Ultra-high-vacuum in situ electron microscopy of growth processes of epitaxial thin films

Extracts from recent results of ultra-high-vacuum in-situ electron microscopy of growth processes of epitaxial thin films are given. As a modified monolayer-by-monolayer mode, the growth process in Fe/(111)Au of the initial Frank-van der Merwe type, followed by the intrinsic γ → α transformation of Fe is mentioned. For the nucleation and growth mode, a systematic selection of epitaxial orientation according to interfacial lattice fitting, nucleation and coalescence features, the validity of Cabrera's suggestion extending Frank and van der Merwe's idea, the cluster mobility and effects of grown-in dislocations in substrate crystals are discussed on the basis of the observations.     

Synthesis of polycrystalline silicon thin films with ‘icosahedral’ symmetry by ceramics hot wire chemical vapor deposition

We report on synthesis and materials physics of polycrystalline silicon thin films deposited on glass with rarely observed ‘five-fold’ symmetry or ‘icosahedral’ symmetry. We invented these ‘novel form’ of polycrystalline silicon thin films by ceramics hot wire chemical vapor deposition (hot-wire CVD). A new physical effect in hot-wire CVD technology has been proposed that controls the nucleation and growth of silicon thin films on glass substrate.     

A study of growth and morphological features of TiOxNy thin films prepared by MOCVD

The growth and morphological features of MOCVD TiO_xN_y films have been characterized to evaluate the effect of various process parameters on film growth. XRD analysis of the films deposited at 600°C on Si(1 1 1) and mica show a TiN(1 1 1) peak at 2θ=36.6°, but only anatase peaks are detected below 550°C. Above 650°C, both anatase and rutile peaks are detected. The presence of ammonia is not effective below 550°C as the deposited film is mostly TiO₂. Also, ammonia does not play any role in homogeneous nucleation in the gas phase, as evident by the deposition of anatase/rutile particles above 650°C. The following changes in the morphological features are observed by varying process parameters. By increasing the ratio of titanium-isopropoxide to ammonia flow, the cluster shape changes from angular to rounded; dilution of the flow results in larger elongated clusters; increase in flow rate at constant precursor to ammonia ratios, changes the cluster shape from rounded to elongated and the cluster size deceases. Deposition at higher temperatures results in finer clusters with a slower growth rate and eventually results in a very thin film with particle deposition at 650°C and above.     

外加氩气流下脉冲激光烧蚀制备纳米硅晶粒成核生长动力学研究

为研究纳米硅晶粒成核生长动力学过程,采用脉冲激光烧蚀(PLA)技术,在室温,50～200 Pa的氩气氛围中,通过引入垂直于烧蚀羽辉轴线的外加气流,在水平放置的衬底上沉积了一系列纳米Si晶薄膜.扫描电子显微镜( SEM)、拉曼(Raman)散射和X射线衍射(XRD)检测结果表明,未引入气流时,衬底上相同位置处晶粒尺寸随气体压强的增大逐渐减小;在距靶1 ～2cm范围内引入气流后,尺寸变化规律与未引入气流时相反.通过分析晶粒尺寸及其在衬底上的位置分布特点,结合流体力学模型和热动力学方程,分析得出在激光能量密度一定的条件下,环境气体压强、烧蚀粒子温度和密度共同影响着纳米晶粒的成核生长.     

Structure and properties of amorphous thin film for optical data storage

In this paper the magnetic and magneto-optical properties of amorphous rare earth-transition metal (RE-TM) alloys as well as the magnetic coupling in the multi-layer thin films for high density optical data storage are presented. Using magnetic effect in scanning tunneling microscopy the clusters structure of amorphous RE-TM thin films has been observed and the perpendicular magnetic anisotropy in amorphous RE-TM thin films has been interpreted. Experimental results of quick phase transformation under short pulse laser irradiation of amorphous semiconductor and metallic alloy thin films for phase change optical recording are reported. A step-by-step phase transformation process through metastable states has been observed. The waveform of crystallization propagation in micro-size spot during laser recording in amorphous semiconductor thin films is characterized and quick recording and erasing mechanism for optical data storage with high performance are discussed. The nonlinear optical effects in amorphous alloy thin films have been studied. By photo-thermal effect or third order optical nonlinearity, the optical self-focusing is observed in amorphous mask thin films. The application of amorphous thin films with super-resolution near field structure for high-density optical data storage is performed.     

