Surfactants: Perfect heteroepitaxy of Ge on Si(111)

The hetero growth of Ge on Si results in formation of 3D clusters with an uncontrolled defect structure. Introduction of a monolayer of a surfactant completely changes the growth mode to a 2D-layer growth (Frankvan der Merwe) with a continuous and smooth Ge film on Si(111). The surfactant is not incorporated but segregates and floates on the growing Ge film. The saturation of the dangling bonds of the semiconductor reduces the surface free energy and drives the strong segregation. The effect on the growth process is the selective change of activation energies which are important for diffusion and the mobility of the Ge. Up to a thickness of 8 MLs (MonoLayers) the misfit-related strain of the pseudomorphic Ge film is relaxed by formation of a micro rough surface. This allows a partial relaxation of the Ge towards its bulk lattice constant which would not be possible for a flat and continuous film. For thicker Ge films the misfit of 4.2% is relieved by a periodic dislocation network, which is confined to the Si-Ge interface. Ge-films thicker than 20 MLs are free of defects and completely relaxed to the Ge bulk lattice constant: a model system for perfect heteroepitaxial growth.     

Nano-scale metal cluster deposition using STM

Received: 27 March 1998     

New growth technique for luminescent layers on silicon

We report the growth of siloxene on crystalline silicon (111) surfaces based on the chemical transformation of a calcium disilicide layer. The siloxene films obtained show a prominent luminescence in the green, with intensities comparable to the luminescence observed from porous silicon. The structural properties of the siloxene films are studied with infrared transmission and TEM micrographs.     

Practical interpretation of X-ray rocking curves from semiconductor heteroepitaxial layers

X-ray rocking curves are widely used to study semiconductor heteroepitaxial structures. Examples are given of the use of rocking curves to investigate crystal growth problems, determine layer growth rates, confirm layer thicknesses and to determine the state of relaxation in layers which are above the critical thickness. The application of dynamic simulation and Fourier transformation to the raw data as tools to interpret data from multilayer structures is discussed.     

C60 growth on Si(100), GaSe(0001) and GeS(001)

C₆₀ films have been grown in ultra high vacuum on various crystalline substrates and the structure of the films has been investigated by low energy electron diffraction (LEED) and high resolution electron energy loss spectroscopy (HREELS). The C₆₀ films form randomly oriented nanocrystals on Si(100), mesoscopic polycrystals on GaSe(0001) and microscopic single crystals on GeS(001). The vibrational structure of the C₆₀/substrate interfaces is analyzed in detail by HREELS carried out in the dipole and impact scattering regimes. It is shown that the epitaxy of C₆₀ on GeS(001) is induced by the weak van der Waals bonding and the peculiar corrugation of the substrate surface.     

Epitaxial growth of metals with high Ehrlich–Schwoebel barriers and the effect of surfactants

Interlayer diffusion in epitaxial systems with a high energy barrier at the atomic steps – the so-called Ehrlich–Schwoebel (ES) barrier – is strongly reduced. As a consequence of this, a continuous accumulation of roughness takes place during growth. This undesirable effect can be corrected by using surfactant agents. We have studied the influence of the ES barrier on the preparation of epitaxial films on Cu(111), and the surfactant effect of a monolayer of Pb. Received: 21 April 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999     

Pseudo-epitaxial C60 films prepared by a hot-wall method

We have used both reflection-geometry and grazing-incidence-geometry X-ray scattering to study thin films of C₆₀ evaporated onto mica substrates via a hot-wall technique. The growth mode yields close-packed C₆₀ planes, which are parallel to the substrate surface and which exhibit out-of-plane correlation lengths of 850 Å. In the film plane the C₆₀ is at best pseudo-epitaxial, with a 0.9° distribution of crystallite orientations, a 450 Å in-plane correlation length, and a 3.7% lattice mismatch, better than obtained by other thin film techniques but far from the accepted definition of single crystal thin film epitaxy.     

Simultaneous formation of contacts and diffusion barriers for VLSI by rapid thermal silicidation of TiW

The formation of (Ti_xW_1–x)Si₂/(Ti_xW_1–x)N, by rapid thermal processing of Ti_xW_1–x on Si in an N₂ ambient is investigated. An activation energy of 1.7 eV is obtained for silicide formation. A distinct snow-ploughing of As atoms is observed during silicide formation whereas the interfacial B concentration decreases with increasing silicide formation temperature. The diffusion barrier properties of the (Ti_xW_1–x)Si₂/(Ti_xWi_1–x)N stack in contact with Al is investigated upon post-metal annealing. No interaction between the layers is found for temperatures as high as 475°C after 60 min. The improved thermal stability of the (Ti_xW_1–x)N layer in contact with Al is attributed to nitrogen blocking of the grain boundaries.     

