The organometallic chemistry of the Ru(001) surface

The organometallic chemistry of the hexagonally close-packed Ru(001) surface has been studied using electron energy loss spectroscopy and thermal desorption mass spectrometry. The molecules that have been studied are acetylene, formamide and ammonia. The chemistry of acetylene and formamide has also been investigated in the presence of coadsorbed hydrogen and oxygen adatoms.

Acetylene is adsorbed molecularly on Ru(001) below approximately 230 K, with rehybridization of the molecule to nearly sp^3 occurring. The principal decomposition products at higher temperatures are ethylidyne (CCH_3) and acetylide (CCH) between 230 and 350 K, and methylidyne (CH) and surface carbon at higher temperatures. Some methylidyne is stable to approximately 700 K. The preadsorption of hydrogen does not alter the decomposition products of acetylene, but reduces the saturation coverage and also leads to the formation of a small amount of ethylene (via an η^2-CHCH_2 species) which desorbs molecularly near 175 K. Preadsorbed oxygen also reduces the saturation coverage of acetylene but has virtually no effect on the nature of the molecularly chemisorbed acetylene. It does, however, lead to the formation of an sp^2-hybridized vinylidene (CCH_2) species in the decomposition of acetylene, in addition to the decomposition products that are formed on the clean surface. There is no molecular desorption of chemisorbed acetylene from clean Ru(001), hydrogen-presaturated Ru(001), or oxygen-presaturated Ru(001).

The adsorption and decomposition of formamide has been studied on clean Ru(001), hydrogen-presaturated Ru(001), and Ru(001)-p(1x2)-O (oxygen adatom coverage = 0.5). On clean Ru(001), the adsorption of low coverages of formamide at 80 K results in CH bond cleavage and rehybridization of the carbonyl double bond to produce an η^2 (C,O)-NH_2CO species. This species is stable to approximately 250 K at which point it decomposes to yield a mixture of coadsorbed carbon monoxide, ammonia, an NH species and hydrogen adatoms. The decomposition of NH to hydrogen and nitrogen adatoms occurs between 350 and 400 K, and the thermal desorption products are NH_3 (-315 K), H_2 (-420 K), CO (-480 K) and N_2 (-770 K). At higher formamide coverages, some formamide is adsorbed molecularly at 80 K, leading both to molecular desorption and to the formation of a new surface intermediate between 300 and 375 K that is identified tentatively as η^1(N)-NCHO. On Ru(001)- p(1x2)-O and hydrogen-presaturated Ru(001), formamide adsorbs molecularly at 80 K in an η^1(O)- NH_2CHO configuration. On the oxygen-precovered surface, the molecularly adsorbed formamide undergoes competing desorption and decomposition, resulting in the formation of an η^2(N,O)-NHCHO species (analogous to a bidentate formate) at approximately 265 K. This species decomposes near 420 K with the evolution of CO and H_2 into the gas phase. On the hydrogen precovered surface, the Η^1(O)-NH_2CHO converts below 200 K to η^2(C,O)-NH_2CHO and η^2(C,O)-NH^2CO, with some molecular desorption occurring also at high coverage. The η^2(C,O)-bonded species decompose in a manner similar to the decomposition of η^2(C,O)-NH_2CO on the clean surface, although the formation of ammonia is not detected.

Ammonia adsorbs reversibly on Ru(001) at 80 K, with negligible dissociation occurring as the surface is annealed The EEL spectra of ammonia on Ru(001) are very similar to those of ammonia on other metal surfaces. Off-specular EEL spectra of chemisorbed ammonia allow the v(Ru-NH_3) and ρ(NH_3) vibrational loss features to be resolved near 340 and 625 cm^(-1), respectively. The intense δ_g (NH_3) loss feature shifts downward in frequency with increasing ammonia coverage, from approximately 1160 cm^(-1) in the low coverage limit to 1070 cm^(-1) at saturation. In coordination compounds of ammonia, the frequency of this mode shifts downward with decreasing charge on the metal atom, and its downshift on Ru(001) can be correlated with the large work function decrease that the surface has previously been shown to undergo when ammonia is adsorbed. The EELS data are consistent with ammonia adsorption in on-top sites. Second-layer and multilayer ammonia on Ru(001) have also been characterized vibrationally, and the results are similar to those obtained for other metal surfaces.

