Influence of surface temperature and surface modifications on the initial layer growth of para-hexaphenyl on mica (0 0 1)

Ultra-thin films of para-hexaphenyl (6P) were prepared on muscovite mica (0 0 1) utilizing organic molecular beam deposition (OMBD) under well defined ultra high vacuum (UHV) conditions. The 6P growth characteristics were studied as a function of substrate temperature and substrate surface conditions. For the initial state of layer growth, thermal desorption spectroscopy (TDS) was used to verify the existence of a wetting layer. In this monomolecular continuous wetting layer, the molecules lie flat on the surface and are rather strongly bonded. For thicker films, in-situ X-ray photoelectron spectroscopy (XPS) in combination with (TDS) was applied to reveal the kinetics of the layer growth. Ex-situ atomic-force microscopy (AFM) was used to determine the film morphology. In particular, the influence of surface modifications (carbon contamination, sputtering) on 6P layer growth was investigated. XPS and low energy electron diffraction (LEED) were used to characterize the mica surface before the film deposition. TDS and AFM revealed a considerable change in film growth, from a needle-like island growth of flat laying molecules on top of the wetting layer (for the air cleaved mica) to terrace-like film growth of standing molecules, without a wetting layer (after surface modifications).     

The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM

The growth of para-sexiphenyl (6P) thin films as a function of substrate temperature on Ir{111} supported graphene flakes has been studied in real-time with Low Energy Electron Microscopy (LEEM). Micro Low Energy Electron Diffraction (μLEED) has been used to determine the structure of the different 6P features formed on the surface. We observe the nucleation and growth of a wetting layer consisting of lying molecules in the initial stages of growth. Graphene defects – wrinkles – are found to be preferential sites for the nucleation of the wetting layer and of the 6P needles that grow on top of the wetting layer in the later stages of deposition. The molecular structure of the wetting layer and needles is found to be similar. As a result, only a limited number of growth directions are observed for the needles. In contrast, on the bare Ir{111} surface 6P molecules assume an upright orientation. The formation of ramified islands is observed on the bare Ir{111} surface at 320 K and 352 K, whereas at 405 K the formation of a continuous layer of upright standing molecules growing in a step flow like manner is observed.     

Ab initio-based approach to the reconstruction on InAs(111)A wetting layer grown on GaAs substrate

The surface reconstructions on InAs(111)A wetting layer grown on GaAs substrate are investigated by our ab initio-based approach incorporating the chemical potentials of In atom and As molecules in the vapor phase as functions of temperature and beam equivalent pressure. The calculated results imply that the most stable surface structure of InAs with/without lattice constraint from the substrate is the In-vacancy surface under conventional growth conditions. The In-vacancy surface is dramatically stabilized on the wetting layer, since the atoms around the In-vacancy are easily displaced to effectively lower the strain energy due to the lattice constraint from the GaAs substrate. Distinctive feature between InAs(111)A surfaces with and without lattice constraint is found in the stable adsorption sites. In adatoms favor the In-vacancy site on the InAs without lattice constraint in contrast to the interstitial sites on the InAs wetting layer. These results suggest that the surface structure and adsorption-desorption behavior on the wetting layer are crucial for investigating the growth processes of nanostructures such as quantum dots and stacking fault tetrahedrons.     

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     

Initial stages of Ge epitaxy on Si(111) under quasi-equilibrium growth conditions

The results of the structural and morphological studies of Ge growth on a Si(111) surface at the initial stages of epitaxy by means of scanning tunneling microscopy and high-resolution transmission electron microscopy are presented. Epitaxy of Ge has been performed in the temperature range of 300 to 550°C under the quasi-equilibrium growth conditions and low deposition rates of 0.001–0.01 bilayers per minute. The stages of the formation and decay of the nanoclusters as a result of the redistribution of the Ge atoms into two-dimensional pseudomorphic Ge islands before the formation of the continuous wetting layer have been experimentally detected. The positions of the preferable nucleation of three-dimensional Ge islands on the wetting layer formed after the coalescence of the two-dimensional islands have been analyzed. The c2 × 8 → 7 × 7 → c2 × 8 phase transitions due to the lateral growth of the islands and the plastic relaxation of the misfit strains occur on the surface of the three-dimensional Ge islands when their strain state changes. The misfit dislocations gather at the interface and two types of steps lower than one bilayer are formed on the surface of the three-dimensional islands during the relaxation process.     

