Comparison of the interaction of Pd with positively and negatively poled LiNbO3(0 0 0 1)

To investigate the possibility of manipulating the surface chemical properties of finely dispersed metal films through ferroelectric polarization, the interaction of palladium with oppositely poled LiNbO₃(0 0 0 1) substrates was characterized. Low energy ion scattering indicated that the Pd tended to form three-dimensional clusters on both positively and negatively poled substrates even at the lowest coverages. X-ray photoelectron spectroscopy (XPS) showed an upward shift in the binding energy of the Pd 3d core levels of 0.9 eV at the lowest Pd coverages, which slowly decayed toward the bulk value with increasing Pd coverage. These shifts were independent of the poling direction of the substrate and similar to those attributed to cluster size effects on inert supports. Thus, the spectroscopic data suggested that Pd does not interact strongly with LiNbO₃ surfaces. The surface chemical properties of the Pd clusters were investigated using CO temperature programmed desorption. On both positively and negatively poled substrates, CO desorption from freshly deposited Pd showed a splitting of the broad 460 K desorption peak characteristic of bulk Pd into distinct peaks at 270 and 490 K as the Pd coverage was decreased below 1.0 ML; behavior that also resembles that seen on inert supports. It was found that a small fraction of the adsorbed CO may dissociate (<2%) for Pd on both positively and negatively poled substrates. The thermal response of the smaller Pd clusters on the LiNbO₃ surfaces, however, was different from that of inert substrates. In a manner similar to Nb₂O₅, when CO desorption experiments were carried out a second time, the adsorption capacity decreased and the higher temperature desorption peak shifted from 490 K to below 450 K. This behavior was independent of the substrate poling direction. Thus, while there was evidence that LiNbO₃ does not behave as a completely inert support, no significant differences between positively and negatively poled surfaces were observed. This lack of sensitivity of the surface properties of the Pd to the poling direction of the substrate is attributed to the three-dimensional Pd clusters being too thick for their surfaces to be influenced by the polarization of the underlying substrate.     

Structure analysis of stoichiometric LiNbO3(0 0 0 1) surfaces using low-energy neutral scattering spectroscopy

The atomic structure of LiNbO₃(0 0 0 1) surface was investigated by low-energy neutral scattering spectroscopy (LENS). Poled stoichiometric LiNbO₃ (SLN) samples were prepared for the measurements. The LENS was developed for surface structure and composition analysis particularly of highly insulating materials and was successfully applied to the structure analysis of the SLN(0 0 0 1) surface. The polar angle dependences of intensity of scattered He⁰ from the poled SLN surfaces indicate obvious differences between the negatively and the positively charged surfaces. It is suggested that O atoms cover the surfaces, and the first metal layers underneath the O layer consist of Li and Nb for negatively and positively charged surfaces, respectively, parallel to the applied electric field.     

The effect of ferroelectric polarization on the interaction of water and methanol with the surface of LiNbO3(0 0 0 1)

Water and methanol temperature programmed desorption (TPD) measurements were performed on the positive (c⁺) and negative (c⁻) surfaces of poled ferroelectric lithium niobate (LiNbO₃) single crystals. The results indicate that the molecule-surface interactions are both coverage and polarization-dependent. From a comparison of the TPD spectra for the positive and negative surfaces, it is shown that the desorption temperatures of water and methanol are consistently lower on the negative surface by 15 K and 20 K, respectively. The TPD spectra were simulated using the Polanyi-Wigner equation with a coverage-dependent energy term. These calculations show that the polarization dependence of the desorption temperature is due to a difference in the zero-coverage desorption energies on the two surfaces equal to a few kJ per mole. The mechanism for the polarization effect is explored with in situ pyroelectric voltage measurements, which indicate that a surface voltage of ±2 mV develops in the LiNbO₃(0 0 0 1) samples during TPD measurements. The magnitude of the pyroelectric-induced surface charge is heating rate dependent.     

