Nucleation and growth mechanisms of Fe on Au(111) in the sub-monolayer regime

The growth of Fe on Au(111) at 300 K in the sub-monolayer regime has been investigated using scanning tunneling microscopy, focusing on the mechanisms of nucleation, coalescence and interlayer diffusion. Below a coverage of 0.1 ML, Fe growth proceeds in a well-ordered fashion producing regular arrays of islands, while approaching the island coalescence threshold (above 0.35–0.4 ML), we observed a consistent increasing of random island nucleation. These observations have been interpreted through rate equation models for the island densities in the presence of preferred nucleation sites. The evolution of the second layer fraction has also been interpreted in a rate equation scheme. Our results show that the ordered to random growth transition can be explained by including in the model bond breaking mechanisms due to finite Fe–Fe bond energy. A moderate interlayer diffusion has been inferred from data analysis between the second and the first layer, which has been used to estimate the energy barrier of the adatoms descending process.     

Surface chemistry of (2,4-dimethylpentadienyl)(ethylcyclopentadienyl)Ru on polycrystalline Ta

The adsorption and desorption of (2,4-dimethylpentadienyl)(ethylcyclopentadienyl)Ru [DER] on polycrystalline Ta have been studied by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). DER exposures to Ta at 140 K result in primarily molecular adsorption and desorption, while a minor surface reaction occurs at defect sites. Monolayer DER desorbs between 278 and 297 K with increasing coverage, exhibiting a first order, zero coverage desorption energy of 2.3 eV. Multilayer DER desorbs between 272 and 263 K, most likely with fractional order kinetics, and exhibits a zero coverage desorption energy of 0.9 eV. XPS Ru 3d binding energies increase with increasing coverage due to core hole screening in the monolayer regime and increasing sample charging as the DER overlayer becomes thicker in the multilayer regime. DER exhibits a three-dimensional (3D) “hit and stick” growth mode in which random 3D structures form due to the lack of adsorbate mobility at 140 K. DER exposures to Ta between 298 and 773 K result in minor decomposition resulting primarily in adsorbed hydrocarbon species on the surface. When the Ta is pre-covered with atomic iodine, DER dissociation is significantly decreased while adsorption is increased.     

Computer simulation of random sequential adsorption of two interacting species on a lattice

A computer-simulation model is introduced to study the variation in the coverage and porosity in a binary system by random sequential adsorption on a periodic square lattice. We study the effects of the range of the repulsive interaction between unlike species and of the probability of deposition of each particle type. For all choices of the interaction range there is a minimum in the total coverage of the lattice which occurs for equal deposition probability of the two species. The saturation coverage decreases on increasing the range of the interaction. For proper choices of the parameters of the model, regimes exist in which either pores or particles of one type form an infinite percolating network.     

Diffusion-limited electrodeposition of ultrathin Au films on Pt(1 1 1)

The electrodeposition of Au on Pt(1 1 1) from electrolytes containing μM concentrations of was studied by in situ scanning tunneling microscopy. Under these conditions the Au flux is limited by diffusion in the electrolyte over a wide potential range, which allows to assess the effect of the electrochemical environment on the growth kinetics. Similar to gas phase metal deposition Au film growth proceeds via nucleation and lateral growth of Au monolayer islands, with the saturation island density strongly depending on the deposition potential and on the anion species in the electrolyte. For deposition in H₂SO₄ solution the saturation island density continuously increases with increasing potential between −0.2 and 0.5 V (SCE), whereas in Cl-containing H₂SO₄ it first decreases and then increases again. Following nucleation and growth theories this behavior can be attributed to potential-induced changes of the Au surface mobility, caused by changes in the density and structure of coadsorbed sulfate/bisulfate and chloride adlayers. Under conditions of high Au surface mobility multilayer growth proceeds via a typical Stranski-Krastanov growth mode, with layer-by-layer growth of a pseudomorphic Au film up to 2 ML and 3D growth of structurally relaxed islands at higher coverage, indicating thermodynamic control under these conditions.     

Heterogeneous nucleation and depletion effect in nanowire growth

Recent experiments by Ross and co-workers proved the possibility of a mononuclear regime with heterogeneous nucleation as well as jerky growth in the vapor–liquid–solid (VLS) process for silicon nanowires. In this work, a theoretical model is presented which incorporates the effects of (i) a mononuclear regime with layer by layer growth, (i) heterogeneous nucleation of each new layer at the edge of a Au–Si droplet, (iii) drop of supersaturation after each successful nucleation and respective fast layer growth, (iv) time-dependent nucleation barrier during each new waiting period and (v) correlation between subsequent waiting periods (non-Markovian sequence of waiting periods).     