Frictional and atomic-scale study of C60 thin films by scanning force microscopy

Scanning force microscopy (SFM) was employed to characterize C₆₀ island films in an ultra-high vacuum (UHV). The initial growth stage of C₆₀ on NaCl cleavage faces and nanotribological properties of this solid lubricant are investigated. In comparison to the NaCl(001) face, higher friction is measured on the C₆₀ islands, resulting in a ratio of friction of 13 for NaClC₆₀. The friction coefficient of the (111) oriented C₆₀ island is determined to be 0.15±0.05. High-resolution SFM images reveal the hexagonal lattice of the unreconstructed (111) top surfaces and the overgrowth relationships of the C₆₀ islands.     

Threading dislocations in GaAs on Si grown with ∼1 nm thick Si interlayers

Threading dislocation morphologies and characteristics have been investigated in 3 m thick GaAs films with ultrathin (1 nm) Si interlayers grown by molecular beam epitaxy on tilted (2° toward [110]) Si (001) substrates using cross-sectional transmission electron microscopy. Four sample structures are studied in which different numbers of ultrathin Si layers are grown at different positions in the GaAs film, and the results are compared for samples observed before and after ex situ annealing. In all of the sample structures, some mixed-type dislocations are clearly blocked by the Si interlayers, although some of them pass through these layers, resulting in propagation of their threading dislocations to the sample surface. After annealing at 900 °C for 10 s or 800 °C for 30 min, the interactions of the dislocations with the interlayers are enhanced, and there is an increase in the number of dislocations which are bent along the 110 directions at the positions of the Si barrier layers. However, a considerable number of dislocations still escape from the Si barriers by gliding on {111} slip planes during annealing. Moreover, ex situ annealing generates new edge-type dislocations through interactions between moving threading dislocations. The nature of the dislocations that cross the Si barriers is especially discussed.     

Influence of domain boundaries on polarity of GaN grown on sapphire

GaN films were grown on sapphire substrates by laser-induced reactive epitaxy. The domains in the films were determined to be the Ga-polarity by the convergent beam electron diffraction (CBED) technique, while the adjacent matrices had the N-polarity. The domain boundaries were characterized as inversion domain boundaries (IDBs). An atomic structure of the IDB is proposed based on high-resolution transmission electron microscopy (HRTEM) investigations. Control of the polarity of GaN/sapphire films was achieved by suppressing the formation of IDBs with an interlayer of AlGaN and a low-temperature GaN buffer layer.     

Structural and morphological characterization of TiO2 nanostructured films grown by nanosecond pulsed laser deposition

TiO₂ has attracted a lot of attention due to its photocatalytic properties and its potential applications in environmental purification and self cleaning coatings, as well as for its high optical transmittance in the visible-IR spectral range, high chemical stability and mechanical resistance. In this paper, we report on the growth of TiO₂ nanocrystalline films on Si (1 0 0) substrates by pulsed laser deposition (PLD). Rutile sintered targets were irradiated by KrF excimer laser (λ = 248 nm, pulse duration ∼30 ns) in a controlled oxygen environment and at constant substrate temperature of 650 °C. The structural and morphological properties of the films have been studied for different deposition parameters, such as oxygen partial pressure (0.05-5 Pa) and laser fluence (2- 4 J/cm²). X-ray diffraction (XRD) shows the formation of both rutile and anatase phases; however, it is observed that the anatase phase is suppressed at the highest laser fluences. X-ray photoelectron spectroscopy (XPS) measurements were performed to determine the stoichiometry of the grown films. The surface morphology of the deposits, studied by scanning electron (SEM) and atomic force (AFM) microscopies, has revealed nanostructured films. The dimensions and density of the nanoparticles observed at the surface depend on the partial pressure of oxygen during growth. The smallest particles of about 40 nm diameter were obtained for the highest pressures of inlet gas.     

Surface morphology of metal films deposited on mica at various temperatures observed by atomic force microscopy

Thin films of eight metals with a thickness of 150 nm were deposited on mica substrates by thermal evaporation at various temperatures in a high vacuum. The surface morphology of the metal films was observed by atomic force microscopy (AFM) and the images were characterized quantitatively by a roughness analysis and a bearing analysis (surface height analysis). The films of Au, Ag, Cu, and Al with the high melting points were prepared at homologous temperatures T/T_m = 0.22-0.32, 0.40, and 0.56. The films of In, Sn, Bi, and Pb with the low melting points were prepared at T/T_m = 0.55-0.70, where T and T_m are the absolute temperatures of the mica substrate and the melting point of the metal, respectively. The surface morphology of these metal films was studied based on a structure zone model. The film surfaces of Au, Ag, and Cu prepared at the low temperatures (T/T_m = 0.22-0.24) consist of small round grains with diameters of 30-60 nm and heights of 2-7 nm. The surface heights of these metal films distribute randomly around the surface height at 0 nm and the morphology is caused by self-shadowing during the deposition. The grain size becomes large due to surface diffusion of adatoms and the film surfaces have individual characteristic morphology and roughnesses as T increases. The surface of the Al film becomes very smooth as T increases and the atomically smooth surface is obtained at T/T_m = 0.56-0.67 (250-350 °C). On the other hand, the atomically smooth surface of the Au film is obtained at T/T_m = 0.56 (473 ± 3 °C). The films of In, Sn, Bi, and Pb prepared at T/T_m = 0.55-0.70 also show the individual characteristic surface morphology.     

