Surfaces: a playground for physics with broken symmetry in reduced dimensionality

With our crystal ball in front of us, we attempt to articulate the opportunities and challenges for a surface physicist in the beginning of the new millennium. The challenge is quite clear: to use the unique environment of a surface or interface to do fascinating physics, while taking full advantage of the skills the community has developed over the last 30 years. The opportunities appear to be endless! In this age of Nanotechnology where the promise is to shape the world atom by atom, leading to the next industrial revolution [Nanotechnology: shaping the world atom by atom, National Science and Technology Council, Committee on Technology, 1999], surface science should be at the very forefront of both technological and scientific advances. The smaller objects become, the more important their surfaces become. In this article we focus on the role of a surface physicist in the emergence of nanoscale collective phenomena in complex materials.     

Structure and electronic properties of ultrathin Co films on W(1 1 0)

The structure and electronic properties of ultrathin Co films on W(1 1 0) grown by molecular beam epitaxy in UHV were investigated by low energy electron diffraction (LEED) and scanning tunneling microscopy and spectroscopy (STM and STS). For coverages above 0.7 ML the pseudomorphic (ps) monolayer is transformed gradually into close-packed (cp-) monolayer areas, showing up as separated islands that increase in size with coverage until the cp-monolayer is complete. Two different structures of the cp-monolayer were observed by atomically resolved STM, both leading to a 8 × 1 superstructure in the LEED pattern. Higher coverages continue to grow in the Stransky–Krastanov growth mode forming simultaneously double layer islands and triple layer islands in fcc(1 1 1) and hcp(0 0 0 1) stacking. STS reveals tunneling spectra that differ considerably depending on the thickness and on the structure. Two different classes of triple layer islands can be distinguished by a resonant peak at +0.3 eV appearing in only one of the two classes. We attributed this behavior to a different stacking according to a fcc or hcp structure.     

Improved growth and the spin reorientation transition of Ni on (√2×2√2)R45° reconstructed O/Cu(0 0 1)

Ni films between 1 and 20 monolayers (ML) thick are deposited at room temperature on clean and (√2×2√2)R45° reconstructed--via oxygen adsorption--Cu(0 0 1). A significant expansion of the out-of-plane Ni phase by about 5 ML is revealed by ferromagnetic resonance experiments. This shift of the spin reorientation transition is attributed to a huge change of about 90 μeV/atom in the surface anisotropy due to the presence of half a monolayer of oxygen atoms on the top of Ni. Furthermore, the growth of Ni on the preoxidized Cu surface is found to be closer to the layer-by-layer one as compared to the growth on the clean Cu(0 0 1) due to the presence of oxygen which acts as a surfactant.     

Magnetism in low dimensionality

The collective creativity of those working in the field of surface magnetism has stimulated an impressive range of advances. Once wary, theorists are now eager to enter the field. The present article attempts to take a snapshot of where the field has been, with an eye to the more speculative issue of where it is going. Selective examples are used to highlight three general areas of interest: (i) characterization techniques, (ii) materials properties, and (iii) theoretical/simulational advances. Emerging directions are identified and discussed, including laterally confined nanomagnetism and spintronics.     

Reactivity of (H)(e) color centers at the MgO surface: formation of O2 and N2 radical anions

We have considered the interaction of O₂ and N₂ molecules with electrons trapped at the surface of MgO by performing embedded cluster DFT calculations. Trapped electrons at the surface of MgO react instantaneously with O₂ and N₂ leading to the formation of the corresponding O₂⁻ and N₂⁻ molecular anions stabilized at specific surface sites. So far, the atomistic model for this process was based on the idea that the electrons are trapped at oxygen vacancies, the F_S⁺ centers. Recently, it has been shown that morphological sites at the MgO surface like a reverse corner, a step or a corner, can adsorb hydrogen and stabilize (H⁺)(e⁻) pairs giving rise to a new class of paramagnetic color centers. Here we show that these centers exhibit reactivity towards O₂ and N₂, which is fully consistent with the experimental observations, providing further support to the new model of electron traps at the MgO surface.     

