases. The onset temperature of superconductivity of the Y(Ca)Ba₂Cu₄O₈ films increases from 79 K to 88 K with an increase Ca-substitution for 5 to 10% of Y.     

Growth behavior of high k LaAlO3 films on Si by metalorganic chemical vapor deposition for alternative gate dielectric application

LaAlO₃ (LAO) is explored in this work to replace SiO₂ as the gate dielectric material in metal–oxide–semiconductor field effect transistor. Amorphous LAO gate dielectric films were deposited on Si (0 0 1) substrates by low pressure metalorganic chemical vapor deposition using La(dpm)₃ and Al(acac)₃ sources. The effect of processing parameters such as deposition temperature and precursor vapor flux on growth, structure, morphology, and composition of LAO films has been investigated by various analytical methods deeply. The film growth mechanism on Si is reaction limiting instead of mass transport control. The reaction is thermally activated with activation energy of 37 kJ/mol. In the initial growth stage, Al element is deficient due to higher nucleation barrier on Si. The LAO films show a smooth surface and good thermal stability and remain amorphous up to a high temperature of 850 °C. The electrical properties of amorphous LAO ultrathin films on Si have also been evaluated, indicating LAO is suitable for high k gate dielectric applications.     

GaSb基PECVD法制备SiO2薄膜的应力研究

为了实现在GaSb衬底上获得低应力的SiO₂薄膜,研究了等离子体增强化学气相沉积法（PECVD）在晶格失配较大的GaSb衬底上沉积SiO₂薄膜的应力情况。通过改变薄膜沉积时的工艺条件,如反应温度、射频功率、反应压强、气体流量比,并基于曲率法模型,对镀膜前后的曲率半径进行了实验测量,利用Stoney公式计算相关应力值并绘制应力变化曲线。详细讨论了PECVD工艺条件的改变对SiO₂薄膜应力所产生的影响。同时通过在Si衬底上沉积SiO₂薄膜,对比分析了导致薄膜应力产生的因素及变化过程。实验结果表明,在沉积温度为300℃、射频功率为20 W、腔体压强为90 Pa、气体流量比SiH₄/N₂O为125/70 cm³·min^-1的工艺参数下,PECVD法在GaSb衬底上沉积的SiO₂薄膜应力相对较小。     

基于FTO/VO2/FTO结构的VO2薄膜电压诱导相变光调制特性

采用直流磁控溅射和后退火工艺在掺氟的SnO₂(FTO)导电玻璃衬底上制备VO₂薄膜, 研究了不同退火时间和不同比例的氮氧气氛对VO₂薄膜性能的影响, 对VO₂薄膜的结晶取向、表面形貌、表面元素的相对含量和透过率随波长变化进行了测试分析, 结果表明在最佳工艺条件下制备得到了组分相对单一的VO₂薄膜. 基于FTO/VO₂/FTO结构在VO₂薄膜两侧的透明导电膜上施加电压并达到阈值电压时, 观察到了明显的电流突变. 当接触面积为3 mm×3 mm时, 阈值电压为1.7 V, 阈值电压随接触面积的增大而增大. 与不加电压的情况相比, FTO/VO₂/FTO结构在电压作用下高低温的红外透过率差值可达28%, 经反复施加电压, 该结构仍保持性能稳定, 具有较强的电致调控能力.     