New concepts for controlled homoepitaxy

On the basis of a kinetic growth model we discuss new methods to grow atomically flat homoepitaxial layers in a controlled way. The underlying principle of these methods is to change the growth parameters during growth of an atomic layer in such a way that nucleation on top of a growing layer is suppressed, and thus, layer-by-layer growth is achieved. Experimentally, this can be realized by changing the substrate temperature or deposition rate during monolayer growth in a well-defined way. The same can be achieved at constant temperature and deposition rate by simultaneous ion bombardment during the early stages of growth of a monolayer, or by adding suitable surfactants to the system. Model experiments on Ag(111) and on Cu(111) using thermal energy atom scattering and scanning tunneling microscopy demonstrate the success of these methods.     

Effect of Electrochemical Treatment in a Lithium Chloride Solution on Field Emission from Carbon Nanotubes

Carbon nanotubes （CNTs） are electrochemically treated in a lithium chloride solution at a concentration 0. 1 mol/L The field emission properties of the CNTs are investigated at different temperatures before and after the electrochemical treatment. After treatment, the turn-on voltage to produce field emission current of 10μA decreases from 4.2kV to 2. 7kV and the field emission current increases distinctly, but the stability falls off. Based on the Fowler-Nordheim plot, the values of the work function for the CNTs are calculated, which reveals that work function decreases after the electrochemical treatment. These results are attributed to the decrease of the work function of the carbon nanotubes.     

Dynamics and stability of nanostructures on metal surfaces

Ultrathin metal films consisting of two-dimensional clusters are typically unstable: the cluster ensemble has the tendency to reduce its total free energy via Ostwald ripening or dynamic coalescence of mobile clusters. In this paper we give an overview of recent model experiments addressing these coarsening mechanisms. The experiments have been performed using STM on ensembles consisting of adatom or vacancy clusters with typical diameters in the nanometer range on fcc(111)-metal surfaces. Agreement with and deviations from conventional theories are discussed. Received: 29 March 1999 / Accepted: 17 August 1999 / Published online: 30 September 1999     

The influence of the oxygen exposure on the thermal faceting of W[1 1 1] tip

The oxygen induced faceting of the macroscopic W[1 1 1] tip has been studied for oxygen exposures in the range 0.5-31 L and annealing temperatures 800-1800 K using the field ion microscopy (FIM) technique. After annealing at temperatures lower than 800 K, higher than 1850 K or for exposures lower than 0.5 L faceting was not observed. For exposures 0.5-1.9 L and annealing temperatures 800-1600 K well developed {1 1 2} facets with sharp edges formed. For exposures higher than 2.0 L edges of the {1 1 2} facets were broadening and disappearing, what has been attributed to the formation of three-dimensional tungsten oxides. The oxides could be easily removed by annealing the tip at 1700 K, what leads to formation of sharp facet edges. On the basis of these results a modified procedure of the ultrasharp tip fabrication has been proposed.     

Electrochromic device based on tungsten oxide and on Nnfion-H as polymeric electrolyte

We describe the preparation, electrical and optical characterization of a prototype of a nearly solid-state electrochromic device. It is fabricated with Nafion-H, a polymeric electrolyte, and involves cathodically coloring tungsten trioxide doped with molybdenum. The device switches rapidly with the applied potential ranging from –2.4 up to 0.8V, between blue and transparent state. The corresponding integrated photopic (T _p) and solar (T _s transmittance is T _p (bleached) = 70.7%, T _s (bleached) = 59.6%, T _p (colored) = 15.5%, and T _s (colored) = 12.2%.     

Selective imaging of self-assembled monolayers by tunneling microscopy

The properties of thin organic films offer many challenging opportunities for science and technology. A crucial requirement for the advancement of molecular film technology is the selective characterization and modification on an atomic level. Local proximal probes like Scanning Tunneling Microscopy (STM) or Atomic Force Microscopy (AFM) bear certainly the potential for this purpose. So far, however, mainly adsorbed organic molecules lying flat on a smooth substrate have been imaged with near atomic resolution. Here, we demonstrate the ability of STM to selectively image self-assembled monolayers of long-chain molecules (hexanethiol) oriented upright on the substrate Au(111) with molecular resolution. Upon proper choice of the tunneling parameters we can image the molecular head-group anchored at the substrate and/or the molecular tail group.     

Aluminium oxide thin films prepared by plasma-enhanced chemical vapour deposition

Thin films of aluminium oxide have been deposited on glass, quartz, Si(100), steel, nickel, and aluminium by plasma-enhanced chemical vapour deposition (PECVD) using aluminium acetylacetonate (Al(acac)₃) as precursor. The deposits are hard (up to 2370 HK) and show good adherence to the substrates. The influence of various experimental parameters on deposition rate, film composition and hardness has been studied. The bias turned out to be the most effective parameter.On leave from Beijing Solar Energy Research Institute, Beijing, P.R. China