Atomic structure of alkali halide surfaces

The atomic structure of surfaces of alkali halide crystals has been revealed by means of high-resolution dynamic force microscopy. True atomic resolution is demonstrated both on steps surrounding islands or pits, and on a chemically mixed crystal. We have directly observed the enhanced interaction at low-coordinated sites by force microscopy. The growth of NaCl films on metal surfaces and radiation damage in a KBr surface is discussed based on force microscopy results. The damping of the tip oscillation in dynamic force microscopy might provide insight into dissipation processes on the atomic scale. Finally, we present atomically resolved images of wear debris found after scratching a KBr surface. PACS 68.37.-d; 68.37.Ps; 75.55.Fv     

High-resolution imaging of C60 molecules using tuning-fork-based non-contact atomic force microscopy

Recent advances in non-contact atomic force microscopy (nc-AFM) have led to the possibility of achieving unprecedented resolution within molecular structures, accomplished by probing short-range repulsive interaction forces. Here we investigate C(60) molecules adsorbed on KBr(111) and Cu(111) by tuning-fork-based nc-AFM. First, measurements of C(60) deposited on KBr(001) were conducted in cryogenic conditions revealing highly resolved nc-AFM images of the self-assembly. Using constant-frequency shift mode as well as three-dimensional spectroscopic measurements, we observe that the relatively weak molecule-substrate interaction generally leads to the disruption of molecular assembled structures when the tip is probing the short-range force regime. This particular issue hindered us in resolving the chemical structure of this molecule on the KBr surface. To obtain a better anchoring of C(60) molecules, nc-AFM measurements were performed on Cu(111). Sub-molecular resolutions within the molecules was achieved which allowed a direct and unambiguous visualization of their orientations on the supporting substrate. Furthermore, three-dimensional spectroscopic measurements of simultaneous force and current have been performed above the single molecules giving information of the C(60) molecular orientation as well as its local conductivity. We further discuss the different imaging modes in nc-AFM such as constant-frequency shift nc-AFM, constant-height nc-AFM and constant-current nc-AFM as well as three-dimensional spectroscopic measurement (3D-DFS) employed to achieve such resolution at the sub-molecular scale.     

Fabrication of rubrene nanowires on vicinal (0 0 0 1) sapphire surfaces

Morphology of high-vacuum deposited rubrene thin films on the annealed (0 0 0 1) vicinal sapphire surfaces was studied by atomic force microscopy in non-contact mode. Atomic force microscopy images of rubrene thin films indicate that a regular array of steps on the sapphire surface acts as a template for the growth of the arrays of rubrene nanosize wires. To further demonstrate that morphological features of a substrate are crucial in determining the morphology of rubrene layers we have grown rubrene on the sapphire surfaces that were characterized by the terrace-and-step morphology with islands. We have found preferential nucleation of rubrene molecules at the intersection between a terrace and a step, as well as around the islands located on terraces.     

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     

The role of charge-induced defects in the growth of gold on an alkali halide surface

Gold on KBr, a prototypical system for studies of metal on insulator growth, is investigated by noncontact atomic force microscopy. It is shown that charge emitted during deposition results in the generation of surface defects via charge-induced desorption. Moreover, the defect and gold nanoparticle number densities follow a highly similar temperature dependence, suggesting that the gold growth is dominated by nucleation at the defects. The defects created at elevated temperatures are monolayer-deep rectangular pits, while those created at room temperature have an irregular structure.     

Critical shape and size for dislocation nucleation in Si1-xGex islands on Si(001)

The critical volume for the onset of plastic strain relaxation in SiGe islands on Si(001) is computed for different Ge contents and realistic shapes by using a three-dimensional model, with position-dependent dislocation energy. It turns out that the critical bases for dome- and barnlike islands are different for any composition. By comparison to extensive atomic force microscopy measurements of the footprints left on the Si substrates by islands grown at different temperatures (and compositions), we conclude that, in contrast with planar films, dislocation nucleation in 3D islands is fully thermodynamic.     

Kinetic effects in the self-assembly of pure and mixed tetradecyl and octadecylamine molecules on mica

The self-assembly of tetradecylamine (C14) and of mixtures of tetradecyl and octadecylamine (C18) molecules from chloroform solutions on mica has been studied using atomic force microscopy (AFM). For pure components self-assembly proceeds more slowly for C14 than for C18. In both cases after equilibrium is reached islands of tilted molecules cover a similar fraction of the surface. Images of films formed by mixtures of molecules acquired before equilibrium is reached (short ripening time at room temperature) show only islands with the height corresponding to C18 with many pores. After a long ripening time, when equilibrium is reached, islands of segregated pure components are formed.     

Stranski-Krastanov growth of CuCl on MgO(001)

Initial growth of CuCl, a zinc-blende-structure I–VII ionic compound, on MgO(001) with NaCl-type structure has been studied using reflection high-energy electron diffraction (RHEED) and atomic force microscopy (AFM). An intermediate layer of adsorbed CuCl, which has a surface structure strongly influenced by the host lattice, was formed before islanding. This layer is easily distinguished from (111) top surfaces of the CuCl islands with trigonal symmetry which have been grown subsequently. This implies that CuCl grows in the Stranski-Krastanov growth mode, which also explains why the nucleation of the islands is insensitive to the step edges of MgO(001).     