光学玻璃基底原子层同质材料沉积薄膜光谱及激光诱导损伤特性研究

通过原子层沉积技术在熔石英玻璃表面制备了同质材料的单层SiO₂薄膜,对光学薄膜的物理化学性质和强激光辐照下的激光诱导损伤性能进行了深入研究。实验中采用双叔丁基氨基硅烷（BTBAS）和臭氧（O₃）作为反应前驱体,在熔石英光学元件表面进行了SiO₂薄膜的原子层沉积工艺研究,以不同沉积温度条件制备了一系列膜样品。首先对原子层沉积特性和薄膜均匀性展开了研究,发现薄膜生长厚度与沉积循环次数之间符合线性生长规律,验证了制备薄膜的原子级逐层生长特性,并且表面沉积膜层的均匀性很好,其测得膜厚波动不超过2%。然后针对不同温度条件下沉积的SiO₂薄膜,对其粗糙度及各类光谱特性展开了研究,对比结果表明：样品的表面粗糙度在镀膜后有轻微的降低;薄膜样品在200～1 000 nm范围内具有出色的透过率,均超过90%并逐渐趋近于93.3%,且其透射光谱与在裸露熔石英衬底上测得的光谱没有明显差异;镀膜前后荧光光谱和傅里叶变换红外光谱的差异证实了原子层沉积SiO₂膜中点缺陷（非桥键氧、氧空位、羟基等）的存在,这将会影响薄膜耐损伤性能。最后对衬底和膜样品进行了紫外激光诱导损伤测试,损伤阈值的变化表明熔石英元件表面沉积薄膜后的激光损伤性能有所降低,其零概率损伤阈值从31.8 J·cm-2减小到20 J·cm-2左右,与光谱缺陷情况表征相符合。薄膜中点缺陷部位会吸收紫外激光能量,导致局域温度升高,进而出现激光诱导损伤现象并降低抗激光损伤阈值。在选定的沉积温度范围内,较高温度条件下沉积的SiO₂薄膜其激光诱导损伤性能更好,可以控制沉积温度条件使得元件的抗损伤性能更为接近衬底本身,后续有望通过其他反应参数的优化来获得薄膜抗损伤性能的进一步提升。     

单靶溅射制备铜锌锡硫薄膜及原位退火研究

采用衬底加热溅射铜锌锡硫(CZTS)四元化合物单靶制备CZTS薄膜,并研究原位退火对制备薄膜的影响.结果表明:在溅射结束后快速升温并保持一段时间,所得到的样品相比于未原位退火的CZTS薄膜结晶质量更好,且表面更平整致密;原位退火后的CZTS薄膜太阳电池性能参数也相应地有所提升,其开路电压(V_(OC))为575 mV,短路电流密度(J_(SC))为8.32 mA/cm~2,光电转换效率达到1.82%.     

H_2气氛退火处理对Nb掺杂TiO_2薄膜光电性能的影响

采用电子束沉积方法,以钛酸锶(SrTiO3)为衬底制备铌(Nb)掺杂TiO2薄膜并研究后续H2气氛退火处理对其薄膜样品光电性能的影响.结果发现H2气氛热退火处理能有效改善Nb掺杂TiO2薄膜的导电率,最佳电阻率达到5.46×10-3Ω·cm,在可见光范围内的透光率为60%—80%.导电性能的改善与H2气氛退火处理后多晶薄膜的晶粒尺寸变大和大量的氧空位形成及H原子掺杂有关.     

ZnSb掺杂的Ge2Sb2Te5薄膜的相变性能研究

本文采用双靶(ZnSb靶和Ge₂Sb₂Te₅靶)共溅射制备了系列ZnSb掺杂的Ge₂Sb₂Te₅(GST)薄膜. 利用X射线衍射、透射电子显微镜、原位等温/变温电阻测量、X射线光电子能谱等测试研究了薄膜样品的非晶形态、电学及原子成键特性. 利用等温原位电阻测试表明ZnSb掺杂的Ge₂Sb₂Te₅薄膜具有更高的结晶温度. 采用Arrhenius 公式计算发现ZnSb掺杂的Ge₂Sb₂Te₅薄膜的十年数据保持温度均高于传统的Ge₂Sb₂Te₅薄膜的88.9℃. 薄膜在200, 250, 300和350℃ 下退火后的X射线衍射图谱表明ZnSb的掺杂抑制了Ge₂Sb₂Te₅薄膜从fcc态到hex态的转变. 通过对薄膜的光电子能谱和透射电镜分析可知Zn, Sb, Te原子之间键进行重组, 形成Zn–Sb 和Zn–Te 键, 且构成非晶物质存在于晶体周围. 采用相变静态检测仪测试样品的相变行为发现ZnSb掺杂的Ge₂Sb₂Te₅薄膜具有更快的结晶速度. 特别是(ZnSb)_24.3(Ge₂Sb₂Te₅)_75.7薄膜, 其结晶温度达到250℃, 十年数据保持温度达到130.1℃, 并且在70 mW激光脉冲功率下晶化时间仅～64 ns, 远快于传统Ge₂Sb₂Te₅薄膜的晶化时间～280 ns. 以上结果表明(ZnSb)_24.3(Ge₂Sb₂Te₅)_75.7薄膜是一种热稳定性好且结晶速度快的相变存储材料.     

