On the origin of pyramids and cones on ion-bombarded copper surfaces

It is shown that ion-bombardment-induced pyramids or cones on pure Cu surfaces originate mainly, at least in the absence of major surface impurities, from pre-existing asperities. Such features can in principle be formed due to mechanical treatment, to chemical treatment, to inclusions, to surface impurities, or to other causes, the precise details being unimportant. Once asperities are present, regions which have a convex-up curvature should, as argued by Carter, Colligon, and Nobes, evolve into facets having an angle near θ̂ between the beam and the target normal, θ̂ being the angle at which the sputtering coefficient, S(θ), maximizes. By considering the velocity of motion of the facets it follows that, after a critical bombardment dose given approximately by $\text{Nh}{}_1\text{[S(}\text{θ}\text{?}\text{)?S(0)]}$, the asperities will be pyramidal. (N = number density, h₁ = height of asperity.) It is also shown that the following play little or no direct role with Cu in causing pyramids or cones: grain boundaries, chemical etch pits, a Ti impurity on a smooth surface, minor surface impurities due to oxide or hydrocarbon films, annealing an otherwise stable surface. Major hydrocarbon contamination appeared to play a role but it was unclear whether it was a direct or indirect one, that is, whether or not pre-existing roughness was involved.     

On the problem of the stability of pyramidal structures on bombarded copper surfaces

The morphological evolution of pyramids, developed on bombarded copper surfaces, as a function of consecutive doses of 12 keV Kr—ions from 2.4 × 10¹⁶ up to 3 × 10¹⁶ ions/cm², has been studied. In disagreement with many previous studies, apparently based on a limited choice of doses which were sometimes not in sequence, we found that the pyramids disappeared at high enough doses. Pyramids are therefore not an equilibrium structure.     

On the relative stability of different topographical features developed on bombarded copper surfaces

The morphological evolution of different topographical features (namely cones, ridges, cliffs, and featureless planes), as developed on bombarded copper surfaces as a function of consecutive doses of mass-separated 12 keV Kr⁺ ions, has been compared. The doses ranged from 1.2 × 10¹⁷ ions/cm² up to 3 × 10¹⁹ ions/cm². We found clear experimental evidence, valid at least for copper as here prepared, that the order of increasing relative stability is cone-ridge-cliff-plane.     

Formation of nanodots on oblique ion sputtered InP surfaces

Using a field emission gun based scanning electron microscopy, we report the formation of nanodots on the InP surfaces after bombardment by 100 keV Ar⁺ ions under off-normal ion incidence (30° and 60° with respect to the surface normal) condition in the fluence range of 1 × 10¹⁶ to 1 × 10¹⁸ ions cm⁻². Nanodots start forming after a threshold fluence of about 1 × 10¹⁷ ions cm⁻². It is also seen that although the average dot diameter increases with fluence the average number of dots decreases with increasing fluence. Formation of such nanostructured features is attributed due to ion-beam sputtering. X-ray photoelectron spectroscopy analysis of the ion sputtered surface clearly shows In enrichment of the sputtered InP surface. The observation of growth of nanodots on the Ar⁺-ion sputtered InP surface under the present experimental condition matches well with the recent simulation results based on an atomistic model of sputter erosion.     

Active sites of adsorption on cleaved and sputtered indium phosphide surfaces

From the initial uptake of atomic hydrogen at room temperature the active sites on cleaved and sputtered InP(110)-surfaces were determined using high resolution electron energy loss spectroscopy (HREELS), low energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS, XAES). It is found that the In-H stretching mode intensity is dominant for the cleavage surface, which is known to be P-rich due to surface relaxation. For the Ar⁺-ion bombarded surface (In-rich) the P–H stretching mode is very strong if compared to the corresponding In-H mode. From these observations it may be deduced that both, the chemical bonding situation and the geometric configuration, are reflected in our HREELS-results. For the cleavage surface the initial adsorption for atomic hydrogen is interpreted in the framework of existing models for the (1×1) relaxation in terms of its chemical bonding configuration. The sputtered surface is assumed to be amorphous consisting of In-clusters and predominantly broken P-bonds, which are passivated after hydrogen exposure. For high hydrogen exposures, a strong decrease of the phosphor hydride lines may be interpreted as phosphine desorption.     

Cathodoluminescence of copper and nickel surfaces

Cathodoluminescence spectra of clean and oxidized Cu(100) and Ni(100) surfaces, using 60–1000 eV electron bombardment, has been measured. A broad peak at 310 nm has been observed for both clean Cu and Ni surfaces. This peak is attributed to radiative recombination of electrons from the point X'₄ with holes at the point X₅ of the energy band diagram. A narrow peak at 520 nm has been found to correlate with the growth of oxide on the Cu and Ni surfaces. This peak can be attributed to electronic transitions involving energy levels of the O^2- ions. The cathodoluminescence technique appears useful for studying the initial growth of metal oxides.     