Structural properties of oxygen on InN(0 0 0 1) surface

First-principles calculations are performed to study the various structures of oxygen (O) adsorbed on InN(0 0 0 1) surfaces. It is found that the formation energy of O on InN(0 0 0 1) decreases with decreasing oxygen coverage. Of all the adsorbate induced surface structures examined, the structure of InN(0 0 0 1)-(2 × 2) as caused by O adsorption at the H₃ sites with 0.25 monolayers coverage is most energetically favorable. Meanwhile, nitrogen (N) vacancy can form spontaneously. Oxygen atoms may also substitute N atoms, or accumulate at the voids inside InN film or simply stay on the surface during growth. The oxygen impurity then acts as a potential source for the n-type conductivity of InN as well as the large energy band gap measured.     

Adsorption of water on TiN (1 0 0), (1 1 0) and (1 1 1) surfaces: A first-principles study

We use first-principles density functional theory-based calculations in the analysis of the interaction of H₂O with (1 0 0), (1 1 0) and (1 1 1) surfaces of TiN, and develop understanding in terms of surface energies, polarity of the surface and chemistry of the cation, through comparison with H₂O adsorption on ZrN. While water molecule physisorbs preferentially at Ti site of (1 0 0) and (1 1 1) surfaces, it adsorbs dissociatively on (1 1 0) surface of TiN with binding stronger than almost 1.32 eV/molecule. Our analysis reveals the following general trends: (a) surfaces with higher energies typically lead to stronger adsorption, (b) dissociative adsorption of H₂O necessarily occurs on a charge neutral high energy surface and (c) lower symmetry of the (1 1 0) plane results in many configurations of comparable stability, as opposed to the higher symmetry (1 0 0) and (1 1 1) surfaces, which also consistently explain the results of H₂O adsorption on MgO available in literature. Finally, weaker adsorption of H₂O on TiN than on ZrN can be rationalized in terms of greater chemical stability of Ti arising from its ability to be in mixed valence.     

Comparison of O adsorption on Ni3Al (0 0 1), (0 1 1), and (1 1 1) surfaces through first-principles calculations

First-principles calculations were performed to study the properties of O adsorption on Ni₃Al (0 0 1), (0 1 1), and (1 1 1) surfaces using the Cambridge serial total package (CASTEP) code. Stable adsorption sites are identified. The atomic and electronic structures and adsorption energies are predicted. The adsorption sites for O on the Ni₃Al (0 0 1) surface are at the 2Ni–2Al fourfold hollow site, whereas O prefers to adsorb at the Ni–Al bridge site on (0 1 1) surface and 2Ni–Al threefold hollow site on (1 1 1) surface. It is found that O shows the strongest affinity for Al and the state of O is the most stabilized when O adsorbs on (0 0 1) surface, while the affinity of O for Al on (0 1 1) surface is weaker than (0 0 1) surface, and (1 1 1) surface is the weakest. The stronger O and Al affinity indicates more stable Al₂O₃ when oxidized. The experiment has shown that the oxidation resistance of single crystal superalloy in different orientations improves in the order of (1 1 1), (0 1 1), and (0 0 1) surface, suggesting that the oxidation in different crystallographic orientations may be related to the affinity of O for Al in the surface.     

Enhanced reactivity and selectivity in oxidation of Cu(1 0 0) and α-Cu-Al(5 at.%)(1 0 0) surfaces studied by electron and ion spectroscopies

In this study we investigate the influence of alloying on the reactivity and bonding of oxygen on α-Cu-Al(5 at.%)(1 0 0) oriented single crystal surfaces by X-ray photoelectron spectroscopy (XPS), ultra-violet spectroscopy (UPS) and low energy ion scattering (LEIS) spectroscopy, at room temperature. It was found that alloying results in an enhanced reactivity of both Cu and Al sites in comparison with the pure metals. According to adsorption curves calculated from XPS, saturation of the alloy surface occurs for exposures of ∼15 L. At saturation the total amount of adsorbed oxygen is similar for the alloy and pure copper surfaces. It was determined that first mostly Al sites are oxidized, followed by simultaneous oxidation of Cu and Al sites. At saturation the amount of oxygen bonded to Cu sites is ∼1.7 larger then that bonded to Al sites. From a comparison of the XPS and LEIS data analysis as a function of oxygen exposure it was found that oxidation of α-Cu-Al(5 at.%)(1 0 0) alloy is a multi-stage process with fast and slow stages. These stages involve an interplay of chemisorption, sub-surface diffusion of oxygen and Al segregation. UPS measurements show an increase in the work function of the alloy surface with oxygen adsorption. This is a contrast to pure Cu surfaces where the work function decreases at the initial stages of oxidation followed by an increase with oxygen exposure. Annealing to 400 °C drives the oxidized alloy surface into its thermodynamic state resulting in the formation of an aluminum oxide layer. Possible mechanisms to explain the enhanced reactivity of the alloy surface compared to that of pure copper are suggested and discussed.     

