Surface properties of titanium nitride: A first-principles study

The low-index surfaces of TiN are calculated using the first-principles method based on density functional theory. It is found that the relaxation effect is mainly localized in the outmost three layers for all surfaces, and the distance reduction of the outmost interlayer for the N-terminated (111) surface is much larger than other surfaces. The N-terminated (111) surface is thermodynamically favorable at high nitrogen chemical potential, which is consistent with the experimental results.     

High-temperature morphology of stepped gold surfaces

Molecular dynamics simulations with a classical many-body potential are used to study the high-temperature stability of stepped non-melting metal surfaces. We have studied in particular the Au(111) vicinal surfaces in the (M + 1,M− 1,M) family and the Au(100) vicinals in the (M,1,1) family. Some vicinal orientations close to the non-melting Au(111) surface become unstable close to the bulk melting temperature and facet into a mixture of crystalline (111) regions and localized surface-melted regions. On the contrary, we do not find high-temperature faceting for vicinals close to Au(100), also a non-melting surface. These (100) vicinal surfaces gradually disorder with disappearance of individual steps well below the bulk melting temperature. We have also studied the high-temperature stability of ledges formed by pairs of monatomic steps of opposite sign on the Au(111) surface. It is found that these ledges attract each other, so that several of them merge into one larger ledge, whose edge steps then act as a nucleation site for surface melting.     

IR absorption enhancement for physisorbed methanol on Ag island films deposited on the oxidized and H-terminated Si(111) surfaces: effect of the metal surface morphology

Infrared absorption measurements using a multiple internal reflection geometry are reported for condensed methanol at 90 K on Ag island films deposited on the oxidized and hydrogen-terminated surfaces of Si(111). The attenuated total reflection (ATR) spectra obtained as a function of methanol exposure (up to 14 L) show that a 1-nm mass thickness of Ag island film on the oxidized Si(111) surface yields an absorption intensity 2–3 times larger than the intensity in the absence of Ag on the oxidized surface. Deposition of the same thickness of Ag on the hydrogen-terminated Si(111) surface results in approximately twice the enhancement. The different magnitudes of the enhancement are discussed based on SEM micrographs for Ag island films formed on the oxidized and H-terminated Si(111) surfaces. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 5 May 1999     

GaAs(111)表面硅烯、锗烯的几何及电子性质研究

基于密度泛函理论的第一性原理计算方法, 系统研究了硅烯、锗烯在GaAs(111) 表面的几何及电子结构. 研究发现, 硅烯、锗烯均可在As-中断和Ga-中断的GaAs(111) 表面稳定存在, 并呈现蜂窝状六角几何构型. 形成能计算结果证明了其实验制备的可行性. 同时发现硅烯、锗烯与GaAs表面存在共价键作用, 这破坏了其Dirac电子性质. 进一步探索了利用氢插层恢复硅烯、锗烯Dirac电子性质的方法. 发现该方法可使As-中断面上硅烯、锗烯的Dirac电子性质得到很好恢复, 而在Ga-中断面上的效果不够理想. 此外, 基于原子轨道成键和杂化理论揭示了GaAs表面硅烯、锗烯能带变化的物理机理. 研究结果为硅烯、锗烯在半导体基底上的制备及应用奠定了理论基础.     

Scanning kinetic spectroscopy (SKS): A new method for investigation of surface reaction processes

Multiple reaction pathways are available to a polyatomic molecule interacting with a solid surface. Delineation of exact temperature regions in which the various pathways are either active or inactive is accomplished using a new method, Scanning Kinetic Spectroscopy (SKS). SKS uses a calibrated and collimated beam of reactant molecules incident upon a clean single crystal surface in UHV. A multiplexed quadrupole mass spectrometer (QMS) is enclosed inside a differentially pumped random flux shield, in line of sight to the crystal surface. The crystal temperature is programmed with a linear ramp (dT/dt = 2K/s.) and reactant consumption, product evolution, and desorption of stable surface species are simultaneously measured in one experiment. SKS data are presented here which characterize the reactions of methanol with the single crystal surfaces Ni(111), Cu(111), and Cu(111) plus preadsorbed oxygen. Application of the SKS method as an efficient probe of surface reaction pathways is illustrated by the contrasting chemistry of these surfaces. The methanol plus Ni(111) system is examined in detail in order to relate the observed SKS features to specific molecular reaction pathways on the Ni(111) surface.     