Angular distribution of copper atoms sputtered with energetic ions

Measurements of the angular distribution of copper atoms which are sputtered by noble gas ions within the energy range between 0.1 and 1 MeV have been carried out for different angles of ion incidence. The hemisphere over the target surface could be studied with a microphotometer inside the sputtering chamber and the distributions can be plotted in tri-dimensional diagrams. The results are in principle similar to those obtained at lower energies. The angle of maximum emission varies with ion energy and with the angle of incidence and can be related to the sputtering yield.     

Study of chemisorption on copper low-index and stepped surfaces

Adsorption of CHCl₃, O₂, and hydrocarbons has been studied on Cu(111) and stepped surfaces using LEED, AES, and UPS at room temperature. We find that ordered Cl overlayers form upon Cu(111), Cu[3(111) × (100)], and Cu[5(111) × (100)] surfaces upon exposure to CHCl₃. Exposure to O₂ results in rearrangement of the Cu[5(111) × (100)] surface to hill-and-valley regions with large (111) areas, whereas Cu[2(111) × (100)] is stable for the same exposure. The photoemission spectra show new energy levels due to C1 above and below the Cu d band region and a small splitting of the halogen p orbitals. Effects consistent with interaction with the Cu d band are observed. Similar effects are observed with oxygen adsorption. The initial rate of Cl or O₂ chemisorption as measured by photoemission is proportional to the density of steps on these surfaces. Apparently, structural effects play an important role in chemisorption on metals (such as copper) with low density of states at the Fermi energy.     

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     

Structure and stability of clusters on metal surfaces

Small clusters of 3d metals Ni/Ni(001), Cu/Cu(001), 4d-Pd/Pd(001), Ag/Ag(001), 5d-Pt/Pt(001), and Au/Au(001) are investigated by semiempirical methods using multiparticle interatomic interaction potentials. It is shown that the same magic numbers (4, 6, and 9) are characteristic for all metals indicated; these numbers are determined by the symmetry characteristics of the clusters, related to the morphology of the fcc (001) substrate. It is shown for Pt/Pt(111) that small clusters of seven, ten, and more atoms are stable for the fcc (111) surface. This confirms that the magic numbers are associated with the symmetry of the clusters. Fiz. Tverd. Tela (St. Petersburg) 41, 1329–1334 (July 1999)     

H processing of copper surfaces

Changes in the crystallographic structure of polycrystalline copper surface due to the atomic hydrogen treatment are described. Samples of polycrystalline OFHC copper plates were exposed to a flux of thermal hydrogen atoms with the density between 1×10²¹ atoms/m²s and 1×10²³ atoms/m²s. Hydrogen atoms partially accommodate and recombine in the potential well on the surface. During these processes copper atoms on the surface displace, which leads to a recrystallization of the samples. The effects were investigated by a scanning electron microscope (SEM).     

The preparation of lotus-like super-hydrophobic copper surfaces by electroplating

The preparation of super-hydrophobic metal surfaces had to combine rough structures and the surface modifications with low surface energy materials. Although there were different views on it, no experiment was done to prove it yet. In this paper, the structure of natural lotus leaf was observed and the lotus-like surfaces on hydrophilic copper substrates were fabricated via electroplating in large current density. These surfaces were super-hydrophobic without any chemical modification. The hydrophobic mechanism was analyzed. It is believed that this was a meta-stable state in Cassie model. As long as the surface structure was suitable, hydrophobic surface, even super-hydrophobic surface, could be got on hydrophilic substrate.     

Further experimental evidence on the importance of tertiary effects in the evolution of pyramids on bombarded copper

Further experimental results relating to the role of tertiary effects in the evolution of pyramids on bombarded Cu surfaces are presented. The observed enlargement of the apex angles during the shrinking process, together with the previously described mushroom-like structures, are taken as evidence for the existence of these effects.     

Electroless deposition of copper and fabrication of copper micropatterns on CVD diamond film surfaces

Electroless deposition of copper on as-grown and amino-modification diamond substrates was investigated. The compact and uniform copper films were successfully electrolessly deposited on as-grown and amino-modification diamond substrates after activation by Pd/Sn colloid nanoparticles. The adhesion interaction between copper films and diamond substrates was roughly estimated by the ultrasonic treatment. The results showed the higher adhesion interaction between copper films and amino-modification diamond substrates than that between the copper films and as-grown diamond substrates due to the greater attractive force between the Pd/Sn colloid nanoparticles and amino-modified diamond surface. The favorable copper micropatterns were successfully constructed on diamond film surfaces by means of the catalyst lift-off method and the copper lift-off method. Furthermore, the electrochemical behavior of copper-modified boron-doped diamond (BDD) was studied for glucose oxidation in 0.2 M sodium hydroxide solution by using cyclic voltammetry, and the result indicated that copper-modified BDD exhibited high catalytic activity to electrochemical oxidation of glucose in alkaline media.     

