Morphological and optical properties of titanyl phthalocyanine films deposited by supersonic molecular beam epitaxy (SuMBE)

We studied the growth and properties of titanyl phthalocyanine (TiOPc) thin films made by supersonic molecular beam epitaxy (SuMBE). Interesting differences in the growth properties on amorphous (quartz) and crystalline (mica) substrates were found, indicating that SuMBE gives rise to an epitaxy of disc-like organic molecules on crystalline substrates. The combined control of the kinetic energy of the molecules in the supersonic beam specific to SuMBE and of the substrate temperature during deposition are the key parameters used to determine the final properties of the films. We show that SuMBE is a well-suited epitaxy method for the deposition of relatively large organic molecules, leading to layers of thin organic (single-)crystals with lateral dimensions in the micrometer range. By SuMBE we can control the growth of different polymorphs of TiOPc. We found and studied two ways to produce films of red and infrared absorbing phase II TiOPc, which is of interest for applications in organic solar cells.     

Effect of annealing on the surface and band gap alignment of CdZnS thin films

Effects of the annealing temperature on structural, optical and surface properties of chemically deposited cadmium zinc sulfide (CdZnS) films were investigated. X-ray diffraction (XRD) results showed that the grown CdZnS thin films formed were polycrystalline with hexagonal structure. Atomic force microscopy (AFM) studies showed that the surface roughness of the CdZnS thin films was about 60-400 nm. Grain sizes of the CdZnS thin films varied between 70 and 300 nm as a function of annealing temperature. The root mean square surface roughness of the selected area, particular point, average roughness profile, topographical area of roughness were measured using the reported AFM software. The band gaps of CdZnS thin films were determined from absorbance measurements in the visible range as 300 nm and 1100 nm, respectively, using Tauc theory.     

Growth and annealing of zinc-blende CdSe thin films on GaAs (0 0 1) by molecular beam epitaxy

CdSe thin films have been grown on GaAs (0 0 1) substrates by molecular beam epitaxy (MBE). The effects of substrate temperature and annealing treatment on the structural properties of CdSe layers were investigated. The growth rate slightly decreases due to the accelerated desorption of Cd from CdSe surface with an increase in the temperature. The sample grown at 260 °C shows a polycrystalline structure with rough surface. As the temperature increases over 300 °C, crystalline CdSe (0 0 1) epilayers with zinc-blende structure are achieved and the structural quality is improved remarkably. The epilayer grown at 340 °C displays the narrowest full-width at half-maximum (FWHM) from (0 0 4) reflection in double-crystal X-ray rocking curve (DCXRC) and the smallest root-mean-square (RMS) roughness of 0.816 nm. Additionally, samples fabricated at 320 °C were annealed in air for 30 min to study the films’ thermal stability. X-ray diffraction (XRD) results indicate that the zinc-blende structure remains unchanged when the annealing temperature is elevated to 460 °C, meaning a good thermal stability of the cubic CdSe epilayers.     

Fe3O4/MgO(100)薄膜的激光分子束外延与磁电学性能

 采用激光分子束外延方法,以烧结α-Fe₂O₃/为靶材,在MgO（100）基底上制备了Fe₃O₄薄膜。通过反射高能电子衍射原位观察了薄膜生长前后的表面结构,结果表明所生长的Fe₃O₄薄膜表面平整。经显微激光拉曼光谱和X光电子能谱分析证实所得薄膜表面成分为纯相Fe₃O₄。磁电学性能采用多功能物性系统测量,结果表明：当温度降至100 K附近时,薄膜电阻率有较大增加,Verwey相转变的范围变宽而且不明显,说明反向晶粒边界的存在;在7 160 kA·m^-1的磁场下,室温磁电阻达到-6.9%,在80和150 K温度下磁电阻分别达到-10.5%和-16.1%;薄膜的室温饱和磁化强度约为260 kA·m^-1,其矫顽磁场约为202 kA·m^-1。     

Morphological and chemical study of the initial growth of CdS thin films deposited using an ammonia-free chemical process

We study the initial growth stages of CdS thin films deposited by an ammonia-free chemical bath deposition process. This ammonia-free process is more environmentally benign because it reduces potential ammonia release to the environment due to its high volatility. Instead of ammonia, sodium citrate was used as the complexing agent. We used atomic force microscopy (AFM), Rutherford backscattering (RBS) and X-ray photoelectron spectroscopy (XPS) to investigate the morphological and chemical modifications at the substrate surface during the first initial stages of the CdS deposition process. Additionally, X-ray diffraction (XRD) and optical transmission spectroscopy measurements were carried out to compliment the study. XPS results show that the first nucleation centers are composed by Cd(OH)₂ which agglomerate in patterns of bands, as demonstrated by AFM results. It is also observed that the conversion to CdS (by anionic exchange) of the first nucleus begins before the substrate surface is completely covered by a homogenous film.     