Substrate-step-induced effects on the growth of CaF2 on Si (111)

The growth of CaF₂ on vicinal Si (111) surfaces was studied by scanning tunneling microscopy (STM) and atomic force microscopy (AFM) for the temperature range from 300 to 750 °C. In the submonolayer range a transition from terrace to step nucleation is observed for increasing temperature. The first monolayer grows in the step-flow growth mode since second layer islands are not nucleated before completion of the wetting layer. For the subsequent growth of CaF₂ on the CaF interface layer, substrate-induced steps do not act as preferential nucleation sites, but rather as growth barriers. Thus CaF₂ films grow very inhomogeneously at high temperatures. At lower deposition temperatures, the film homogeneity increases due to the increased (homogeneous) nucleation rate on terraces. The lattice mismatch leads to (lateral) relaxation of thicker CaF₂ film close to substrate steps. In addition, CaF₂ self-decoration effects are caused by the relaxed regions close to the film steps at temperatures above 500 °C. Received: 7 August 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002     

Nanostructure evolution during thin film deposition

It is shown how that the combination of atomic deposition and nonlinear diffusion may lead, below a critical temperature, to the growth of nonuniform layers on a substrate. The dynamics of such a system is of the Cahn–Hilliard type, supplemented by reaction terms representing adsorption–desorption processes. The instability of growing uniform layers leads to the formation of nanostructures which correspond to regular spatial variations of substrate coverage. Patterns wavelengths and symmetries are selected by the dynamics and not by variational arguments. For temperatures below critical, one should observe hexagonal arrays of high coverage dots on the surface of otherwise uniform growing layers. On decreasing further the temperature, these structures should transform into hexagonal arrays of low coverage domains, within the growing layer.     

The nucleation of pentacene thin films

Photoemission Electron Microscopy was used to determine basic factors for nucleation and growth of thin pentacene films. Dependence of both substrate chemistry and deposition rate on the nucleation density was observed. On SiO₂ pentacene shows a high nucleation density and forms small islands consisting of almost vertically oriented molecules. On Si(001) the nucleation density of this thin-film phase is much smaller, but the pentacene film first forms a flat-lying wetting layer. The thin-film phase only forms on top of this wetting layer. Adsorption of a cyclohexene self-assembled monolayer on Si(001) prior to the pentacene growth suppresses the initial pentacene wetting layer but maintains diffusion parameters similar to pentacene on Si(001). The nucleation of pentacene layers on cyclohexene/Si(001) can be described by classical nucleation theory with a critical nucleus size i6. Simple surface modification techniques such as e-beam irradiation of the substrates prior to pentacene adsorption can also have a significant effect on the pentacene nucleation density. PACS 68.37.Nq; 68.43.Fg; 68.47.Fg; 68.55.Ac     

Direct observation of strain relaxation in iron layers on W(110) by time-resolved STM

Time-resolved,in-situ-applied STM has been used to study the epitaxial growth of iron on W(110) at room temperature. By this way, sequences of STM images show directly the atomistics of the growth process on the surface. The first layer of iron on W(110) grows pseudomorphically without a preferred growth direction. Beginning with the second layer, the islands grow anisotropically with preferred growth in the [001]-direction. The generation of an ordered two-dimensional dislocation network starts at a coverage of 1.4 pseudomorphic monolayers to relax the misfit of 9.4%. A direct correlation of the creation of misfit dislocations in the second layer and the nucleation of the third-layer islands was found. Together with the onset of strain relaxation, the growth mode abruptly changes from layer-by-layer to statistical growth. A quantitative statistical analysis of the data allows to exactly determine the onset of relaxation, the vertical location of the dislocation lines, and the lateral extension of an island that is necessary to induce the formation of dislocations.     

Nanofabrication of tungsten supertip by electron-beam-induced deposition

Two methods were used to fabricate tungsten supertips by electron-beam-induced deposition using 200 keV electrons. The first method is stationary deposition of self-standing tips. The smallest lateral size is less than 10 nm with a rather low aspect ratio of tip. High aspect ratio (up to 30) can only be obtained at a big lateral size with a saturated root diameter of 60–65 nm. The other method is scan deposition of self-supporting tip, with a root width of 7–10 nm and a sharp apex in size of 3 nm. Using this method a higher aspect ratio (more than 72) can be achieved at a smaller lateral size, which is better to fabricate fine supertips for usage.     