InAs wetting layer evolution on GaAs(0 0 1)

The evolution of two-dimensional (2D) strained InAs wetting layers on GaAs(0 0 1), grown at different temperatures by molecular beam epitaxy, was studied by in situ high-resolution scanning tunneling microscopy. At low growth temperature (400 °C), the substrate exhibits a well-defined GaAs(0 0 1)-c(4 × 4) structure. For a disorientation of 0.7°, InAs grows in the step-flow mode and forms an unalloyed wetting layer mainly along steps, but also in part on the terrace. The wetting layer displays some local c(4 × 6) reconstruction, for which a model is proposed. 1.2 monolayer (ML) InAs deposition induces the formation of 3D islands. At a higher temperature (460 °C), the wetting layer is obviously alloyed even at low InAs coverage. The critical thickness of the wetting layer for the 2D-to-3D transition is shifted to 1.50 ML in this case presumably since the strain is reduced by alloying.     

The influence of oxygen on the growth of silver on Cu(110)

The influence of the (2 × 1)O reconstruction on the growth of Ag on a Cu(110) surface was studied by scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). On the bare Cu(110) surface, Stranski–Krastanov growth of silver is observed at sample temperatures between 277 K and 500 K: The formation of a Ag wetting layer is followed by the growth of three-dimensional Ag wires. In contrast, on the oxygen-precovered Cu(110) surface, the growth of silver depends heavily on the substrate temperature. Upon Ag deposition at room temperature, a homogeneous, polycrystalline Ag layer is observed, whereas at 500 K, three-dimensional wires separated by (2 × 1)O reconstructed areas are formed. The behavior of a deposited Ag layer upon annealing is also influenced greatly by the presence of oxygen. On the bare surface, annealing does not change the Ag wetting layer and gives rise to Ostwald ripening of the Ag wires. On the oxygen-precovered surface, however, the initial polycrystalline Aglayer first transforms into Ag wires at around 500 K. Above this temperature, the depletion of the (2 × 1)O reconstructed areas due to Ag-induced O desorption is balanced by the formation of a Ag wetting layer. On both, the bare and the oxygen-precovered Cu(110) surface, the deposited silver diffuses into the Cu bulk at temperatures above 700 K.     

Effect of self-assembled Ge nanostructures on Si surface electronic properties

Incorporating self-assembled Ge islands on Si surfaces into electronic devices has been suggested as a means of forming small features without fine-scale litho- graphy. For use in electronic devices, the electrical properties of the deposited Ge and their relation to the underlying Si substrate must be known. This report presents the results of a surface photovoltage investigation of the surface energy barrier as increasing amounts of Ge are added to a Si surface by chemical vapor deposition. The results are interpreted in terms of band discontinuities and surface states. The surface barrier increases as a wetting layer is deposited and continues to increase as defect-free islands form. It saturates as the islands grow. As the amount of Ge continues increasing, defects form, and the surface barrier decreases because of the resulting allowed states at the Ge/Si interface. Qualitatively similar behavior is found for Si(001) and Si(111). Covering the Ge with Si reduces the surface-state density and possibly modifies the wetting layer, decreasing the barrier to one more characteristic of Si. Initial hydrogen termination of the surface decreases the active surface-state density. As the H desorbs, the surface barrier increases until it stabilizes as the surface oxidizes. The behavior is briefly correlated with scanning-tunneling spectroscopy data. Received: 13 November 2000 / Accepted: 14 November 2000 / Published online: 23 May 2001     

Experimental studies of solid state surface wetting of tin (Sn) on aluminium (Al)