Effects of intermediate zinc pulses on properties of TiN and NbN films deposited by atomic layer epitaxy

The reasons for the improvements gained by using intermediate zinc pulses in atomic layer epitaxy growth of TiN and NbN films were examined by a comprehensive characterization and comparison of films prepared from TiCl₄ or NbCl₅ and NH₃ with and without zinc. The characterization techniques used comprise time-of-flight elastic recoil detection analysis, secondary ion mass spectrometry, Rutherford backscattering spectrometry, nuclear resonance broadening, proton backscattering spectrometry, deuteron induced reactions, proton induced X-ray emission, atomic force microscopy, scanning electron microscopy, X-ray diffraction, and Hall effect and reflectance measurements. The effect of zinc was found to be manifold: both compositional and structural changes were observed. In the case of TiN the major improvement gained by using zinc was significantly decreased oxygen contamination whereas a marked increase of grain size was the dominant effect observed with NbN. A clear correlation between the compositional and structural changes and the improvements of the electrical properties was established.     

Surface kinetics of GaN evaporation and growth by molecular-beam epitaxy

The kinetics of surface processes during the growth of GaN by molecular-beam epitaxy (MBE) with ammonia as the source of reactive nitrogen is studied theoretically and experimentally. A model of surface processes is developed taking into account specific effects of the blocking of NH₃ adsorption sites by Group III and Group V surface species. Parameters of the model (respective kinetic rate constants) are determined from comparison with experimental data. It is shown that the evaporation rate of GaN in ammonia atmosphere is much lower than that in vacuum. Kinetics of GaN growth under gallium-rich and nitrogen-rich conditions are compared. Under nitrogen-rich conditions the GaN surface is predicted to be enriched by NH_x surface radicals, in contrast to the case of growth under gallium-rich conditions or of free evaporation in vacuum. It is shown that use of the nitrogen-rich conditions allows one to increase the growth temperature by 80–90°C compared with the case of gallium-rich conditions or plasma-activated MBE. The increased growth temperature is favorable in improving the optical and electrical properties of the material grown.     

垂直磁各向异性L10-Mn1.67Ga超薄膜分子束外延生长与磁性研究

具有超强垂直磁各向异性的L1₀-Mn_xGa薄膜由于其与半导体材料结构及工艺的高度兼容性而受到广泛关注, 其超高垂直磁各向异性能和极低的磁阻尼因子预示着L1₀-Mn_xGa薄膜在高热稳定性自旋电子学器件中将发挥重要作用. 而L1₀-Mn_xGa超薄膜对于降低L1₀-Mn_xGa基垂直磁各向异性隧道结中的磁矩翻转临界电流密度有着重要的意义. 本文采用分子束外延的方法, 在半导体GaAs衬底上成功制备出了一系列不同厚度的L1₀-Mn_1.67Ga薄膜, 厚度范围为1-5 nm. 生长过程中反射式高能电子衍射原位检测以及X射线衍射结果均表明了其良好的单晶相. 磁性测量结果表明, 厚度在1 nm以上的L1₀-Mn_1.67Ga薄膜均可以保持垂直磁各向异性特征, 厚度为5 nm的L1₀-Mn_1.67Ga薄膜的垂直磁各向异性能可达到14.7 Merg/cm³. 这些结果为基于L1₀-Mn_1.67Ga的垂直磁各向异性隧道结在自旋转移扭矩驱动的磁随机存储器等低功耗器件的集成及应用提供了重要的实验支持.     

Molecular beam epitaxy of GaSb on ZnTe/GaAs: Influence of the chemical composition of ZnTe surface

We have studied the molecular beam epitaxy (MBE) of GaSb films on GaAs (0 0 1) substrates by using ZnTe as a new buffer layer. GaSb films were grown on two distinct ZnTe surfaces and the influence of surface chemical composition of ZnTe on the morphological and structural properties of GaSb films has been investigated. Initial 2-dimensional (2D) growth of GaSb films is obtained on Zn-terminated surface consequently smooth morphology and high crystal quality GaSb films are achieved. The thin GaSb film (0.4 μm) grown on Zn-terminated ZnTe surface reveals considerably narrow X-ray diffraction linewidth (113 arcsec) along with small residual strain, which strongly supports the availability of ZnTe buffer for the growth of high-quality GaSb film.     