Studies of molecular bonding, interactions and decomposition reactions on the (001) surface of ruthenium

The interactions of N₂, formic acid and acetone on the Ru(001) surface are studied using thermal desorption mass spectrometry (TDMS), electron energy loss spectroscopy (EELS), and computer modeling.

Low energy electron diffraction (LEED), EELS and TDMS were used to study chemisorption of N₂ on Ru(001). Adsorption at 75 K produces two desorption states. Adsorption at 95 K fills only the higher energy desorption state and produces a (√3 x √3)R30° LEED pattern. EEL spectra indicate both desorption states are populated by N₂ molecules bonded "on-top" of Ru atoms.

Monte Carlo simulation results are presented on Ru(001) using a kinetic lattice gas model with precursor mediated adsorption, desorption and migration. The model gives good agreement with experimental data. The island growth rate was computed using the same model and is well fit by R(t)^m - R(t₀)^m = At, with m approximately 8. The island size was determined from the width of the superlattice diffraction feature.

The techniques, algorithms and computer programs used for simulations are documented. Coordinate schemes for indexing sites on a 2-D hexagonal lattice, programs for simulation of adsorption and desorption, techniques for analysis of ordering, and computer graphics routines are discussed.

The adsorption of formic acid on Ru(001) has been studied by EELS and TDMS. Large exposures produce a molecular multilayer species. A monodentate formate, bidentate formate, and a hydroxyl species are stable intermediates in formic acid decomposition. The monodentate formate species is converted to the bidentate species by heating. Formic acid decomposition products are CO₂, CO, H₂, H₂O and oxygen adatoms. The ratio of desorbed CO with respect to CO₂ increases both with slower heating rates and with lower coverages.

The existence of two different forms of adsorbed acetone, side-on, bonded through the oxygen and acyl carbon, and end-on, bonded through the oxygen, have been verified by EELS. On Pt(111), only the end-on species is observed. On dean Ru(001) and p(2 x 2)O precovered Ru(001), both forms coexist. The side-on species is dominant on clean Ru(001), while O stabilizes the end-on form. The end-on form desorbs molecularly. Bonding geometry stability is explained by surface Lewis acidity and by comparison to organometallic coordination complexes.

Kinetic investigations of heterogeneously catalyzed reactions on the Ru(001) and Pt(110)-(1x2) surfaces

The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

Broadband Emitting Superluminescent Diodes With InAs Quantum Dots in AlGaAs Matrix

Superluminescent diodes were fabricated by using InAs-AlGaAs self-assembled quantum dots (QDs) as the active region. The ultrawide emitting spectrum of 142 nm was achieved. The short migration length of indium adatoms on AlGaAs surface increases the size dispersion of InAs QDs, resulting in the broadening of optical gain spectrum.

Kinetically controlled InN nucleation on GaN templates by metalorganic chemical vapour deposition

This paper presents a study on the nucleation and initial growth kinetics of InN on GaN, especially their dependence on metalorganic chemical vapour deposition conditions. It is found that the density and size of separated InN nano-scale islands can be adjusted and well controlled by changing the V/III ratio and growth temperature. InN nuclei density increases for several orders of magnitude with decreasing growth temperature between 525 and 375 degrees C. At lower growth temperatures, InN thin films take the form of small and closely packed islands with diameters less than 100 nm, whereas at elevated temperatures the InN islands grow larger and become well separated, approaching an equilibrium hexagonal shape due to enhanced surface diffusion of adatoms. The temperature dependence of InN island density gives two activation energies of InN nucleation behaviour, which is attributed to two different kinetic processes related to In adatom surface diffusion and desorption, respectively.