Magnetic pole pinning at rectangular defects on MnAs/GaAs(0 0 1)

Strong magnetic poles at characteristic rectangular defects have been observed using a magnetic force microscope on a MnAs(  1 0 0) thin film with the thickness of 30 nm. The MnAs thin film was epitaxially grown on a GaAs(0 0 1) substrate. The magnetic poles were in one-arranging direction, being independent of the magnetization direction of the film. The poles were pinned at the edges of the rectangular defects until just below the Curie temperature, and formed a stable magnetic-field loop on the MnAs surface. The stability of the magnetic pole pinning shows the distinctive feature of the magnetic domain structure on the surface with a strong anisotropy, which was built in the heterostructure of MnAs and GaAs.     

Effect of surface roughness on the electron-stimulated desorption of D from microporous D2O ice

The electron-stimulated desorption (ESD) of D⁺ from microporous D₂O ice films condensed on Pt(111) has been investigated. The total D⁺ yield as a function of temperature from 90–180 K depends sensitively on the film roughness, surface temperature and ice phase. In particular, we observe an irreversible increase in the cation yield as the microporous thin film is heated from 90–120 K, which we associate with a decrease in surface roughness as the micropores collapse. We present evidence which suggests that the number of surface sites available for emission, the surface roughness, and reneutralization or reactive scattering of the D⁺ desorbate play major roles in determining the ion yield. A simple model which qualitatively addresses the role of surface roughening on ESD ion yields shows good agreement with the data.     

Phase transitions and domain structures in thin ferroelectric films

Recent advances in technology made available high quality thin ferroelectric films and ferroelectric–paraelectric multilayers. But understanding of the properties of these systems is far from being complete. In particular, it is not clear why various anomalies observed at phase transitions here are different from those in high quality bulk systems. The aim of the paper is to discuss some specific features of ferroelectric phase transitions in thin films and multilayers which are taken into account only partially by the theory. The discussion is limited to revealing the character of ferroelectric state forming just after the transition, i.e. if it is single-domain or multi-domain, if it is single-phase or two-phase. First, thin films with electrodes and on a substrate are discussed. The role of non-ideality of electrodes in realization of one of the first pairs of possibilities is emphasized. A more recent idea is that even for ideal electrodes a domain formation is possible when some conditions on the electrode–ferroelectric interface and the material constants of the material are met. This seems to be quite possible for the considered systems. Clamping by the substrate may lead to formation of a two-phase state which is practically unexplored for very thin films on substrates. Second, ferroelectric–paraelectric multilayers are considered which are more challenging for theoretical study than the thin films. Indeed, despite periodicity in the composition the domain structures are almost never periodic along the multilayer. The non-ideality of electrodes seems to lead to practical impossibility of single-domain ferroelectric phase transition in the multilayers of the considered type.     

Correlations between magnetic properties and bond formation in Rh-MgO(0 0 1)

We present the results of first principles calculations for the magnetism of Rh adlayers on MgO(0 0 1), at three different adsorption sites and three different coverages, corresponding to 1, 1/2 and 1/8 monolayers. Finite magnetization is found in all cases except that of one Rh monolayer above the oxygen site, which is also the most stable. We examine how the magnetization changes as a function of the Rh-surface distance and relate this to changes in the real-space charge density and in the density of states (DOS) as the Rh adlayer interacts with the surface. We find that increasing either the Rh-Rh interaction strength or the Rh-surface interaction strength leads to reduced magnetization, while increasing the former drives a crossover from localized (atomic) to itinerant magnetism. Neither the magnetic transition itself, nor the localized-to-itinerant magnetism crossover, is found to be directly related to the formation of Rh-surface bonds. From a practical point of view, we predict that magnetism in the Rh-MgO(0 0 1) system is most likely to be found experimentally at reduced coverages and at low temperatures.     