分子束外延制备的垂直易磁化MnAl薄膜结构和磁性

系统地研究了利用分子束外延方法在GaAs(001) 衬底上外延生长的MnAl_x薄膜的结构和垂直易磁化特性随组分及生长温度的依赖关系. 磁性测试表明, 可在较大组分范围内 (0.4≤x≤1.2) 获得大矫顽力的垂直易磁化MnAl_x薄膜, 然而同步辐射X射线衍射和磁性测试发现当x≤0.6时MnAl薄膜出现较多的软磁相, 当x >0.9时, MnAl薄膜晶体质量和化学有序度逐渐降低, 组分为MnAl_0.9时制备的薄膜有最好的[001]取向. 随着生长温度的增加, MnAl_0.9薄膜的有序度、垂直磁各向异性常数、矫顽力和剩磁比均增加, 350℃时制备的MnAl_0.9薄膜化学有序度高达0.9, 其磁化强度、剩磁比、矫顽力和垂直磁各向异性常数分别为265emu/cm³、93.3%、8.3kOe (1 Oe=79.5775A/m)和7.74Merg/cm³ (1 erg=10^-7J). 不含贵金属及稀土元素、良好的垂直易磁化性质、 与半导体材料结构良好的兼容性以及磁性能随不同生长条件的可调控 性使得MnAl薄膜有潜力应用于多种自旋电子学器件. 关键词： 分子束外延 大矫顽力材料 磁各向异性     

Properties of NiO thin films deposited by intermittent spray pyrolysis process

NiO thin films have been grown on glass substrates by intermittent spray pyrolysis deposition of NiCl₂·6H₂O diluted in distilled water, using a simple “perfume atomizer”. The effect of the solution molarity on their properties was studied and compared to those of NiO thin films deposited with a classical spray system. It is shown that NiO thin films crystallized in the NiO structure are achieved after deposition. Whatever the precursor molarity, the grain size is around 25-30 nm. The crystallites are preferentially oriented along the (1 1 1) direction. All the films are p-type. However, the thickness and the conductivity of the NiO films depend on the precursor contraction. By comparison with the properties of films deposited by classical spray technique, it is shown that the critical precursor concentration, which induces strong thin films properties perturbations, is higher when a perfume atomizer is used. This broader stability domain can be attributed to better chlorides decomposition during the rest time used in the perfume atomizer technique.     

Bioactive glass thin films deposited by magnetron sputtering technique: The role of working pressure

Bioglass coatings were prepared by radio frequency magnetron sputtering deposition at low temperature (150 °C) onto silicon substrates. The influence of argon pressure values used during deposition (0.2 Pa, 0.3 Pa and 0.4 Pa) on the short-range structure and biomineralization potential of the bioglass coatings was studied. The biomineralization capability was evaluated after 30 days of immersion in simulated body fluid. SEM-EDS, XRD and FTIR measurements were performed. The tests clearly showed strong biomineralization features for the bioglass films. The thickness of the chemically grown hydroxyapatite layers was more than twice greater for the BG films deposited at the highest working pressure, in comparison to those grown on the films obtained at lower working pressures. The paper attempts to explain this experimental fact based on structural and compositional considerations.     

Investigation on the effect of Zr doping in ZnO thin films by spray pyrolysis

Zirconium doped zinc oxide thin films with enhanced optical transparency were prepared on Corning 1737 glass substrates at the substrate temperature of 400 °C by spray pyrolysis method for various doping concentrations of zirconium (IV) chloride in the spray solution. The X-ray diffraction studies reveal that the films exhibit hexagonal crystal structure with polycrystalline grains oriented along (0 0 2) direction. The crystalline quality of the films is found to be deteriorating with the increase of doping concentration and acquires amorphous state for higher concentration of 8 at.% in precursor solution. The average transmittance for 5 at.% (solution) zirconium doped ZnO film is significantly increased to ∼92% in the visible region of 500-800 nm. The room temperature photoluminescence (PL) spectra of films show a band edge between 3.41 and 3.2 eV and strong blue emission at 2.8 eV irrespective of doping concentration and however intensity increases consistently with doping levels. The vacuum annealing at 400 °C reduced the resistivity of the films significantly due to the coalescence of grains and the lowest resistivity of 2 × 10⁻³ Ω cm is observed for 3 at.% (solution) Zr doped ZnO films which envisages that it is a good candidate for stable TCO material.     

