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.

Influence of AlN Buffer Thickness on GaN Grown on Si(111) by Gas Source Molecular Beam Epitaxy with Ammonia

Hexagonal GaN is grown on a Si(111) substrate with AlN as a buffer layer by gas source molecular beam epitaxy (GSMBE) with ammonia. The thickness of AlN buffer is changed from 9 to 72 nm. When the thickness of AlN buffer is 36 nm, the surface morphology and crystal quality of GaN is optimal. The in-situ reflection high energy electron diffraction (RHEED) reveals that the transition to a two-dimensional growth mode of AlN is the key to the quality of GaN. However, the thickness of AlN buffer is not so critical to the residual in-plane tensile stress in GaN grown on Si(111) by GSMBE for AlN thickness between 9 to 72 nm.

Ordering growth of InAs quantum dots on ultra-thin InGaAs strained layer

InAs quantum dots (QDs) were grown On Ultra-thin In0.15Ga0.85As strained layers by molecular beam epitaxy on GaAs (00 1) substrates. Combining reflection high-energy electron diffraction, atomic force microscopy and transmission electron microscopy, we analyzed the stress field of dislocations in the strained layer/substrate interface. Specially, we revealed the relative position of QDs and dislocations. We found that the difference of the stress field around dislocations is prominent when the strained layer is ultra-thin and the stress field will directly affect the following growth. On the strained layer surface, In0.15Ga0.85As ridges will form at the inclined upside of dislocations. Then, InAs QDs will prefer nucleating on the ridges, there is relatively small stress between InAs and In0.15Ga0.85As. By selecting ultra-thin In0.15Ga0.85As layer (50 nm) and controlling the QD layer at just form QDs, we obtained ordered InAs QDs. (C) 2004 Elsevier B.V. All rights reserved.

Growth and characterization of InN on sapphire substrate by RF-MBE

Indium nitride (InN) films were grown on sapphire substrates by radio-frequency plasma-excited molecular beam epitaxy (RF-MBE). Atomic force microscopy (AFM), reflection high-energy electron diffraction (RHEED), double-crystal X-ray diffraction (DCXRD) and photoluminescence (PL) spectroscopy were used to characterize the InN films. The results show that the InN films have good crystallinity, with full-width at half-maximum (FWHM) of InN (0 0 0 2) DCXRD peak being 14 arcmin. At room temperature, a strong PL peak at 0.79eV was observed. At 1.9eV or so, no peak was observed. In addition, it is found that the InN films grown with low-temperature (LT) InN buffer layer are of better quality than those without LT-InN buffer layer. (c) 2004 Elsevier B.V. All rights reserved.

Structural and optical properties of InAs/GaAs quantum dots emitting at 1.5 mu m

We have demonstrated 1.5 mum light emission from InAs quantum dots (QDs) capped with a thin GaAs layer. The extension of the emission wavelength can be assigned to the large QD height. We also investigate the effect of growth interruption on the PL properties and the shape of InAs QDs fabricated by migration-enhanced growth (MEG). Contrary to expectation, we observed a remarkable blueshift of the emission energy with the growth interruption in MEG mode. Detailed investigations reveal that the blueshift is related to the reduced island height with the growth interruption, which is confirmed by reflection high-energy electron diffraction (RHEED) patterns and atomic force microscopy (AFM) measurement results. Accordingly, the structure changes of the islands are interpreted in terms of thermodynamic and kinetic theories. (C) 2004 Elsevier B.V. All rights reserved.

Effects of growth temperature of AlGaN buffer layer on the properties of A1(0.58)Ga(0.42)N epilayer by NH3-MBE

Al0.58Ga0.42N epilayers are grown by ammonia gas source molecular beam epitaxy (NH3-MBE) on (0001) sapphire substrate using AlGaN buffer layer. The effects of the buffer layer growth temperature on the properties of Al0.58Ga0.42N epilayer are especially investigated. In-situ high-energy electron diffraction (RHEED), double-crystal X-ray diffraction (DCXRD), atomic force microscopy (AFM), photoconductivity measurement and cathodoluminescence (CL) are used to characterize the samples. It is found that high growth temperature of AlGaN buffer layer would improve the crystalline quality, surface smoothness, optical quality and uniformity of the Al0.58Ga0.42N epilayer. The likely reason for such improvements is also suggested. (C) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The role of Sb in the molecular beam epitaxy growth of 1.30-1.55 mu m wavelength GaInNAs/GaAs quantum well with high indium content