Oxidation of Pt(1 0 0)-hex-R0.7° by gas-phase oxygen atoms

We utilized temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (ELS), and low energy electron diffraction (LEED) to investigate the oxidation of Pt(1 0 0)-hex-R0.7° at 450 K. Using an oxygen atom beam, we generated atomic oxygen coverages as high as 3.6 ML (monolayers) on Pt(1 0 0) in ultrahigh vacuum (UHV), almost 6 times the maximum coverage obtainable by dissociatively adsorbing O₂. The results show that oxidation occurs through the development of several chemisorbed phases prior to oxide growth above about 1 ML. A weakly bound oxygen state that populates as the coverage increases from approximately 0.50 ML to 1 ML appears to serve as a necessary precursor to Pt oxide growth. We find that increasing the coverage above about 1 ML causes Pt oxide particle growth and significant surface disordering. Decomposition of the Pt oxide particles produces explosive O₂ desorption characterized by a shift of the primary TPD feature to higher temperatures and a dramatic increase in the maximum desorption rate with increasing coverage. Based on thermodynamic considerations, we show that the thermal stability of the surface Pt oxide on Pt single crystal surfaces significantly exceeds that of bulk PtO₂. Furthermore, we attribute the high stability and the acceleratory decomposition rates of the surface oxide to large kinetic barriers that must be overcome during oxide formation and decomposition. Lastly, we present evidence that structurally similar oxides develop on both Pt(1 1 1) and Pt(1 0 0), therefore concluding that the properties of the surface Pt oxide are largely insensitive to the initial structure of the Pt single crystal surface.     

Scattering of F atoms and anions on a TiO2(1 1 0) surface

Results of a study of energy losses and electron transfer processes for grazing scattering of fluorine atoms and anions scattering along different azimuthal orientations of the TiO₂ crystal are presented. We observe strong variations in the overall intensity of scattered particles which are due to channelling effects. The energy losses do not show strong variations as a function of crystal azimuth except for the case of scattering along the (0 0 1) direction between the bridging oxygen atom rows, where we also observe differences in the energy losses of scattered ions and neutrals. We attribute this to the fact that larger F⁻ survival occurs for trajectories staying farther from the surface, when also the energy losses remain small. The overall characteristics of energy losses are attributed mainly to trajectory effects due to scattering in regions of different electron density. Measurements of the ratio of scattered ions to the total scattered flux, i.e. the ion fractions which reflect electron capture and loss processes, show that these are not the same for incident anions and atoms. A strong difference for scattering along the (0 0 1) direction is observed, where at low incident energies a strong survival of incident ions occurs. These results are tentatively discussed in terms of non resonant electron capture at lattice O⁻ sites and electron loss into the conduction band or by collisional detachment with bridging O atoms.     

Hydroxylated α-Al2O3 (0 0 0 1) surfaces and metal/α-Al2O3 (0 0 0 1) interfaces

X-ray photoelectron spectroscopy was applied to study the hydroxylation of α-Al₂O₃ (0 0 0 1) surfaces and the stability of surface OH groups. The evolution of interfacial chemistry of the α-Al₂O₃ (0 0 0 1) surfaces and metal/α-Al₂O₃ (0 0 0 1) interfaces are well illustrated via modifications of the surface O1s spectra. Clean hydroxylated surfaces are obtained through water- and oxygen plasma treatment at room temperature. The surface OH groups of the hydroxylated surface are very sensitive to electron beam illumination, Ar⁺ sputtering, UHV heating, and adsorption of reactive metals. The transformation of a hydroxylated surface to an Al-terminated surface occurs by high temperature annealing or Al deposition.     