Effect of interface layer on growth behavior of atomic-layer-deposited Ir thin film as novel Cu diffusion barrier

Growth and nucleation behavior of Ir films grown by atomic layer deposition (ALD) on different interfacial layers such as SiO₂, surface-treated TaN, and 3-nm-thick TaN were investigated. To grow Ir thin film by ALD, (1,5-cyclooctadiene) (ethylcyclopentadienyl) iridium (Ir(EtCp)(COD)) and oxygen were employed as the metalorganic precursor and reactant, respectively. To obtain optimal deposition conditions, the deposition temperature was varied from 240 to 420 °C and the number of deposition cycles was changed from 150 to 300. The Ir film grown on the 3-nm-thick TaN surface showed the smoothest and most uniform layer for all the deposition cycles, whereas poor nucleation and three-dimensional island-type growth of the Ir layer were observed on Si, SiO₂, and surface-treated TaN after fewer number of deposition cycles. The uniformity of the Ir film layer was maintained for all the different substrates up to 300 deposition cycles. Therefore we suggest that the growth behavior of the Ir layer on different interface layer is related to the chemical bonding pattern of the substrate film or interface layer, resulting in better understand the growth mechanism of Ir layer as a copper diffusion barrier. The ALD-grown Ir films show the preferential direction of (1 1 1) for all the reflections, which indicates the absence of IrO₂ in metallic Ir.     

Temperature and reconstruction dependence of the initial Al growth on GaAs(001)

The development of the interface between Al and MBE-grown GaAs(001) surfaces has been analyzed up to a mean Al coverage of 0.5 nm. Interdiffusion, chemical reactivity and nucleation have been studied by Auger electron spectroscopy and reflection high energy electron diffraction for the c(2 × 8) and the (4 × 6) surface reconstructions in the temperature interval 268 to 673 K. Above 550 K no nucleation was observed and the growth process was governed by As outdiffusion followed by formation of AlAs. At lower temperatures three characteristic regions of Al coverage were found. The different growth mechanisms in these regions are discussed. An AlGa exchange reaction was observed only on the Ga-rich (4 × 6) structure where it was also correlated to the nucleation. The particular deposition measurement procedure used was found to be an important parameter, since interdiffusion was observed even at room temperature. The coverage at which 3D nucleation occurred was dependent on both substrate temperature and surface reconstruction but always appeared between 1.5 and 3.5 monolayer coverage. A strong temperature dependence of the nucleation was observed.     

Theory of multiple-pass two-photon Doppler-free spectroscopy

Electron stimulated desorption (ESD) of CO on Ru (001) leads to emission of CO⁺ and O⁺ ions from the same adsorption states. Following earlier work on this system, a correlated study of its ESD behaviour together with LEED, Δϕ, and TPD measurments has been carried out. The filling of the two states found earlier can be seen in ESD also. The dividing line between the high and low energy states is different in room temperature adsorption on the one hand, and desorption or equilibrium measurements at elevated temperatures on the other, which is explained by incomplete attainment of equilibrium in the layer under the first condition. The behaviour of the ESD ion currents with coverage showstthat part of the molecules occupying high energy sites in the ordered layer of intermediate coverage are shifted to less favourable sites at higher coverage, so that the full layer consists of a mixture of states due to the occupation of different sites in the compressed layer, possibly accompanied by lateral interactions. ESD also suggests that the high energy sites are the on-top sites rather than the threefold sites.     

AES investigations of growth of very thin silver films deposited on the copper and nickel (110) faces

Growth of very thin silver films deposited under UHV conditions on the Ni(110) and Cu(110) faces was studied with the Auger Electron Spectroscopy. Silver 360eV and nickel 61eV Auger peaks kinetics show the Stranski-Krastanov growth mechanism. Two stages of the first ML growth at room temperature was observed. During annealing of 2 ML layer (the rate of temperature increase of 4 K/s) the silver Auger peak increases by about 10% atT 620 K. This indicates that reconstruction of silver islands takes place. The first monolayer desorbs atT=840 K. The Cu-Ag system was studied with silver 360eV and copper 62eV Auger peaks. The adsorption kinetics, up to 440 K, show the Stranski-Krastanov growth mechanism. After 1 ML deposition, the increase of the substrate temperature leads to the slope decrease of the adsorption kinetics. Adsorption kinetics forT=560–620 K show that after 1.5 ML deposition the silver dissolution occurs and the surface alloy is formed. Above 770 K the shape of kinetics drastically changes due to the decrease of a sticking coefficient.Presented at the Seminar on Secondary Electrons in Electron Spectroscopy, Microscopy, and Microanalysis, Chlum (The Czech Republic), 21–24 September, 1993.The authors would like to thank B. Stachnik and Z. Jankowski for the preparation of the measuring system.The work was supported by the Polish Committee for Scientific Research under Grant Nr. 20119 91 01.     