Sb-assisted GaInNAs/GaAs quantum wells (QWs) with high (42.5%) indium content were investigated systematically. Transmission electron microscopy, reflection high-energy electron diffraction and photoluminescence (PL) measurements reveal that Sb acts as a surfactant to suppress three-dimensional growth. The improvement in the 1.55 mu m range is much more apparent than that in the 1.3 mu m range.. which can be attributed to the difference in N composition. The PL intensity and the full-width at half maximum of the 1.55 mu m single-QW were comparable with that of the 1.3 Am QWs. (c) 2006 Elsevier B.V. All rights reserved.

Fabrication of novel double-hetero-epitaxial SOT structure Si/gamma-Al2O3/Si

In this paper, we report the fabrication of Si-based double-hetero-epitaxial silicon on insulator (SOI) structure Si/gamma-Al2O3/Si. Firstly, single crystalline gamma-Al2O3(100) insulator films were grown epitaxially on Si(100) using the sources of TMA (Al(CH3)(3)) and O-2 by very low-pressure chemical vapor deposition. Afterwards, Si(100) epitaxial films were grown on gamma-Al2O3 (100)/Si(100) epi-substrates using a chemical vapor deposition method similar to the silicon on sapphire epitaxial growth. The Si/gamma-Al2O3/Si SOL materials are characterized in detail by reflect high-energy electron diffraction, X-ray diffraction and Auger energy spectrum (AES) techniques. The insulator layer of gamma-Al2O3 has an excellent dielectric property. The leakage current is less than 1 x 10(-10) A/cm(2) when the electric field is below 1.3 MV/ cm. The Si film grown on gamma-Al2O3/Si epi-substrates was single crystalline. Meanwhile, the AES depth profile of the SOL structure shows that the composition of gamma-Al2O3 film is uniform, and the carbon contamination is not observed. Additionally, the gamma-Al2O3/Si epi-substrates are suitable candidates as a platform for a variety of active layers such as GaN, SiC and GeSi. It shows a bright future for microelectronic and optical electronics applications. (C) 2002 Elsevier Science B.V. All rights reserved.

Abnormal effect of growth interruption on GaSb quantum dots formation grown by molecular beam epitaxy

The growth interruption (GI) effect on GaSb quantum dot formation grown on GaAs by molecular beam epitaxy was investigated. The structure characterization was performed by reflection high-energy electron diffraction (RHEED), along with photoluminescence measurements. It is found that the GI can significantly change the surface morphology of GaSb QDs. During the GI, the QDs structures can be smoothed out and turned into a 2D-like structure. The time duration of the GI required for the 3D/2D transition depends on the growth time of the GaSb layer. It increases with the increase of the growth time. Our results are explained by a combined effect of the stress relaxation process and surface exchange reactions during the GI. (C) 2002 Elsevier Science B.V. All rights reserved.

Heteroepitaxial growth and annealing of gamma-Al2O3 thin films on silicon

The gamma-Al2O3 films were grown on Si (100) substrates using the sources of TMA (Al (CH3)(3)) and O-2 by very low-pressure chemical vapor deposition (VLP-CVD). It has been found that the gamma-Al2O3 film has a mirror-like surface and the RMS was about 2.5nm. And the orientation relationship was gamma-Al2O3(100)/Si(100). The thickness uniformity of gamma-Al2O3 films for 2-inch epi-wafer was less than 5%. The X-ray diffraction (XRD) and reflection high-energy electron diffraction (RHEED) results show that the crystalline quality of the film was improved after the film was annealed at 1000degreesC in O-2 atmosphere. The high-frequency C-V and leakage current of Al/gamma-Al2O3/Si capacitor were also measured to verify the annealing effect of the film. The results show that the dielectric constant increased from 4 to 7 and the breakdown voltage for 65-nm-thick gamma-Al2O3 film on silicon increases from 17V to 53V.