Under ultra high vacuum (UHV) conditions tin (Sn) forms a monoatomic wetting layer on aluminium (Al) surfaces if Sn-islands formed by a preceding deposition process are present. Previous experimental observations and Kinetic Monte Carlo (KMC) simulations suggest that wetting layer formation is governed by thermally activated surface diffusion and adsorption processes.This paper presents a systematic study of the wetting of the inner and outer interfaces of Al by Sn in sandwich systems consisting of a 400 nm Al-base layer, a 10 nm Sn interlayer and a 400 nm thick Al capping layer. The morphology and chemical composition of the sandwich systems is investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The wetting process is studied by scanning auger electron spectroscopy (AES) under UHV conditions. Depositing the Al-capping layer at different deposition rates allows for the assessment of the influence of the grain boundary density on the velocity of Sn-transport through the Al-capping layer. Studying the permeation speed of Sn through the capping layer at different temperatures shows that Sn penetrates the capping layer much more rapidly at elevated temperatures thus corroborating the involvement of thermally activated mechanisms in the transport process.     

Formation of InAs quantum dots and wetting layers in GaAs and AlAs analyzed by cross-sectional scanning tunneling microscopy

We have used cross-sectional scanning-tunneling microscopy (X-STM) to compare the formation of self-assembled InAs quantum dots (QDs) and wetting layers on AlAs (1 0 0) and GaAs (1 0 0) surfaces. On AlAs we find a larger QD density and smaller QD size than for QDs grown on GaAs under the same growth conditions (500 °C substrate temperature and 1.9 ML indium deposition). The QDs grown on GaAs show both a normal and a lateral gradient in the indium distribution whereas the QDs grown on AlAs show only a normal gradient. The wetting layers on GaAs and AlAs do not show significant differences in their composition profiles. We suggest that the segregation of the wetting layer is mainly strain-driven, whereas the formation of the QDs is also determined by growth kinetics. We have determined the indium composition of the QDs by fitting it to the measured outward relaxation and lattice constant profile of the cleaved surface using a three-dimensional finite element calculation based on elasticity theory.     

Hydrodynamic-flow-driven wetting in thin film polymer blends: growth kinetics and morphology

A thin film of deuterated poly(methyl methacrylate) (A) and poly(styrene-ran-acrylonitrile) at the critical composition is annealed in the two phase region to induce simultaneous phase separation and wetting of the A-rich phase at the surface. Using forward recoil spectrometry, the wetting layer thickness is found to grow linearly with time at 185 degrees C and 190 degrees C. After selective etching of A, atomic force microscopy reveals a depletion layer having a bicontinuous, phase separated morphology. The A-rich tubes in this layer provide a pathway for rapid transport of the wetting phase from the bulk to the surface via hydrodynamic flow. Taken together, fast wetting layer growth t(1) and connectivity between the wetting layer and bulk provide unambiguous support for hydrodynamic-flow-driven wetting in thin film polymer blends.     

Influence of a predeposited Si1−x Gex layer on the growth of self-assembled SiGe/Si(001) islands

The growth of self-assembled Ge(Si) islands on a strained Si_1?xGe_x layer (0% < x < 20%) is studied. The size and the surface density of islands are found to increase with Ge content in the Si_1?xGe_x layer. The increased surface density is related to augmentation of the surface roughness after deposition of the SiGe layer. The enlargement of islands is accounted for by the decrease of the wetting layer in thickness due to the additional elastic energy accumulated in the SiGe layer and to enhanced Si diffusion from the Si_1?xGe_x layer into the islands. The increase in the fraction of the surface occupied by islands leads to a greater order in the island arrangement.     

Epitaxial growth of Au and Pt on Fe3O4(1 1 1) surface

We have studied the epitaxial growth of Au and Pt layers on Fe₃O₄(1 1 1) as a function of the deposition temperature and thickness. The layers were deposited by UHV sputtering and the structural properties were investigated by reflection high energy electron diffraction (RHEED), X-ray experiments and transmission electron microscopy (TEM). The epitaxial growth of both metals was obtained whatever the deposition conditions but the wetting is however different for the two metals. Comparison between the coverage ratios of Au and Pt is correlated with their surface and interfaces energies. The optimum conditions to achieve a 2D flat epitaxial metallic layer are determined.     

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.     