Surface chemistry of NO and NO2 on the Pt(1 1 0)-(1 × 2) surface: A comparative study

The surface chemistry of NO and NO₂ on clean and oxygen-precovered Pt(1 1 0)-(1 × 2) surfaces were investigated by means of high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). At room temperature, NO molecularly adsorbs on Pt(1 1 0), forming linear NO(a) and bridged NO(a). Coverage-dependent repulsive interactions within NO(a) drive the reversible transformation between linear and bridged NO(a). Some NO(a) decomposes upon heating, producing both N₂ and N₂O. For NO adsorption on the oxygen-precovered surface, repulsive interactions exist between precovered oxygen adatoms and NO(a), resulting in more NO(a) desorbing from the surface in the form of linear NO(a). Bridged NO(a) experiences stronger repulsive interactions with precovered oxygen than linear NO(a). The desorption activation energy of bridged NO(a) from oxygen-precovered Pt(1 1 0) is lower than that from clean Pt(1 1 0), but the desorption activation energy of linear NO(a) is not affected by the precovered oxygen. NO₂ decomposes on Pt(1 1 0)-(1 × 2) surface at room temperature. The resulted NO(a) (both linear NO(a) and bridged NO(a)) and O(a) repulsively interact each other. Comparing with NO/Pt(1 1 0), more NO(a) desorbs from NO₂/Pt(1 1 0) as linear NO(a), and both linear NO(a) and bridged NO(a) exhibit lower desorption activation energies. The reaction pathways of NO(a) on Pt(1 1 0), desorption or decomposition, are affected by their repulsive interactions with coexisting oxygen adatoms.     

Surface morphology of epitaxial lattice-matched Ba0.7Sr0.3O on Si(0 0 1) and vicinal Si(0 0 1)-4°[1 1 0] substrates

Exploring ways for self-organized structuring of insulating thin films, we investigated the possibility to produce replicas of step trains, given by a vicinal Si(0 0 1)-4°[1 1 0] surface, in layers of crystalline and perfectly lattice-matched Ba_0.7Sr_0.3O. For this purpose, we carried out high-resolution spot profile analyses in low-energy electron diffraction (SPA-LEED) both on flat Si(0 0 1) and on Si(0 0 1)-4°[1 1 0]. Oxide layers were generated by evaporating the metals in oxygen ambient pressure with the sample at room temperature. Our G(S) analysis of these mixed oxide layers reveals a strong influence of local compositional fluctuations of Sr and Ba ions and their respective scattering phases, which appears as an unphysically large variation of layer distances. Nevertheless, we are able to show that quite smooth and closed oxide films are obtained with an rms roughness of about 1 ML. These Ba_0.7Sr_0.3O films directly follow the step train of Sr-modified vicinal Si surfaces that form (1 1 3) oriented facets after adsorption of a monolayer of Sr. This proves that self-organized structuring of insulating films can indeed be an effective method.     

Low temperature adsorption of oxygen on reduced V2O3(0 0 0 1) surfaces

Well ordered V₂O₃(0 0 0 1) films were prepared on Au(1 1 1) and W(1 1 0) substrates. These films are terminated by a layer of vanadyl groups under typical UHV conditions. Reduction by electron bombardment may remove the oxygen atoms of the vanadyl layer, leading to a surface terminated by vanadium atoms. The interaction of oxygen with the reduced V₂O₃(0 0 0 1) surface has been studied in the temperature range from 80 to 610 K. Thermal desorption spectroscopy (TDS), infrared reflection absorption spectroscopy (IRAS), high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) were used to study the adsorbed oxygen species. Low temperature adsorption of oxygen on reduced V₂O₃(0 0 0 1) occurs both dissociatively and molecularly. At 90 K a negatively charged molecular oxygen species is observed. Upon annealing the adsorbed oxygen species dissociates, re-oxidizing the reduced surface by the formation of vanadyl species. Density functional theory was employed to calculate the structure and the vibrational frequencies of the O₂ species on the surface. Using both cluster and periodic models, the surface species could be identified as η²-peroxo () lying flat on surface, bonded to the surface vanadium atoms. Although the O-O vibrational normal mode involves motions almost parallel to the surface, it can be detected by infrared spectroscopy because it is connected with a change of the dipole moment perpendicular to the surface.     