The size effect on the ice nucleating behaviour of PbI2 thin films

A relationship exists between the size of the particle and nucleation temperature. There exists an optimum particle size below which nucleation is inhibited. The behaviour of lead iodide thin films as a substrate for ice nucleation is reported in this study. It is found that the supercooling increases with increase in the thickness of the film. But the change in nucleation temperature above 1250 Å is negligible.     

Properties of non‐stoichiometric nitrogen doped LPCVD silicon thin films

The influence of nitrogen on the internal structure and so on the electrical properties of silicon thin films obtained by low‐pressure chemical vapor deposition (LPCVD) was studied using several investigation methods. We found by using Raman spectroscopy and SEM observations that a strong relationship exists between the structural order of the silicon matrix and the nitrogen ratio in film before and after thermal treatment. As a result of the high disorder caused by nitrogen on silicon network during the deposit phase of films, the crystallization phenomena in term of nucleation and crystalline growth were found to depend upon the nitrogen content. Resistivity measurements results show that electrical properties of NIDOS films depend significantly on structural properties. It was appeared that for high nitrogen content, the films tend to acquire an insulator behavior. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Use of cadmium selenide thin films as a carbon dioxide gas sensor

Cadmium Selenide (CdSe) thin films were prepared in different growth conditions by thermal evaporation. The films were characterised using transmission electron microscopy and X-ray diffraction. The electrical parameters such as resistivity, carrier mobility, and concentration were determined. The sensitivity of carbon dioxide (CO₂) gas on CdSe thin films were studied. A tentative mechanism was proposed, in which the role of CO₂ gas in increasing the conductivity of CdSe thin films were explained by Molecular Orbital (MO) theory. CO₂ gas sensing alarm system was fabricated.     

On the mechanism of formation of amorphous condensates from the vapour phase (I). General theory

The thermodynamic and kinetic conditions for the vapour condensation of non-crystalline thin films are formulated within the framework of the classical nucleation theory. The conditions for the predominant formation of crystalline or amorphous thin films are given and the acting supersaturation and the activity of the substrate are taken into account. Generalized criteria for the formation of amorphous (liquid or glassy) thin films are given and a temperature diagram is established which enables the concrete determination of the limits within which amorphous condensates are to be expected. It is thus possible to give the theoretical background of a technically and experimentally interesting process; the applications of the obtained results to the existing experimental data are also given in some detail. Further problems of the vapour condensation and stability of amorphous thin films, especially some effects of secondary crystallization will be discussed in more detail in Parts II and III of this series of papers, which report on experimental investigations of the formation of amorphous condensates.     

Effect of Mn concentration and growth temperature on nanostructures and magnetic properties of Ge1−xMnx grown on Si

The nanostructures and magnetic properties of Ge_1−xMn_x thin films grown on Si substrates by molecular beam epitaxy, with different nominal Mn concentrations (1−4%) and different growth temperatures, have been systematically investigated by transmission electron microscopy and superconducting quantum interference device. It was discovered that when Ge_1−xMn_x thin films were grown at 70 °C, with increase in Mn concentration, Mn-rich tadpole shaped clusters started to nucleate at 1% Mn and become dominate in the entire film at 4% Mn. While for the thin films grown at 150 °C, tadpoles was firstly seen in the film with 1% Mn and subsequently Mn-rich secondary precipitates became dominant. The magnetic properties show specific features, which are mainly related to the nature and amount of Mn-rich clusters/precipitates within these thin films.     

Microcrystalline silicon prepared at magnetic field modified nucleation

We present a complex characterization of thin silicon films, the growth of which has been influenced by permanent magnet, placed under the substrate. The pattern of microcrystalline regions in otherwise amorphous film varied with the orientation of the magnetic field. Study by atomic force microscopy and by micro-Raman spectroscopy revealed that the microcrystalline regions resulted from increased nucleation density of crystalline grains at the locations where the magnetron effect could be expected. This phenomenon allowed us to study in detail the transition between amorphous and microcrystalline growth. Moreover, it can be used as a kind of ‘magnetic lithography’ for preparation of predefined microcrystalline patterns in otherwise amorphous silicon films.     