Intermixing at the interface of the system Nb/Fe(1 1 0) investigated by STM

The growth of niobium on the Fe(1 1 0) surface at a deposition temperature between room temperature (RT) and 680 K was studied using in situ STM and LEED. At RT we observe no indication of intermixing. Although a final roughness of only 1.7 Å is reached, the crystalline quality is low. At elevated growth temperatures the development of a surface alloy was observed, whose formation is ascribed to an exchange mechanism through which Nb adatoms are incorporated into the Fe surface. These Nb atoms arrange themselves in chains along the [0 0 1] direction. The expelled Fe atoms form islands on the Nb/Fe-alloy substrate. At higher coverage additionally a Nb wetting layer and intermixed 3D islands evolve.     

Features of atomic processes at the formation of a wetting layer and nucleation of three-dimensional Ge islands on Si(111) and Si(100) surfaces

The intermediate stages of the formation of a Ge wetting layer on Si(111) and Si(100) surfaces under quasiequilibrium grow conditions have been studied by means of scanning tunneling microscopy. The redistribution of Ge atoms and relaxation of mismatch stresses through the formation of surface structures of decreased density and faces different from the substrate orientation have been revealed. The sites of the nucleation of new three-dimensional Ge islands after the formation of the wetting layer have been analyzed. Both fundamental differences and common tendencies of atomic processes at the formation of wetting layers on Si(111) and Si(100) surfaces have been demonstrated. The density of three-dimensional nuclei on the Si(111) surface is determined by changed conditions for the surface diffusion of Ge adatoms after change in the surface structure. Transition to three-dimensional growth on the Si(100) surface is determined by the nucleation of single {105} faces on the rough Ge(100) surface.     

Thermodynamic analysis on the stability and evolution mechanism of self-assembled quantum dots

A quantitative thermodynamic model addressing the stability and evolution mechanism during growth process of quantum dots (QDs) in Stranski-Krastanow (SK) system is established by taking into account the thickness-dependent surface energy of wetting layer (WL). It is found that the thickness-dependent surface energy of WL prevents QDs from growing up without limit. The competition between relaxation energy of QDs and thickness-dependent surface energy of WL results in a puzzling phenomenon that WL not only can hardly capture atoms to grow, but also need release atoms into QDs during deposition process and annealing. Agreement between theoretical results and experiments implies that the established thermodynamic model could be expected to be a general approach to pursue the physical mechanisms of self-assembly of quantum dots.     

Ag/Si(111)-(7X7) Heteroepitaxy—STM Experiment and KMC Simulations

Heteroepitaxial growth of Ag on Si(111)-(7X7) surface at various conditions was experimentally studied by scanning tunneling microscopy. A growth model based on experiments was used for kinetic Monte Carlo (KMC) simulations. The simulations of nucleation and island growth at low coverage and fitting experimental data provided basic growth parameters. Further growth—formation of a discontinuous transition film (wetting layer)—was implemented into the basic model. The suggested growth mechanism was successfully tested using the KMC simulations. The choice of experiments, the role of minimizing processes and parameters in the model, and efficiency of the used approach is demonstrated and discussed.     

Surface mobility difference between Si and Ge and its effect on growth of SiGe alloy films and islands

Based on first-principles calculations of surface diffusion barriers, we show that on a compressive Ge(001) surface the diffusivity of Ge is 10(2)-10(3) times higher than that of Si in the temperature range of 300 to 900 K, while on a tensile surface, the two diffusivities are comparable. Consequently, the growth of a compressive SiGe film is rather different from that of a tensile film. The diffusion disparity between Si and Ge is also greatly enhanced on the strained Ge islands compared to that on the Ge wetting layer on Si(001), explaining the experimental observation of Si enrichment in the wetting layer relative to that in the islands.     

Effect of oxygen on the stability of Ag islands on Si(111)-7 × 7

We have used scanning tunneling microscopy to probe the effect of oxygen exposure on an ensemble of Ag islands separated by a Ag wetting layer on Si(111)-7 × 7. Starting from a distribution dominated by islands that are 1 layer high (measured with respect to the wetting layer), coarsening in ultrahigh vacuum at room temperature leads to growth of 2-layer islands at the expense of 1-layer islands, which is expected. If the sample is exposed to oxygen, 3-layer islands are favored, which is unexpected. There is no evidence for oxygen adsorption on top of Ag islands, but there is clear evidence for adsorption in the wetting layer. Several possible explanations are considered.