GaN/LiNbO3 (0 0 0 1) interface formation calculated from first-principles

The stable adsorption sites for both Ga and N ions on the ideal and on the reconstructed LiNbO₃ (0 0 0 1) surface are determined by means of first-principle total energy calculations. A single N layer is found to be more strongly bound to the substrate than a single Ga layer. The adsorption of a GaN monolayer on the polar substrate within different orientations is then modeled. On the basis of our results, we propose a microscopic model for the GaN/LiNbO₃ interface. The GaN and LiNbO₃ (0 0 0 1) planes are parallel, but rotated by 30° each other, with in-plane epitaxial relationship [1 0 0]_GaN‖ [1 1  0]_LiNbO3. In this way the (0 0 0 1) plane lattice mismatch between GaN and LiNbO₃ is minimal and equal to 6.9% of the GaN lattice constant. The adsorbed GaN and the underlying LiNbO₃ substrate have parallel c-axes.     

Density functional study of oxygen adsorption on the Mg3Nd (0 0 1) surface

The adsorption of oxygen atoms on Mg₃Nd (0 0 1) surface was studied based on density function theory (DFT), in which the exchange-correlation potential was chosen as the generalized gradient approximation (GGA) in the Perdew and Wang (PW91). The most preferred adsorption position was at the top-hollow site. Upon the optimization on top-hollow site with different coverage, it was found that the adsorption energy decreased with oxygen coverage. The density of states analysis showed that obvious charge transfer took place between O atom and the nearest Nd atom and chemical bond formed between O atom and the nearest Nd atom after O adsorption. The result of surface energy as a function of chemical potential change of oxygen indicated the clean Mg₃Nd (0 0 1) surface was easy to adsorb oxygen and form 1.00 ML surface.     

Soft X-ray appearance potential spectroscopy (SXAPS) study of TiO2(1 1 0)-1 × 2 and (0 0 1)-1 × 1 surfaces

A soft X-ray appearance potential spectroscopy (SXAPS) apparatus with high sensitivity was built to measure non-derivative spectra. SXAPS spectra (non-derivative) of Ti 2p and O 1s for TiO₂(1 1 0)-1 × 2 and (0 0 1)-1 × 1 surfaces have been measured using low incident currents (about 10 μA/cm²) and a photon counting mode. Density of empty states on Ti and O sites are deduced by self-deconvoluting the spectra. The self-deconvoluted SXAPS spectra are qualitatively similar to those measured by X-ray absorption spectroscopy (XAS). The Ti 2p_3/2 spectrum shows two strong peaks which correspond to t_2g and e_g states. For the O 1s spectrum two strong peaks near the threshold are also found which can be ascribed to O 2pπ and O 2pσ states. These results suggest that the spectra almost obey the dipole selection rule, so-called the “approximate dipole selection rule”. The SXAPS spectra of Ti 2p and O 1s for the (1 1 0) and (0 0 1) surfaces resemble qualitatively, which is consistent with the XAS results. The spectra measured on the (1 1 0)-1 × 2 surface at an incident angle of 45° off normal to the surface and on the (1 1 0) surface sputtered by Ar ions indicate that SXAPS is very sensitive to the surface electronic states.     

Theoretical study of oxygen adsorption at the Fe(1 1 0) and (1 0 0) surfaces

Electronic, magnetic and structural properties of atomic oxygen adsorbed in on-surface and subsurface sites at the two most densely packed iron surfaces are investigated using density functional theory combined with a thermodynamics formalism. Oxygen coverages varying from a quarter to two monolayers (MLs) are considered. At a 1/4 ML coverage, the most stable on-surface adsorption sites are the twofold long bridge sites on the (1 1 0), and the fourfold-hollow sites on the (1 0 0) surface. The presence of on-surface oxygen atoms enhances the magnetic moments of the atoms of the two topmost Fe layers. Detailed results on the surface magnetic properties, due to O incorporation, are presented as well. Subsurface adsorption is found unfavored. The most stable subsurface O, in tetrahedral positions at the (1 0 0) and octahedral ones at the (1 1 0) surface, are characterized by substantially lower binding than that in the on-surface sites. Subsurface oxygen increases the interplanar distance between the uppermost Fe layers. The preadsorbed oxygen overlayer enhances binding of subsurface O atoms, particularly for tetrahedral sites beneath the (1 1 0) surface.     