ZnWO4单晶衬底上ZnO薄膜的晶核发育与形貌分析

ZnWO4单晶的a晶面与氧化锌c晶面晶格匹配很好,是制备氧化锌薄膜的优良衬底.本文采用溶胶-凝胶法在ZnWO4单晶衬底上制备出透明的ZnO薄膜.通过光学显微镜对薄膜晶核发育过程和形貌进行了详细的分析.实验结果表明:在结晶刚开始,系统将经历成核--长大的过程,随着生长过程的进行,在主晶轴上(一次轴)上又长出二次轴、三次轴等等,最后逐渐形成树枝状晶核.由于ZnO晶核是在非平衡条件下生长的,故在晶核发育过程中又出现了三种不同的生长形态--成核生长、枝晶生长和分形生长.     

VHF-PECVD制备微晶硅薄膜的微结构研究

用甚高频等离子体化学气相沉积(VHF-PECVD)法在玻璃衬底上低温制备了不同沉积时间微晶硅薄膜.用拉曼散射光谱仪、X射线衍射(XRD)、原子力显微镜(AFM)等表征手段对薄膜的微观结构进行了研究.研究结果表明:随着沉积时间的延长,薄膜呈岛状生长,薄膜晶粒度在微晶核形成后迅速升高并逐渐饱和;其微观结构经历了"非晶相→非晶/微晶混合相→微晶相"的演变过程.本实验制备的微薄膜仍以(111)为优化取向.     

气相输运沉积制备c轴择优取向的碘化铋薄膜

铋基卤化物材料因其无毒和优良的光电性能而显示出巨大的应用潜力。BiI₃作为一种层状重金属半导体,已被用于X射线检测、γ射线检测和压力传感器等领域,最近其作为一种薄膜太阳能电池吸收材料备受关注。本文采用简单的气相输运沉积(VTD)法,以BiI₃晶体粉末作为蒸发源,在玻璃基底上得到高质量c轴择优取向的BiI₃薄膜。并通过研究蒸发源温度和沉积距离对薄膜物相和形貌的影响,分析了BiI₃薄膜择优生长的机理。结果表明VTD法制备的BiI₃薄膜属于三斜晶系,其光学带隙为~1.8 eV。沉积温度对薄膜的择优取向有较大影响,在沉积温度低于270 ℃时,沉积的薄膜具有沿c轴择优取向生长的特点,超过此温度,c轴择优取向生长消失。在衬底温度为250 ℃、沉积距离为15 cm时制备的薄膜结晶性能最好,晶体形貌为片状八面体。     

衬底温度对直流反应磁控溅射法制备的N掺杂p型ZnO薄膜性能的影响

利用直流反应磁控溅射法(纯金属锌作为靶材,Ar-N2-O2混合气体作为溅射气体)在石英玻璃衬底上制备了N掺杂p型ZnO薄膜.通过XRD、Hall和紫外可见透射谱分别研究了衬底温度对ZnO薄膜结构性能、电学性能和光学性能的影响.XRD结果显示所有制备的薄膜都具有垂直于衬底的c轴择优取向,并且随着衬底温度的增加,薄膜的晶体质量得到了提高.Hall测试表明衬底温度对p型ZnO薄膜的电阻率具有较大影响,400℃下生长的p型ZnO薄膜由于具有较高的迁移率(1.32 cm2/Vs)和载流子浓度(5.58×1017cm-3),因此表现出了最小的电阻率(8.44Ω·cm).     

Effect of annealing on the properties of chemical bath deposited nanorods of CdSe thin films

Cadmium selenide (CdSe) thin films have been deposited by chemical bath deposition (CBD) on a glass substrate and they are annealed at 450 °C for 1 h. Scanning electron microscopic (SEM) image of as‐deposited CdSe shows the spherical shaped grains distributed over entire glass substrate. When it is annealed at 450 °C, clusters of nano‐rods with star shaped grains are formed. The X‐ray diffraction (XRD) study of the as‐deposited films exhibits a polycrystalline nature and it undergoes a structural phase transition from the metastable cubic to the stable hexagonal phase when annealed at 450 °C. Optical band gap of as‐deposited films (2.0 eV) has a blue shift with respect to the bulk value (1.7 eV) due to quantum confinement. The band gap energies of the films are decreased from 2.0 eV to 1.9 eV due to annealing at the temperature of 450 °C. The electrical resistivity, Hall mobility and carrier concentration of as‐deposited and annealed films are determined.     