SiO production from Si(100) and (111) surfaces by reaction with O2 beams

Desorption kinetics of SiO in the reaction of O₂ with Si(100) and (111) surfaces were investigated at surface temperatures between 1000 and 1300 K by using a pulsed molecular beam technique. The gaseous SiO product was detected by a mass spectrometer above 1000 K. At temperatures lower than 1050 K, the SiO signal appeared with an induction time after the O₂ beam irradiation onto the surface, which means that the desorption occurs via sequential steps. The rate constants for two steps were obtained by a computer simulation of the relaxation waveforms of the SiO signal. The values obtained are in the same range as those of D'Evelyn et al. However, they are one order of magnitude larger than those of Yu and Eldridge. The activation energies for the two steps are 2.8 and 2.4 eV for both Si(100) and (111) surfaces. No significant difference between the two kinds of surfaces was found from these values. However, many etch pits were observed on the Si(100) surface after the reaction, while no such etch pits were formed on the Si(111) surface. The planes of the etch pits formed on the (100) surfaces consisted mostly of the {111} facets.     

A vibrational study of ammonia chemisorbed on Ni(110) and Ni(111): whither goest the metal-nitrogen stretching mode on FCC (111) surfaces?

The adsorption of ammonia on the Ni(110) and Ni(111) surfaces has been studied with high resolution (≤ 65 cm_?1) electron energy loss spectroscopy (EELS) combined with thermal desorption spectroscopy. The EELS spectra of the initial chemisorbed layer or α state on each surface are very different. Ammonia chemisorbed on the Ni(110) surface exhibits a strong Ni-N stretching mode at 570 cm^?1 which is absent on the Ni(111) surface. The Ammonia adsorption site appears to be different on the Ni(110) and Ni(111) surfaces. We suggest that the absence of the M-N stretching mode on the Ni(111) surface is a general characteristic of the ammonia adsorption site on the (111) surfaces of fcc Group VIII metals.     

Hydrogen adsorption and surface structures of silicon

The adsorption of atomic hydrogen on silicon (111)2 × 1 cleaved, (111) 7 × 7, and (100) 2 × 1 surfaces has been studied by using electron energy loss spectrscopy (ELS) and Photoemission spectroscopy (UPS). On all surfaces the hydrogen removes the “dangling bond” surface state and a new peak in the density of states at lower energies corresponding to the SiH bond is found. The LEED pattern of the equilibrium surfaces (111) 7 × 7 and (100) 2 × 1 is not altered by hydrogen adsorption, while on the cleaved (111) 2 × 1 surface the fractional order spots are extinguished. The Haneman surface-buckling model therefore provides an explanation for the surface reconstruction of the cleaved (111) 2 × 1 surfaces. For the equilibrium surfaces, (111) 7 × 7 and the (100) 2 × 1, the data are consistent with the Lander-Phillips model.     

Surface Structure of Large Synthetic Diamonds by High Temperature and High Pressure

With NiMnCo and FeCoNi alloys as solvent metals, large single-crystal diamonds of about 3mm across are grown by temperature gradient method （TGM） under high temperature and high pressure （HPHT）. Although both {100} and {111} surfaces are developed by a layer growth mechanism, some different characteristic patterns are seen clearly on the different surfaces, no matter whether NiMnCo or FeCoNi alloys are taken as the solvent metals. For {100} surface, it seems to have been melted or etched greatly, no dendritic patterns to be found, and only a large number of growth hillocks are dispersed net-likely; while for {111} surface, it often seems to be more smooth-faced, no etched or melted traces are present even when a lot of depressed trigonal growth layers. This distinct difference between {111} and {100} surfaces is considered to be related to the difference of surface-atom distribution of different surfaces, and {111} surfaces should be more difficult to be etched and more steady than {100} surfaces.     

Structural,electronic and magnetic properties of the (001), (110) and (111) surfaces of rocksalt sodium sulfide: A first-principles study

First principles study of the structural, electronic and magnetic properties of the (111), (110) and (001) surfaces of rocksalt sodium sulfide (rs-NaS) are reported. The results show that the bulk half-metallicity of this compound is well preserved on the surfaces considered here except for Na-terminated (111) surface. The spin-flip gap at the S-terminated (111), (001) and (110) surfaces are close to the bulk value. Using ab-initio atomistic thermodynamics, we calculate the surface energies as a function of chemical potential to find the most stable surface. We find that the Na-terminated (111) surface is the most stable one over the whole allowed range of chemical potential, while the surface energies of the (001) and (110) surfaces approach the most stable surface energy at the sulfur rich environment. We have also calculated the interlayer exchange interaction in bulk and Na-terminated (111) surface by classical Heisenberg model and we found that the surface effects do not change these kinds of interactions significantly.     

Stability and electronic properties of the O-terminated Cu2O(111) surfaces: First-principles investigation

The effect of different vacancies on the morphology of the O-terminated Cu₂O(111) surface has been studied through the first-principles calculations. Our results show that Cu and O vacancies trigger large relaxations and formation of two different facets. Our emulated STM images are in consistent with the experimental STM patterns. A sizeable magnetic moment (∼1.0 μ_B) was found for surfaces with either Cu or O vacancies. The calculated formation energies of surface vacancies indicate that the deficient surfaces are more stable than the stoichiometric O-terminated (1×1) surface, which is also in line with our results obtained from ab initio atomistic thermodynamics studies.     