LEED studies of adsorption on vicinal copper surfaces

As a means for studying the role of atomic steps in adsorption phenomena LEED has been used to investigate the properties of vicinal copper surfaces. Single crystalline surfaces were cut at angles up to 20° from the (100) pole along [001] and [011̄] zones. The diffraction patterns obtained for the clean surfaces and after adsorption of oxygen, nitrogen ions, carbon and sulphur are described. The emphasis of the paper is on the method of interpretation of the geometry of the patterns, which may be done by straightforward kinematic analyses. In the case of nitrogen it is found that if the steps are widely separated the structure of the layer adsorbed on the terrace is the same as that on the low index surface. When the step spacing is small, and comparable with the crystalline parameter of the adsorbed layer, modifications occur which give rise to different superlattices which extend over several terraces. Adsorption of sulphur on 〈11〉 steps can produce a change in the periodicity of the adsorbed layer parallel to the step direction. The study of diffraction patterns for vicinal surfaces with different step spacings may provide an interesting technique for verifying the interpretation of patterns for low index surfaces.     

Molecule-metal interaction of pentacene on copper vicinal surfaces

A combined X-ray photoemission and absorption spectroscopy study of the adsorption of pentacene layers grown on the Cu(1 1 9) vicinal surface is presented. A significant interaction between the π molecular orbitals delocalized on the aromatic rings and the underlying copper substrate is evicted by C 1s core levels manifold peaks at the interface. Adsorption geometry with pentacene molecules almost flat-lying along the Cu terraces is confirmed by the polarization dependence of the C 1s absorption features.     

Bromine atom diffusion on stepped and kinked copper surfaces

The rates of Br atom diffusion on several single crystalline Cu surfaces have been studied because of the potential impact of Br diffusion on the selectivity of alkyl bromide surface chemistry on Cu. Density functional theory (DFT) has been used to study the diffusion of isolated bromine atoms on a flat Cu surface, Cu(1 1 1), two Cu surfaces with straight steps, Cu(2 2 1) and Cu(5 3 3), and two kinked Cu surfaces, Cu(6 4 3) and Cu(5 3 1). Bromine diffusion is rapid on the flat Cu(1 1 1) surface with a barrier of ΔE_diff = 0.06 eV and a hopping frequency of ν = 4.8 × 10¹⁰ s⁻¹ at 150 K. On the stepped and kinked surfaces the effective diffusion barriers lie in the range ΔE_diff = 0.18-0.31 eV. Thus the rates of diffusion are many orders of magnitude slower on stepped and kinked Cu surfaces than on the Cu(1 1 1) surface. Nonetheless, at temperatures relevant for alkyl bromide debromination on Cu surfaces, bromine atoms remain sufficiently mobile that they can explore all available binding sites on the timescale of the debromination reaction.     

Correlations between electron and positron workfunctions on copper surfaces

We have performed contact potential difference measurements on low-index faces of copper in ultrahigh vacuum using positrons as positive test particles in a retarding field analyzer. For negative positron affinity surfaces bombarded with keV positrons we also measured energy distributions of reemitted slow positrons and found them to sharply peaked in energy about a value which we label ?φ⁺. Both adsorbing sulfur on a Cu(111) sample and raising its temperature cause changes in φ⁺ which are equal and opposite to the contact potential change of the sample, i.e. the electron workfunction change. This result is in complete accordance with φ⁺ being a measure of the negative positron workfunction of the sample and high temperature or adsorbates inducing a change only in the electrostatic surface dipole layer.     

An empirical relationship between atoms and ions sputtered from single crystal surfaces

The temperature dependence of long range order at a (100) surface of Cu₃Au has been determined by low energy electron diffraction. Auger electron spectroscopy revealed that the composition of the alloy near the surface is changed by ion bombardment, but the stoichiometric composition is reconstituted by annealing. The order parameter of the surface, which was obtained from the temperature dependence of a superlattice beam, appears to be a continuous function of temperature, unlike the bulk order parameter. The disordering process at the surface begins about 60°K below a critical temperature which is common to both the surface and the volume. Monte Carlo calculations of the order parameter as a function of temperature for a model incorporating nearest- and next-nearest-neighbor interactions reproduce the experimental results and also provide an evaluation of the change in order parameter as a function of layer number for boundary conditions corresponding to a copper or a copper-gold surface.