溶剂热法制备Al掺杂ZnO薄膜的机理研究

采用溶剂热法在玻璃衬底上制备Al掺杂的ZnO薄膜,研究了溶剂热过程中升温、恒温和降温三个阶段分别对薄膜物相和形貌的影响,探讨了薄膜的生长机理.结果表明,升温阶段只是形核过程,基片仅在升温阶段与前驱液接触不能形成薄膜;基片在升温-恒温阶段与前驱液接触可制备(002)择优取向的薄膜;恒温阶段既有成核过程又有晶体生长过程,基片仅在恒温阶段与前驱液接触可以制备薄膜;降温阶段薄膜继续生长.     

Optical properties of ZnO nano fiber thin films grown by spray pyrolysis of zinc acetate precursor

Good homogeneous and stoichiometric ZnO nanofiber thin films have been deposited onto cleaned glass substrate by a simple spray pyrolysis technique under atmospheric pressure using zinc acetate precursor at temperature 200 °C. Films of various thicknesses have been obtained by varying the deposition time, while all other deposition parameters such as spray rate, carrier gas pressure and distance between spray nozzle to substrate were kept constant. Surface morphology and optical properties of the as deposited thin films have been studied by Scanning Electron Microscopy (SEM) attached with an EDX and UV visible spectroscopy. From EDX data, atomic weight% of Zinc and Oxygen were found to be 49.22% and 49.62% respectively. The SEM micrograph of the film shows uniform deposition and scattered nano fiber around the nucleation centers. The optical band gap of the ZnO thin films was found to be in the range 3.3 to 3.4 eV and the band gap decreases with thickness of the film. Optical constants such as refractive index, extinction coefficient, real and imaginary parts of dielelectric constants were evaluated from reflectance and absorbance spectra. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The microstructure and magnetic property of TiO2‐terminated SrTiO3 substrate selected growth cubic phase CaRuO3 film

CaRuO₃ thin films with various thicknesses were synthesized by pulsed laser deposition respectively on SrTiO₃ substrates with SrO‐ and TiO₂‐termination. The microstructure of these films was studied by transmission electron microscopy. The results demonstrate that the CaRuO₃ thin films grown on TiO₂‐terminated substrates show quite uniform morphology, whilst they do the facet morphology when the substrates are SrO‐terminated. In addition, there is a 5∼7 unit‐cell‐thickness cubic CaRuO₃ layer in the films grown on TiO₂‐terminated substrates. The measured ferromagnetic hysteresis loop is attributed to the cubic CaRuO₃ layer, which is supported by a first‐principles calculations. On the contrary, there is free of cubic CaRuO₃ layer in samples grown on SrO‐terminated substrates. The crystallographic domains, the orientation relationship between domains and substrates and crystal defects in these films were studied as well. The different growth mechanism of CaRuO₃ on SrO‐ and TiO₂‐terminated SrTiO₃ substrates may be correlated with the selective nucleation and growth.     

Seeding acceleration of perovskite crystallization in lead calcium titanate thin films

Seeding to enhance the kinetics of phase transformation was demonstrated with a special seeding process using crystallized ultrafine lead titanate powder to lower the temperature of perovskite formation of the modified lead calcium titanate thin films. X-ray diffraction and scanning electron microscopy show that the pyrochlore-to-perovskite phase transformation temperature of the seeded lead calcium titanate film can be lowered by as much as 50°C when compared with the unseeded lead calcium titanate film. This is most likely related to the decrease of activation energies of nucleation which, in turn, increases the kinetics of the perovskite formation, since numerous nucleation sites are provided. The similarity, or small lattice mismatch of crystal structure between the lead titanate and perovskite of the modified lead calcium titanate film supports these explanations.