Epitaxial growth of C<Subscript>60</Subscript> thin films on the Bi(0001)/Si(111) surface

The morphology and atomic structure of C₆₀ fullerene films on the Bi(0001)/Si(111)?7 × 7 surface with different coverages have been studied by scanning tunneling microscopy and spectroscopy and low-energy electron microscopy in high vacuum. It is shown that the most favorable sites for nucleation of C₆₀ islands are double steps and domain boundaries on the surface of epitaxial Bi film.     

Effect of dislocations on the shape of islands during silicon growth on the oxidized Si(111) surface

The formation of dislocation-rich and dislocation-free silicon islands during growth in the absence of mechanical stresses has been studied by scanning tunneling microscopy. The rounded shape of islands obtained at growth temperatures of 400–500°C on the oxidized Si(111) surface is associated with the presence of dislocations within them. The transfer of atoms from the oxidized surface to the islands occurs due to the barrier of the potential energy at the SiO₂/Si boundary. The {111} and {311} facets dominate in the shape of the islands grown at 500–550°C. Their appearance indicates the absence of the threading dislocations in the islands and that the growth is limited by the stage of the nucleation of a new atomic layer.     

Crucial role of substrate steps in de-wetting of crystalline thin films

Using low-energy electron microscopy, we show that de-wetting of Ag and Cu films on Ru(0 0 0 1) occurs by 3-D islands migrating across step edges in the “downhill” direction. We have observed islands thicken by more than 50 atomic layers in this manner. The island migration allows 3-D growth to occur in a way that avoids the nucleation barrier associated with forming 2-D islands on top of 3-D islands. Indeed, without substrate steps this nucleation barrier is not surmounted, and no 3-D islands are formed in the films studied.     

红荧烯薄膜生长及稳定性的研究

利用原子力显微镜研究了二氧化硅衬底上红荧烯薄膜的生长及稳定性。在较低沉积速率下,较低衬底温度时,红荧烯分子有充足的扩散时间,利于薄膜的横向生长,形成连续性、均匀性较好的薄膜。快速蒸镀及较高衬底温度使红荧烯薄膜转变为纵向生长模式,形成团粒状岛。横向生长的红荧烯薄膜在退火和空气中表现为亚稳特性,随着退火温度的升高和空气中放置时间的延长,红荧烯分子会自发地进行质量传输,发生纵向转移,转变为团粒状岛。获得了二氧化硅界面上红荧烯薄膜的生长及亚稳定机制模型。研究结果证明红荧烯分子与二氧化硅界面之间的作用力小于红荧烯分子间的作用力。     

Imaging of surface morphologies of l-arginine trifluoroacetate crystals

The growth mechanism and defect-mediated surface morphologies are investigated by atomic force microscopy (AFM). Both screw-dislocation-controlled growth and 2D nucleation growth operate simultaneously during growth. Hollow core locating at the top of spiral hillock validates that the dislocation has a large Burgers vector. 2D nuclei introduce growth islands and steps with wavy fronts are observed. Impurity-induced step bunching is presumably formed as a result of the imbalance of step speed. The formation of the hollow channels is due to instability of the interface and these may ultimately cause other defects such as liquid inclusions come into being.     

AFM investigation on surface evolution of amorphous carbon during ion-beam-assisted deposition

Hydrogen-free amorphous carbons (a-C) have been prepared on mirror-polished Si(1 1 1) wafers through thermally evaporated C₆₀ with simultaneous bombardments of Ne⁺ ions. The time evolution of film surfaces has been characterized by atomic force microscopy (AFM) at two temperatures of 400 and 700 °C, respectively. Based on the topography images and the root-mean-square (rms) roughness analysis, it is found that the a-C surfaces present roughening growth at the initial stage. With increasing growth time, the cooperative nucleation of the islands and pits appears on the surfaces, suggesting three-dimensional growth, and then they continue to evolve to irregular mounds at 400 °C, and elongated mounds at 700 °C. At the steady growth stage, these surfaces further develop to the structures of bamboo joints and ripples corresponding to these two temperatures, respectively. It is believed that besides ion sputtering effect, the chemical bonding configurations in the amorphous carbon films should be taken into considerations for elucidating the surface evolutions.     