Study of the Elementary Growth Processes During Vapor-Phase Epitaxy of Semiconducting III–V Compounds

A review of studies performed at the V. D. Kuznetsov Siberian Physical-Technical Institute at Tomsk State University and aimed at obtaining detailed information on the elementary growth processes proceeding at the crystallization front during vapor-phase epitaxy of semiconducting III–V compound films is presented in the paper. The general approach to the problem and methods of its solution are described. Results of investigations of the adsorption layer composition, surface diffusion processes, and incorporation of growth components into a crystal are presented. The mechanism of epitaxial layer growth in semiconducting III–V compounds is discussed.     

Structure of Al deposits on nanometer-size islands of aluminum-oxide

Because of the immense structural mismatch between a crystal and a quasicrystal, the aluminum-oxide domains that grow on the pentagonal surface of icosahedral Al–Pd–Mn at high temperatures are in the order of a few nm large. Here, we exploit the small lateral extension of the oxide domains to grow crystalline Al particles in the same size-region by vapor deposition on them. Low-energy-electron diffraction and secondary-electron imaging investigations show that the nanocrystals expose their (1 1 1) faces parallel to the pentagonal surface of the quasicrystal, while the in-plane orientation of the crystallites is random. Spot-profile analysis of the diffracted beams indicate that the Al nanocrystals grow in 3 nm large domains up to a deposition thickness of 51 monolayers.     

Simulation study on nanocluster growth deposited on a substrate

We present a model equation that describes nucleation and growth of hemispherical nanoclusters or islands deposited on a substrate for the small surface coverage case. The model is formulated in terms of a set of rate equations for the island sizes, combined with the time-dependent behavior of supersaturation and island nucleation rate. As an example to demonstrate the usefulness of the model, we study effects of the deposition rate of adatoms on the nanocluster growth. Large-scale computer simulation results show that the broadness of island size distribution is a decreasing function of the deposition rate for small rates, and bimodal distributions are obtained for large rates.     

Scanning tunneling microscopy and spectroscopy investigations of copper phthalocyanine adsorbed on Al2O3/Ni3Al(1 1 1)

Low temperature scanning tunneling microscopy (LT-STM) and scanning tunneling spectroscopy (STS) have been used to investigate adsorbed copper phthalocyanine (C₃₂H₁₆N₈Cu) molecules on an ordered ultrathin Al₂O₃ film on the Ni₃Al(1 1 1) surface as a function of coverage and annealing temperature. For sub-monolayer coverage and a deposition temperature of 140 K two different planar molecular adsorption configurations rotated by 30° with respect to each other were observed with submolecular resolution in the STM images. The template effect of the underlying oxide film on the CuPc orientation, however, is only weak and negligible at higher coverages. For θ_CuPc ≈ 1 ML, before completion of the first layer, the growth of a second layer was already observed. The measured spacing of 3.5 Å between first and second layer corresponds to the distance between the layers in the α-modification of crystalline CuPc. The molecules deposited at 140 K are thermally stable upon prolonged annealing to temperatures up to 250 K. By the use of STS the lowest unoccupied molecular orbital (LUMO) of the adsorbed copper phthalocyanine molecules has been identified at an energy of 1.2 eV above E_F. The lateral distribution of the electronic states of the CuPc has been analyzed and mapped by STS.     

Random walk in a random multiplicative environment

We investigate the dynamics of a random walk in a random multiplicative medium. This results in a random, but correlated, multiplicative process for the spatial distribution of random walkers. We show how the details of these correlations determine the asymptotic properties of the walk, i.e., the central limit theorem does not apply to these multiplicative processes. We also study a periodic source-trap medium in which a unit cell contains one source, followed byL–1 traps. We calculate the asymptotic behavior of the number of particles, and determine the conditions for which there is growth or decay in this average number. Finally, we discuss the asymptotic behavior of a random walk in the presence of randomly distributed, partially-absoprbing traps. For this case, a temporal regime of purely exponential decay of the density can occur, before the asymptotic stretched exponential decay, exp(–at ^1/3), sets in.