Growth mode and strain evolution during InN growth on GaN(0001) by molecular-beam epitaxy

Epitaxial growth of InN on GaN(0001) by plasma-assisted molecular-beam epitaxy is investigated over a range of growth parameters including source flux and substrate temperature. Combining reflection high-energy electron diffraction (RHEED) and scanning tunneling microscopy (STM), we establish a relationship between film growth mode and the deposition condition. Both two-dimensional (2D) and three-dimensional (3D) growth modes of the film are observed. For 2D growth, sustained RHEED intensity oscillations are recorded while STM reveals 2D nucleation islands. For 3D growth, less than three oscillation periods are observed indicating the Stranski-Krastanov (SK) growth mode of the film. Simultaneous measurements of (reciprocal) lattice constant by RHEED suggest a gradual relaxation of the strain in film, which commences during the first bilayer (BL) deposition and almost completes after 2-4 BLs. For SK growth, 3D islanding initiates after the strain has mostly been relieved, presumably by dislocations, so the islands are likely strain free. (C) 2002 American Institute of Physics.

Investigation of GaN layer grown on Si(111) substrate using an ultrathin AlN wetting layer

High-quality GaN epilayers were grown on Si (1 1 1) substrate by metalorganic chemical vapor deposition. The growth process was featured by using an ultrathin AlN wetting layer (WL) in combination with a low-temperature (LT) GaN nucleation layer (NL). The full-width at half-maximum (FWHM) of the X-ray rocking curve for the GaN (0 0 0 2) diffraction was 15 arcmin. The dislocation density estimated from TEM investigation was found to be of the order of 10(9)cm(-2). The FWHM of the dominant band edge emission peak of the GaN was measured to be 47 meV by photoluminescence measurement at room temperature. The ultrathin AlN WL was produced by nitridation of the aluminium pre-covered substrate surface. The reflection high-energy electron diffraction showed that the AlN WL was wurtzite and the surface morphology was like the nitridated surface of sapphire by the atomic force microscopy measurement. X-ray photoelectron spectroscopy measurement showed that Si and SixNy at a certain concentration were intermixed in the AlN WL. This study suggests that by employing an appropriate WL combined with a LT NL, high-quality heteroepitaxy is achievable even with large mismatch. (C) 2002 Elsevier Science B.V. All rights reserved.

Carbonization process of Si(100) by ion-beam bombardment

The evolution of carbonization process on Si as a function of ion dose has been carried out by mass-selected ion-beam deposition technique. 3C-SiC layer has been obtained at low ion dose, which has been observed by reflection high energy electron diffraction and X-ray photoelectron spectroscopy (XPS). The chemical states of Si and carbon have also been examined as a function of ion dose by XPS. Carbon enrichment was found regardless of the used ion dose here, which may be due to the high deposition rate. The formation mechanism of SiC has also been discussed based on the subplantation process. The work will also provide further understanding of the ion-bombardment effect. (C) 2001 Published by Elsevier Science B.V.

Quality improvement of GaInNAs/GaAs quantum wells grown by plasma-assisted molecular beam epitaxy

The optimum growth condition of GaInNAs/GaAs quantum wells (QWs) by plasma-assisted molecular beam epitaxy was investigated. High-resolution X-ray diffraction and photoluminescence (PL) measurements showed that ion damage drastically degraded the quality of GaNAs and GaInNAs QWs and that ion removal magnets can effectively remove the excess ion damage. Remarkable improvement of PL intensity and obvious appearance of pendellosung fringes were observed by removing the N ions produced in the plasma cell. When the growth rate increased from 0.73 to 1.2 ML/s, the optimum growth temperature was raised from 460 degreesC to 480 degreesC and PL peak intensity increased two times. Although the N composition decreased with increasing growth rate, degradation of optical properties of GaInNAs QWs was observed when the growth rate was over 0.92 ML/s. Due to low-temperature growth of GaInNAs QWs, a distinctive reflection high-energy electron diffraction pattern was observed only when the GaAs barrier was grown under lower As-4 pressure. The samples with GaAs barriers grown under lower As-4 pressure (V/III ratio about 24) exhibited seven times increase in PL peak intensity compared with those grown under higher As-4 pressure (V/III ratio about 50). (C) 2001 Elsevier Science B,V. All rights reserved.