The influence of growth temperature and input V/III ratio on the initial nucleation and material properties of InN on GaN by MOCVD

The effects of growth temperature and V/III ratio on the InN initial nucleation of islands on the GaN (0 0 0 1) surface were investigated. It is found that InN nuclei density increases with decreasing growth temperature between 375 and 525 degrees C. At lower growth temperatures, InN thin films take the form of small and closely packed islands with diameters of less than 100 nm, whereas at elevated temperatures the InN islands can grow larger and well separated, approaching an equilibrium hexagonal shape due to enhanced surface diffusion of adatoms. At a given growth temperature of 500 degrees C, a controllable density and size of separated InN islands can be achieved by adjusting the V/III ratio. The larger islands lead to fewer defects when they are coalesced. Comparatively, the electrical properties of the films grown under higher V/III ratio are improved.

Comparative study of InAs quantum dots grown on different GaAs substrates by MOCVD

We present a comparative study of InAs quantum dots grown on Si-doped GaAs (10 0) substrates, Si-doped GaAs (10 0) vicinal substrates, and semi-insulating GaAs (10 0) substrates. The density and size distribution of quantum dots varied greatly with the different substrates used. While dots on exact substrates showed only one dominant size, a clear bimodal size distribution of the InAs quantum dots was observed on GaAs vicinal substrates, which is attributed to the reduced surface diffusion due to the presence of multiatomic steps. The emission wavelength is blueshifted during the growth of GaAs cap layer with a significant narrowing of FWHM. We found that the blueshift is smaller for QDs grown on GaAs (10 0) vicinal substrates than that for dots on exact GaAs (100) substrates. This is attributed to the energy barrier formed at the multiatomic step kinks which prohibits the migration of In adatoms during the early stage of cap layer growth. (c) 2005 Elsevier B.V. All rights reserved.

The correlation between preferred orientation and performance of ITO thin films

The tin-doped indium oxide (ITO) thin films were prepared by reactive thermal evaporation on the glass substrates. The effects of substrate temperatures (T-s) on the grain preferred orientation, the electrical and optical properties of ITO films were studied. X-ray diffraction (XRD) patterns indicated that the preferred orientation of film changes from (222) to (400) as T, > 200 degrees C. It can be explained by that the low-index crystallographic planes are easier to be formed when the adatoms have high surface mobility. The Hall measurements indicated that both the concentration and mobility of carrier increase with increasing T,,,. The grain orientation of film does not influence the transmissivity and the carrier concentration, but enhances the carrier mobility. The transmissivity of ITO films is over 90% in the visible wavelength region (except that of the film deposited at 125 degrees C). A minimum resistivity of 5 X 10-4 Omega cm is achieved for the (400) preferred orientation film. Thus, the highest figure of merit of 3.5 x 10(-2) square/Omega is obtained for the film with (400) preferred orientation. The correlation between the preferred orientation and electrical and optical properties are discussed.

Al compositional inhomogeneity of AlGaN epilayer with a high Al composition grown by metal-organic chemical vapour deposition

The A1 compositional distribution of A1GaN is investigated by cathodoluminescence (CL). Monochromatic CL images and CL spectra reveal a lateral A1 compositional inhomogeneity, which corresponds to surface hexagonal patterns. Cross-sectional CL images show a relatively uniform Al compositional distribution in the growth direction, indicating columnar growth mode of A1GaN films. In addition, a thin A1GaN layer with lower Al composition is grown on top of the buffer A1N layer near the bottom of the A1GaN epilayer because of the larger lateral mobility of Ga adatoms on the growth surface and their accumulation at the grain boundaries.

The effects of LT AlN buffer thickness on the optical properties of AlGaN grown by MOCVD and Al composition inhomogeneity analysis

We have investigated the growth of AlGaN epilayers on a sapphire substrate by metalorganic chemical vapour deposition using various low-temperature ( LT) AlN buffer thicknesses. Combined scanning electron microscopy and cathodoluminescence investigations reveal the correlation between the surface morphology and optical properties of AlGaN films in a microscopic scale. It is found that the suitable thickness of the LT AlN buffer for high quality AlGaN growth is around 20 nm. The Al compositional inhomogeneity of the AlGaN epilayer is attributed to the low lateral mobility of Al adatoms on the growing surface.