Tailoring magnetism in artificially structured materials: the new frontier

The current standard of electronic devices and data storage media has reached a level such that magnetic materials have to be fabricated on a nanometer scale. In particular, the emerging concept of spintronics, which is based on fact that current carriers have not only charge but also spin, requires the assembling of nanometer-sized magnetic structures with desired magnetic properties. It is this background that motivates scientists and engineers to attempt to grow and characterize magnetic objects at smaller and smaller length scales, from 2D films and multilayers to 1D wires and eventually to 0D dots. In this article, some of the most significant progress in recent years in the effort of growing artificially structured magnetic materials are reviewed. The new structural and magnetic properties of these materials are discussed, with an emphasis on the correlation between structure and magnetism, which also serves as guidance for improving their magnetic properties. The emerging emphasis is on converting the existing knowledge into growing and studying low-dimensional complex materials, which promise to have considerably higher “tuning” ability for desired properties.     

Surface properties of platinum thin films as a function of plasma treatment conditions

We examined the surface properties of platinum (Pt) thin films exposed to oxygen and argon plasma treatments and compared them to as-deposited Pt films. The surface wetting properties, refractive index and extinction coefficient of the Pt films were monitored as a function of time after different plasma treatments. Surfaces treated with an oxygen plasma were dramatically different from as-deposited Pt, whereas argon plasma treated surfaces were similar to as-deposited films. X-ray photoelectron spectroscopy confirmed the formation of platinum oxide on films treated with an oxygen plasma, while such oxide diminished after argon plasma treatment. Surface morphology studied with atomic force microscopy indicated a strong dependence of the surface roughness of the Pt films on the power and duration of the argon plasma used for the treatment. Based on these studies, an oxygen plasma treatment followed by a brief low-power argon plasma etch was developed for the purpose of regenerating clean and metallic Pt surfaces, and at the same time providing the smoothest possible surface morphology.     

Tight-binding study of ammonia and hydrogen adsorption on magnetic cobalt systems

The semi-empirical self-consistent tight-binding model of ammonia and hydrogen adsorption at Co(0001) and small Co clusters is used to study the chemisorption role in surface magnetism. The adsorbate choice has been suggested by recent experiments. At the Co(0001) surface the atomic magnetization is predicted to diminish locally by 0.26 μ_B due to an isolated hydrogen atom adsorption; for Co₁₃ clusters the change is somewhat smaller but less localized. At H(1×1)–Co(0001) the magnetization of surface Co atoms drops to 0.88 μ_B. The hydrogen magnetic moment is very small and couples antiferromagnetically to Co. Ammonia adsorption is found to reduce the Co atom magnetization locally by 0.1 μ_B or less. We discuss the possibility of adsorbate–metal antiferromagnetic coupling in more detail.     

Sulfur adsorption on Fe(1 1 0): a DFT study

The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers.     

Clusters as new materials

Over the past two decades methods have been developed to produce clusters with an exactly determined number of atoms. Due to their finite size these small particles have totally different structures and `materials properties' than their bulk crystalline counterparts. Even more, these properties sometimes change drastically whenever a single atom is added to or removed from the cluster. This opens the pathway for a whole new world of tailor made materials in the future. In this article we describe the present state of the knowledge of the properties of clusters of atoms which in their bulk form conventional metals or semiconductors. The questions addressed include the development of the electronic structure as a function of cluster size and for example what remains of the `metallic' properties of the bulk solid in these very small clusters. Technological advances are expected using clusters on a specific support material in the areas of catalysis, magnetic storage media or electronic materials, and even solids assembled totally from clusters. Examples from each of these fields will be discussed in the context of this article.     

Molecular scale structure formation by folding

A conception of a structure formation suitable for nano-technology is proposed, which is programmable and suitable for mass production-like lithography. This conception utilizes the controlled folding of chains like the scan-lines of television. Its possibility and property were studied theoretically using the modeled chains consist of beads. By adopting the interaction among the beads which can distinguish the kind of the partner by its polarity and is chiral to break the chiral symmetry of the folded state, the special chains which have the unique ground states could be designed. In these ground states, the chains are folded like the scan-lines of television. The thermodynamic properties of the suggested chains were studied by the Monte Carlo simulations and the suggested chains showed the phase-transition-like behavior which is distinct compared to both the random chains and the chain that has only the non-specific attraction. The size dependence and the effects of adding the non-specific attraction and modifying the border of the folded conformation were also studied.     