Adsorption and reactivity of SO2 on Ir(1 1 1) and Rh(1 1 1)

The adsorption and reactivity of SO₂ on the Ir(1 1 1) and Rh(1 1 1) surfaces were studied by surface science techniques. X-ray photoelectron spectroscopy measurements showed that SO₂ was molecularly adsorbed on both the Ir(1 1 1) surface and the Rh(1 1 1) surface at 200 K. Adsorbed SO₂ on the Ir(1 1 1) surface disproportionated to atomic sulfur and SO₃ at 300 K, whereas adsorbed SO₂ on the Rh(1 1 1) surface dissociated to atomic sulfur and oxygen above 250 K. Only atomic sulfur was present on both surfaces above 500 K, but the formation process and structure of the adsorbed atomic sulfur on Ir(1 1 1) were different from those on Rh(1 1 1). On Ir(1 1 1), atomic sulfur reacted with surface oxygen and was completely removed from the surface, whereas on Rh(1 1 1), sulfur did not react with oxygen.     

FeO(1 1 1) formation by exposure of Fe(1 1 0) to atomic and molecular oxygen

The growth, structure, and morphology of ultrathin iron oxide layers formed on a Fe(1 1 0) single crystal surface are investigated by Auger electron spectroscopy, low energy electron diffraction, and grazing ion scattering. For Fe oxidation by atomic instead of molecular oxygen, the gas exposure can be reduced by almost two orders of magnitude because surface sticking and dissociation are not limiting the growth process. A well-ordered FeO(1 1 1) film with low defect density is only obtained with atomic oxygen. Compared to the bulk, the FeO lattice is laterally compressed by about 5-6% resulting in an in-plane oxygen (Fe) nearest-neighbor distance of 2.87 Å. Independent of the preparation method, long-range structural order is poor if the oxide film thickness is increased to 3-5 layers. This is attributed to the relatively large lattice mismatch between FeO(1 1 1) and Fe(1 1 0).     

Water adsorption and dissociation on BeO(0 0 1) and (1 0 0) surfaces

Plateaus in water adsorption isotherms on hydroxylated BeO surfaces suggest significant differences between the hydroxylated (1 0 0) and (0 0 1) surface structures and reactivities. Density functional theory structures and energies clarify these differences. Using relaxed surface energies, a Wulff construction yields a prism crystal shape exposing long (1 0 0) sides and much smaller (0 0 1) faces. This is consistent with the BeO prisms observed when beryllium metal is oxidized. A water oxygen atom binds to a single surface beryllium ion in the preferred adsorption geometry on either surface. The water oxygen/beryllium bonding is stronger on the surface with greater beryllium atom exposure, namely the less-stable (0 0 1) surface. Water/beryllium coordination facilitates water dissociation. On the (0 0 1) surface, the dissociation products are a hydroxide bridging two beryllium ions and a metal-coordinated hydride with some surface charge depletion. On the (1 0 0) surface, water dissociates into a hydroxide ligating a Be atom and a proton coordinated to a surface oxygen but the lowest energy water state on the (1 0 0) surface is the undissociated metal-coordinated water. The (1 0 0) fully hydroxylated surface structure has a hydrogen bonding network which facilitates rapid proton shuffling within the network. The corresponding (0 0 1) hydroxylated surface is fairly open and lacks internal hydrogen bonding. This supports previous experimental interpretations of the step in water adsorption isotherms. Further, when the (1 0 0) surface is heated to 1000 K, hydroxides and protons associate and water desorbs. The more open (0 0 1) hydroxylated surface is stable at 1000 K. This is consistent with the experimental disappearance of the isotherm step when heating to 973 K.