Determination of the nanoscale dielectric properties in ferroelectric lead zirconate titanate (PZT) thin films

We report on nanoscale experiments with <100 nm lateral resolution being able to differentiate the effective dielectric polarisation P_z, deposited charge density σ, surface dielectric constant ε_surface, its voltage dependence ε_surface(U), as well as the built-in electric bias voltage U_int in ferroelectric lead zirconate titanate (PZT) thin films. This is possible by combining piezoresponse force microscopy (PFM) and pull-off force spectroscopy (PFS), both methods based on scanning force microscopy (SFM). The differentiation becomes possible since both P_z and σ contribute additively in PFS, while they are subtractive in PFM, hence allowing the two contributions to be separated. ε_surface can be quantified by means of the experimental PFS data and the calculated effective penetration depth of PFM developed in a finite element modelling. Finally, U_int and ε_surface(U) are derived by an absolute matching of the P_z values measured by PFM and PFS.Our nanoscale results obtained on PZT thin films reveal values for the above specified quantities that have the same order of magnitude as those obtained from macroscopic measurements reflecting the integral response using large electrode areas. However, we stress that the data reported here reveal physical properties deduced on the nanometer scale. Furthermore, they are recorded during one single experimental investigation, using one single set-up only.     

The electrical, optical properties of AlSb polycrystalline thin films deposited by magnetron co-sputtering without annealing

In order to fabricate AlSb polycrystalline thin films without post annealing, this paper studies a technology of magnetron co-sputtering onto intentionally heated substrate. It compares the structural characteristics and electrical properties of AlSb films which are deposited at different substrate temperatures. It finds that the films prepared at a substrate temperature of 450 oC exhibit an enhanced grain growth with an average grain size of 21 nm and the lattice constant is 0.61562 nm that goes well with unstained lattice constant (0.61355 nm). The ln(σ_dark) ～1/T curves show that the conductivity activation energy is about 0.38 eV when the film is deposited at 450 oC without an annealing. The transmittance and reflectance spectra show that the film deposited at 450 oC has an optical band gap of 1.6 eV. These results indicate that we have prepared AlSb polycrystalline films which do not need a post annealing.     

Structural and morphological properties of thin ZnO films grown by pulsed laser deposition

The pulsed laser deposition technique was used to produce zinc oxide thin films onto silicon and Corning glass substrates. Homogeneous surfaces exhibiting quite small Root Mean Square (RMS) roughness, consisting of shaped grains were obtained, their grain diameters being 40-90 nm at room temperature and at 650 °C growth respectively. Films were polycrystalline, even for growth at room temperature, with preferential crystallite orientation the (0 0 2) basal plane of wurtzite ZnO. Temperature increase caused evolution from grain to grain agglomeration structures, improving crystallinity. Compressive to tensile stresses transition with temperature was found while the lattice constant decreased.     

Evolution of stress and strain relaxation of Ge and SiGe alloy films on Si(0 0 1)

The growth of Ge and SiGe alloy films on Si substrates has attracted considerable interest in the last years because of their importance for optoelectronic devices as well as Si-based high speed transistors. Here we give a short overview on our recent real time stress measurements of Ge and SiGe alloy films on Si(0 0 1) performed with a sensitive cantilever beam technique and accompanied by structural investigations with atomic force microscopy. Characteristic features in the stress curves provide detailed insight into the development and relief of the misfit strain. For the Stranski–Krastanow system Ge/Si(0 0 1) as well as for SiGe films with Si contents below 20%, the strain relaxation proceeds mainly into two steps: (i) by the formation of 3D islands on top of the Ge wetting layer; (ii) via misfit dislocations in larger 3D islands and upon their percolation.     

Physical properties of ZnO thin films deposited by spray pyrolysis technique

Thin films of ZnO have been prepared on glass substrates at different thicknesses by spray pyrolysis technique using 0.2 M aqueous solution of zinc acetate. X-ray diffraction reveals that the films are polycrystalline in nature having hexagonal wurtzite type crystal structure. The resistivity at room temperature is of the order 10⁻² Ω cm and decreased as the temperature increased. Films are highly transparent in the visible region. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for a sprayed film is also reported. Optical bandgap, E_g, has been reported for the films. A shift from E_g = 3.21 eV to 3.31 eV has been observed for deposited films.     

立方氮化硼薄膜的光学带隙

用射频溅射法在p型Si(100)衬底上沉积立方氮化硼(c-BN)薄膜,薄膜的成分由傅里叶变换红外谱标识,用紫外-可见分光光度计测量了c-BN薄膜的反射光谱,利用K-K(Kramers-Kroning)关系从反射谱计算出c-BN薄膜的光吸收系数,进而确定c-BN薄膜的光学带隙.对于立方相含量为55.4%的c-BN薄膜,光学带隙为5.38eV. 关键词： 立方氮化硼薄膜 光学带隙 K-K关系