Cluster model approach for electronic structure of Si and Ge(111) and GaAs(110) surfaces

For the purpose of exploring how realistic a cluster model can be for semiconductor surfaces, extended Huckel theory calculations are performed on clusters modeling Si and Ge(111) and GaAs(110) surfaces as prototypes. Boundary conditions of the clusters are devised to be reduced. The ideal, relaxed, and reconstructed Si and Ge(111) surfaces are dealt with. Hydrogen chemisorbed (111) clusters of Si and Ge are also investigated as prototypes of chemisorption systems. Some comparison of the results with finite slab calculations and experiments is presented. The cluster-size dependence of the calculated energy levels, local densities of states, and charge distributions is examined for Si and Ge(111) clusters. It is found that a 45-atom cluster which has seven layers along the [111] direction is large enough to identify basic surface states and study the hydrogen chemisorption on Si and Ge(111) surfaces. Also, it is presented that surface states on the clean Si and Ge(111) clusters exist independent of relaxation. Further, the calculation for the relaxed GaAs(110) cluster gives the empty and filled dangling-orbital surface states comparable to experimental data and results of finite slab calculations. The cluster approach is concluded to be a highly useful and economical one for semiconductor surface problems.     

Adsorption studies on a stepped Pt(111) surface: O2, CO,C2H4, C2N2

A comparative study of the adsorption of several gases on a Pt(S)-[9(111) × (111)] surface was performed using LEED, Auger spectroscopy, flash desorption mass spectrometry and work function changes as surface sensitive techniques. Adsorption was found to be generally less ordered on the stepped surface than on the corresponding flat surface with the exception of the oxygen, where r well ordered overlayer in registry over many terraces was found. Absolute coverages were determined from flash desorption experiments for O₂, CO and C₂N₂. Similar values were obtained as on flat Pt surfaces. Two different surface species seem to be formed upon adsorption of C₂H₄ depending on the adsorption temperature. Contrary to reports from Pt(111) surfaces conversion between the two surface species is heavily restricted on the stepped surface. Work function changes revealed nonlinear adsorbate effects where the adsorbate is electronegative with respect to the substrate. Various adsorption models are discussed in the light of complementary experimental evidence. The results of this study are compared with data available from flat Pt surfaces and possible influences of steps are discussed. No general trends, however, emerge from this comparison and it seems that eventual influences of steps have to be considered individually for every adsorbate.     

氧化镁纳米多晶的微结构和磁性

实验发现,宏观晶体是非磁性的氧化镁时,其多晶样品有弱铁磁性.本文用第一性原理电子结构方法研究了氧化镁表面、纳米颗粒和晶界的磁性.计算结果表明:绝缘的氧化镁表面可以是导电的,并且有与之相关的铁磁性;磁性表面的共同特征是在表面上有氧原子富集,包括(111)表面的纯氧原子层,(114)表面的氧原子链;其他高晶面指数表面也会有氧原子富集区域;氧化镁纳米颗粒的磁性出现在高晶面指数表面以及不同晶面交界的棱及其顶角等有氧原子富集的区域,这种由氧原子富集而形成的磁性有巡游特征.氧化镁Σ7[111]和Σ5[001]晶界的计算结果表明:在没有氧原子富集的情况下,多晶样品中晶界的磁性很弱,而在有氧原子富集的情况下,晶界磁性比较强.因此可以推断多晶样品的磁性主要出现在多晶表面、晶粒包围孔隙、微裂纹界面、晶界和其他晶体缺陷等有氧原子富集的区域.这种残余磁性可以通过热处理等结构优化过程而削弱甚至消除.     

CHaracterization of CO binding sites on Rh{111} and Rh{331} surfaces by XPS and LEED: Comparison to EELS results

Changes in the nature of the binding site of chemisorbed CO on the Rh{111} and Rh{331} single crystal surfaces during adsorption and desorption have been monitored by X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). Two bonding states of molecular CO have been identified from the O 1s photoemission line. These states are assigned as atop and bridge-bonded species and are observed to be coverage and temperature dependent. On both surfaces atop sites are populated first and at higher CO coverages bridge sites are filled. On Rh{111} the bridge sites are filled at a CO coverage of θ_CO ～ 0.50 and their presence is correlated with a change in the LEED pattern. The presence of the step atoms on the Rh{331} surface markedly influenced the sequential filling of binding sites in comparison to that observed on the Rh{111} surface. A comparison of our data to previous Electron Energy Loss Spectroscopy (EELS) work on Rh{111} is in remarkable quantitative agreement with EELS peak heights.     