Modeling structural metastability of irradiated thin films

The nucleation of crystalline or amorphous phases in irradiated binary metallic, as well as non-metallic compound thin films is interpreted using the atomistic interface migration-charge transfer (IMCT) model. The space and time evolution of dense collision cascades, which form upon ion bombardment of the target, lead to non-equilibrium compositional and electronic density profiles at the interface between each cascade and the surrounding crystalline matrix. This occurs because one of film constituents preferentially migrates to the interface, which becomes enriched in it. Cascade relaxation to metastable equilibrium is simulated by local charge transfer reactions (CTR), each involving a pair of dissimilar atoms of the initial compound, which constitute a dimer of an effective compound. The energy cost to introduce an effective compound dimer into the matrix, the difference of formation enthalpy between effective and initial compound and the local strain suffered by the film as a consequence of ion formation by a CTR are evaluated. Threshold values are found in the above structure stability parameters that allow for a qualitative separation of amorphised from crystalline compounds, both metallic and non-metallic.     

Hydrophilicity of amorphous TiO2 ultra-thin films

The UV-light-induced hydrophilicity of amorphous titanium dioxide thin films obtained by radio frequency magnetron sputtering deposition was studied in relation with film thickness. The effect of UV light irradiation on the film hydrophilicity was fast, strong and did not depend on substrate or thickness for films thicker than a threshold value of about 12 nm, while for thinner films it was weak and dependent on substrate or thickness. The weak effect of UV light irradiation observed for the ultra-thin films (with thickness less than 12 nm) is explained based on results of measurements of surface topography, UV-light absorption and photocurrent decay in vacuum. Comparing to thicker films, the ultra-thin films have a smoother surface, which diminish their real surface area and density of defects, absorb partially the incident UV light radiation, and exhibit a longer decay time of the photocurrent in vacuum, which proves a spatial charge separation. All these effects may contribute to a low UV light irradiation effect on the ultra-thin film hydrophilicity.     

Adhesion of elastic films on mound rough surfaces

In this work, we have investigated the adhesive behaviour of elastic films in contact with solid substrates, which are bounded by mound surface roughness. This type of roughness is described by the rms roughness amplitude w, the average mound separation Λ, and the system correlation length ζ. It is shown that both lateral roughness parameters Λ and ζ strongly influence adhesive characteristics. Indeed, with increasing elastic film modulus E, film adhesion is only possible for sufficiently large mound separations Λ. Moreover, the critical elastic modulus E_c (for which spontaneous film decohesion takes place for E>E_c) is shown to increase fast with increasing mound separation Λ when Λ?ζ, while as a function of the system correlation length ζ it increases relatively fast when ζ?Λ.     

Preparation and characterizations of amorphous nanostructured SiC thin films by low energy pulsed laser deposition

Amorphous silicon carbide (SiC) thin films were deposited on silicon substrates by pulsed laser ablation at room temperature. Thicknesses and surface morphology of the thin films were characterized using optical profilers, atomic force and field emission scanning electron microscopy. Nanohardnes, modulus and scratch resistance properties were determined using XP nanoindenter. The results show that crack free, smooth and nanostructured thin films can be deposited using low laser energy densities.     

Surface pre-melting and surface flattening of Bi nanofilms on Si(1 1 1)-7 × 7

We report on the in situ observation of temperature-driven drastic morphology evolution and surface pre-melting of the Bi(0 0 1) nanofilm deposited on the Si(1 1 1)-7 × 7 surface by use of spot-profile-analyzing low-energy electron diffraction (SPA-LEED). Surface step density of the single-crystalline, epitaxial Bi(0 0 1) film decreases above 350 K in a critical manner. On annealed Bi(0 0 1) films, we have detected surface pre-melting with a transition temperature of 350 K, which yields reversible diffraction intensity drop in addition to the harmonic Debye-Waller behavior. The observed surface flattening of the as-deposited film is driven by the increased amount of mobile adatoms created through the surface pre-melting.