Effect of annealing on properties of electrochemically deposited CdTe thin films

Thin films of CdTe have been deposited onto stainless steel and fluorine-doped tin oxide (FTO)-coated glass substrates from aqueous acidic bath using electrodeposition technique. The different preparative parameters, such as deposition time, bath temperature and pH of the bath have been optimized by photoelectrochemical (PEC) technique to get good quality photosensitive material. The deposited films are annealed at different temperature in presence of air. Annealing temperature is also optimized by PEC technique. The film annealed at 200 °C showed maximum photosensitivity. Different techniques have been used to characterize as deposited and also as annealed (at 200 °C) CdTe thin film. The X-ray diffraction (XRD) analysis showed the polycrystalline nature, and a significant increase in the XRD peak intensities is observed for the CdTe films after annealing. Optical absorption shows the presence of direct transition with band gap energy 1.64 eV and after annealing it decreases to 1.50 eV. Energy dispersive analysis by X-ray (EDAX) study for the as-deposited and annealed films showed nearly stoichiometric compound formation. Scanning electron microscopy (SEM) reveals that spherically shaped grains are more uniformly distributed over the surface of the substrate for the CdTe film.     

X-ray diffraction studies of epitaxy in orthorhombic- DyMnO3/Er1Ba2Cu3O7-δ thin film heterostructures on LaAlO3 (100) substrates

The heteroepitaxy in DyMnO₃/Er₁Ba₂Cu₃O_7-δ bilayer thin films on LaAlO₃ (100) substates was characterized by four-circle X-ray diffractometry. The Er₁Ba₂Cu₃O_7-δ thin films on LaAlO₃ (100) substrates were prepared by molecular-beam deposition (MBD) and post-growth annealing in wet and dry O₂ at 880°C, whereas the DyMnO₃ thin films on the Er₁Ba₂Cu₃O_7-δ/LaAlO₃ (100) heterostructure were deposited by MBD and post-growth annealing in dry O₂ at 750°C. The conventional X-ray diffraction (XRD) patterns as well as pole figures (φ-scans) for specific (hkl) reflections were acquired. The Er₁Ba₂Cu₃O_7-δ thin film in the DyMnO₃/Er₁Ba₂Cu₃O_7-δ/LaAlO₃ (100) heterostructure showed [001] oriented epitaxial growth, as expected. The DyMnO₃ thin film on the Er₁Ba₂Cu₃O_7-δ epilayer in the heterostructure grew with (110) epitaxy in its metastable orthorhombic phase (lattice constants: a_o=5.272 Å, b_o=5.795 Å and c_o=7.38 Å). The heteroepitaxial relationships at the orthorhombic-DyMnO O₃ (110) /Er₁Ba₂Cu₃O_7-δ (001) interface was determined as the following: DyMnO₃ (110) Er₁Ba₂Cu₃O_7-δ (001), DyMnO₃ [1 0] ¶r; Er₁Ba₂Cu₃O_7-δ[100] or Er₁Ba₂Cu₃O_7-δ[010], and DyMnO₃ [001] ¶r; Er₁Ba₂Cu₃O _7-δ[010] or Er₁Ba₂Cu₃O_7-δ [100].