Self-organized InAs quantum wires on GaAs (331)A substrates

Self-organized InAs quantum wires (QWRs) were fabricated on the step edges of the GaAs (331)A surface by molecular beam epitaxy. The lateral size of InAs QWRs was saturated by the terrace width (i.e., 90 nm) while the size along the step lines increased with the increasing thicknesses of the InAs layers, up to 1100 nm. The height of InAs QWRs varied from 7.9 nm to 13 nm. The evolution of the morphology of InAs QWRs was attributed to the diffusion anisotropy of In adatoms.

Symmetry in the diagonal self-assembled InAs quantum wire arrays on InP substrate

Diagonal self-assembled InAs quantum wire (QWR) arrays with the stacked InAs/In0.52Al0.48As structure are grown on InP substrates, which are (001)-oriented and misoriented by 6degrees towards the [100] direction. Both the molecular beam epitaxy (MBE) and migration enhanced epitaxy (MEE) techniques are employed. Transmission electron microscopy reveals that whether a diagonal InAs QWR array of the stacked InAs/InAlAs is symmetrical about the growth direction or not depends on the growth method as well as substrate orientation. Asymmetry in the diagonal MEE-grown InAs QWR array can be ascribed to the influence of surface reconstruction on upward migration of adatoms during the self-assembly of the InAs quantum wires.

A new method to fabricate InGaN quantum dots by metalorganic chemical vapor deposition

A new method to form nanoscale InGaN quantum dots using MOCVD is reported, This method is much different from a method. which uses surfactant or the Stranski-Krastannow growth mode. The dots were formed by increasing the energy barrier for adatoms, which are hopping by surface passivation, and by decreasing the growth temperature. Thus, the new method can be called as a passivation-low-temperature method. Regular high-temperature GaN films were grown first and were passivated. A low-temperature thin layer of GaN dot was then deposited on the surface that acted as the adjusting layer. At last the high-density InGaN dots could be fabricated on the adjusting layer. Atomic force microscopy measurement revealed that InGaN dots were small enough to expect zero-dimensional quantum effects: The islands were typically 80 nm wide and 5 nm high. Their density was about 6 x 10(10) cm(-2). Strong photoluminescence emission from the dots is observed at room temperature, which is much stronger than that of the homogeneous InGaN film with the same growth time. Furthermore, the PL emission of the GaN adjusting layer shows 21 meV blueshift compared with the band edge emission of the GaN due to quantum confine effect. (C) 2002 Elsevier Science B.V. All rights reserved.

Low-temperature growth of cubic GaN by metalorganic chemical-vapor deposition

Low-temperature growth of cubic GaN at 520 degrees C was achieved using CCl4 as an additive by metalorganic chemical-vapor deposition (MOCVD) on GaAs substrate. X-Ray measurement confirmed that the films are single-phase cubic GaN. Scanning electron microscopy (SEM) and reflection high-energy electron diffraction (RHEED) were also used to analyze the surface morphology and the quality of films. The evolution of surface morphology suggests that CCl4 can reduce the hopping barrier and thus Ga adatoms are able to diffuse easily on the GaN surface. (C) 1998 Elsevier Science S.A. All rights reserved.

Self-assembled GaAs quantum rings by MBE droplet epitaxy

Fabrication of semiconductor nanostructures such as quantum dots (QDs), quantum rings (QRs) has been considered as the important step for realization of solid state quantum information devices, including QDs single photon emission source, QRs single electron memory unit, etc. To fabricate GaAs quantum rings, we use Molecular Beam Epitaxy (MBE) droplet technique in this report. In this droplet technique, Gallium (Ga) molecular beams are supplied initially without Arsenic (As) ambience, forming droplet-like nano-clusters of Ga atoms on the substrate, then the Arsenic beams are supplied to crystallize the Ga droplets into GaAs crystals. Because the morphologies and dimensions of the GaAs crystal are governed by the interplay between the surface migration of Ga and As adatoms and their crystallization, the shape of the GaAs crystals can be modified into rings, and the size and density can be controlled by varying the growth temperatures and As/Ga flux beam equivalent pressures(BEPs). It has been shown by Atomic force microscope (AFM) measurements that GaAs single rings, concentric double rings and coupled double rings are grown successfully at typical growth temperatures of 200 C to 300 C under As flux (BEP) of about 1.0 x 10(-6) Torr. The diameter of GaAs rings is about 30-50 nm and thickness several nm.