Self‐assembly and structure formation in liquid crystalline phthalocyanine thin films studied by Raman spectroscopy and AFM

This work presents an investigation of films prepared by doctor blade casting, the formation of self‐assembled microstructures of a liquid crystalline phthalocyanine with highly oriented molecules. Raman Spectroscopy in combination with atomic force microscopy is applied to study the structures within the films. By keeping the substrate at room temperature or at 353 K during coating, different geometric structures namely rods and islands form. Rod‐like structures are growing in coating direction, whereas directional growth of the islands is not observed. The distribution of the rod lengths varies widely, whereas the width appears more uniform. Annealing of the samples shows a different behavior of the two textures. Islands tend to melt, and rods smooth their structural form, which is extracted from Raman imaging in combination with atomic force microscopy. Additionally, Raman imaging gives insight into laterally different relative crystallinity. These observations are discussed in the context of the molecular orientation as probed by polarized Raman spectroscopy. These polarized Raman spectra indicate azimuthal alignment of the molecules within the rods (edge on alignment). This alignment occurs along and also perpendicular to the growth direction. In contrast to the alignment in the rods, the molecules inside the islands occurring at higher temperature do not show preferential molecular orientation. After annealing, no preferential molecular orientation is observed in rods because of the loss of anisotropy, too. Copyright © 2012 John Wiley & Sons, Ltd.     

Low-dimensional nanostructures and fullerene films on semiconductor surface

The morphology and atomic structures of C₆₀ fullerene films on a Bi(0001)/Si(111)-7 × 7 surface and adsorption of fluorofullerene C₆₀F _x molecules on a Si(111)-7 × 7 surface have been studied by scanning tunneling microscopy/spectroscopy and low-energy electron microscopy under ultra high-vacuum conditions. It has been shown that initial nucleation of C₆₀ islands on the surface of an epitaxial Bi film occurs on double steps and domain boundaries, while tunnel spectra do not exhibit any significant charge transfer to the lowest unoccupied molecular orbital states. Fluorofullerene molecules allow local (at the nanoscale level) modification of Si surface through local etching.     

Crystallization kinetics in ferroelectric thin films: Viability of atomic force microscopy

The pyrochlore to perovskite phase transformation was studied in lead zirconate titanate (PZT) thin films. The films were fabricated on platinum electrodes and annealed by rapid thermal processing (RTP). The phases which formed and their location in the film were analyzed using glancing angle XRD and depth profiling was demonstrated. Grain size and structure, nucleation sites and surface morphology were determined with transmission electron microscop (TEM) and atomic force microscopy (AFM). The role of AFM in this type of transformation study was assessed.

The PZT films crystallized with a (100) orientation which was preferentially nucleated at the platinum/film interface. RTP at 650°C for 15 s was sufficient to complete the transformation. However, columnar grain growth and improvements in the ferroelectric properties were obtained with increased RTP time. A PZT film with RTP at 650°C for 1 min possessed a remanent polarization of 25 μC/cm² and a dielectric constant of ε = 650.     

The influence of substrate temperature on the structure and morphology of sexiphenyl thin films on Au(111)

The layer growth of ultra-thin films of sexiphenyl on Au(111) has been studied as a function of substrate temperature under well-defined ultra-high-vacuum conditions. In situ X-ray photoelectron spectroscopy in combination with thermal desorption spectroscopy was applied to reveal the kinetics of layer growth and recrystallisation. Ex situ atomic force microscopy and X-ray diffraction were used to determine the film morphology and film structure. A continuous small-grain film is obtained at 93 K. The crystalline structure of the grains has been confirmed by X-ray diffraction. However, the grains are not preferentially oriented with respect to the substrate. Around room temperature, recrystallisation takes place and the molecules within the crystallites orient parallel to the substrate surface. Further small substrate temperature changes during growth lead to further changes of the film morphology and to reorientation of the crystallites. However, the molecules in the crystallites stay aligned parallel to the surface. At temperatures greater than 350 K, terraced islands of standing molecules are observed, in addition to needle-like islands with flat-lying molecules. PACS 68.55.-a; 61.66.Hq; 81.10.Bk     

The effects of sapphire nitridation on GaN growth by metalorganic chemical vapour deposition

In situ optical reflectivity measurements are employed to monitor the GaN epilayer growth process above a low-temperature GaN buffer layer on a c-plane sapphire substrate by metalorganic chemical vapour deposition. It is found that the lateral growth of the GaN islands and their coalescence are promoted in the initial growth stage if optimized nitridation time and temperature are selected when the substrate is pre-exposed to ammonia. As confirmed by atomic force microscopy observations, the quality of the GaN epilayers is closely dependent on the surface morphology of the nitridated buffer layer, especially grain size and nucleation density.     

Influence of patterning on the nucleation of Ge islands on Si and SiO2 surfaces

Surface patterning is expected to influence the nucleation site of deposited nanostructures. In the present study, clean Si and SiO₂ surfaces were patterned by a nanolithographic process using a Focused Ion Beam (FIB). Ge was evaporated in ultra high vacuum at 873 K on these substrates, resulting in the formation of island arrays. Based on scanning tunneling microscopy and atomic force microscopy images, a statistical analysis was performed in order to highlight the effect of patterning on the size distribution of islands compared to a non-patterned surface. We find that the self-organization mechanism on patterned substrates results in a very good arrangement and positioning of Ge nanostructures, depending on growth conditions and holes distance, both on Si and SiO₂ surfaces.