The interplay between geometry,electronic structure,and reactivity of Cu-Ni bimetallic (111) surfaces

The mutual influence of surface geometry (e.g. lattice parameters, morphology) and electronic structure is discussed for Cu-Ni bimetallic (111) surfaces. It is found that on flat surfaces the electronic d-states of the adlayer experience very little influence from the substrate electronic structure which is due to their large separation in binding energies and the close match of Cu and Ni lattice constants. Using carbon monoxide and benzene as probe molecules, it is found that in most cases the reactivity of Cu or Ni adlayers is very similar to the corresponding (111) single crystal surfaces. Exceptions are the adsorption of CO on submonolayers of Cu on Ni(111) and the dissociation of benzene on Ni/Cu(111) which is very different from Ni(111). These differences are related to geometric factors influencing the adsorption on these surfaces. Received: 26 August 2002 / Accepted: 4 September 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +44-1223/76-2829, E-mail: gh10009@cam.ac.uk [+1pt] Present address: University of Cambridge, Lensfield Road, Department of Chemistry, Cambridge CB2 1EW, UK     

Exploring the molecular mechanisms of reactions at surfaces

The study of the molecular mechanism of chemical reactions occurring at solid surfaces is of primary importance to understand heterogeneous catalysis from a microscopic point of view. The present paper reviews the state of the art methods of electronic structure and the surface models currently used in this type of studies by making use of three different examples. Those are the decomposition of azomethane on Pt(111), the study of the different selectivity of Cu(111) and Ag(111) towards ethene partial oxidation and the comparative study of NO dissociation on Rh(111) and bimetallic RhCu(111) surfaces. These examples illustrate the power of the electronic structure computational approaches to predict the structure and stability of different intermediates and to unravel the molecular mechanism of these surface reactions.     

Analyses of HF/NH4F buffer-treated Si(111) surfaces using XPS,REM and SIMS

The effect of different cleaning procedures on Si(111) wafers has been studied. A three-step cleaning process was used. The first two steps (thermal oxidation followed by RCA cleaning) were common to all samples. The final step involved rinsing in one of a set of HF/NH4F buffer solutions with a wide range ofpH values. Three different surface techniques were used for characterizing the chemical condition and morphology of the treated surfaces: XPS (X-ray Photoemission Spectroscopy), REM (Reflection Electron Microscopy) and SIMS (Secondary-Ion Mass Spectroscopy). It has been found that thepH value of an HF solution does significantly affect the etching rate and morphology of the Si(111) surface: For the same type of solution, the smaller thepH value, the higher the etching rate. Basic solutions withpH values larger than eight have a much weaker etching effect on the surface, which is contradictory to some previous reports. The most effective solutions for the etching of the Si(111) surface are the solutions of HF buffered by NH₄F, with thepH in the range of 2–6. REM images indicate that the surface morphology after etching in the HF solution is strongly affected by the length of the etching time: Overetching will roughen the surface. The SIMS data show that water rinsing in air during the cleaning process does speed up oxidation, but it is necessary to use water to clean off the residuals from the HF solutions.     

Observation of disorder-induced 2D mott-hubbard states of the alkali-earth metal (Mg,Ba)-adsorbed Si(111) surface

We report evidence of a disorder-driven Mott-Hubbard-type localization on the alkali-earth metal (AEM) (Mg,Ba)-adsorbed Si(111)-(7x7) surface. The clean metallic Si(111) surface is found to undergo a two-dimensional (2D) metal-insulator transition as randomly distributed AEM adsorbates cause disorder on the surface. A well-defined electron-energy-loss peak unique to the insulating phase is attributed to an interband excitation between the split Hubbard bands originated from a metallic surface band at Fermi energy. A quantitative analysis of the loss peak reveals that the AEM-induced insulating surfaces are of a Mott-Hubbard type driven essentially by disorder.     

Growth kinetics of self-assembled monolayers of thiophene and terthiophene on Au(111): An infrared spectroscopic study

The growth kinetics of self-assembled monolayers (SAMs) of thiophene compounds on Au(111) surfaces was revealed by Fourier-transform infrared reflection absorption spectroscopy (FT-IR-RAS). Thiophene and terthiophene form well-ordered SAMs on Au(111) surfaces by immersing gold substrates into their ethanol solutions for ca. 15 h. Gibbs free energies for the adsorption processes of thiophene and terthiophene were found to be identical. However, the growth and molecular orientation of SAMs are different between two thiophene compounds. Terthiophene in SAMs orients parallel to the surface. The SAM growth of terthiophene obeys a time-dependent Langmuir scheme. On the other hand, the thiophene SAM undergoes a two-step growth process with unique molecular orientations. In the primary phase, thiophene assumes a parallel orientation on the Au(111) surface. In the second phase, thiophene is oriented close to the normal of the surface. The different growth process between thiophene and terthiophene is attributable to the topology of sulfur positions in the molecules. Received 23 May 2001 and Received in final form 11 February 2002