DFT study of Pt adsorption on low index SrTiO3 surfaces: SrTiO3(1 0 0), SrTiO3(1 1 1) and SrTiO3(1 1 0)

Density Functional Theory has been used to determine the energetically preferred structures of submonolayer, monolayer, and multilayer Pt films on both ideal terminations of SrTiO₃(1 0 0), SrTiO₃(1 1 1), and SrTiO₃(1 1 0). The strength of the resulting metal/metal oxide interfaces was characterized by the adsorption energy of the film and the film’s work of separation. The two polar surfaces, SrTiO₃(1 1 1) and SrTiO₃(1 1 0), form significantly stronger interfaces than the non-polar SrTiO₃(1 0 0) surface. Approximate criteria were applied to predict the growth mode of Pt on each surface.     

First principle study of SrTiO3 (0 0 1) surface and adsorption of NO on SrTiO3 (0 0 1)

The results of first-principles calculations about the two possible terminations of (0 0 1) surface of SrTiO₃ perovskite and adsorption of NO on SrTiO₃ (0 0 1) surface were presented. Both surface parameters (atomic structures and electronic configurations) and adsorption parameters (bond, energy and charge) of NO on SrTiO₃ (0 0 1) surface, which have never been investigated before as far as we know were investigated using density functional theory calculations with the local-density approximation (DFT-LDA). It was found that the two possible terminations of SrTiO₃ (0 0 1) surface have large surface relaxation, which leads to surface polarization and exhibits different reactivity toward the dissociative adsorption of NO. The electronic states of TiO₂-terminated surface have larger difference than that of bulk, so it is more favorable for adsorption of NO than SrO-terminated surface.     

Effects of N adsorption on the structural and electronic properties of SrTiO3(0 0 1) surface

The atomic configurations, bonding characteristics, and electronic structures of the N-adsorbed (directly and substitutionally) SrTiO₃(0 0 1) surface are studied by using first-principles method based on the density functional theory. From the analysis of the energetics and density of states, it is found that the stability of the directly adsorbed N depends on the relative position of N atom to the surface. To better understand the effects of the substitutionally adsorbed N on the surface, as an example, the behavior of Au atoms adsorbed on the N-substituted surface is discussed in detail. There is clearly a synergy effect between the substitution of N for O_s(I) and the adsorption of Au atoms on the SrTiO₃(0 0 1) surface.     

The CuGaSe2(0 0 1) surface: A (4 × 1) reconstruction

We report on the formation of a stable (4 × 1) reconstruction of the chalcopyrite CuGaSe₂(0 0 1) surface. Using Ar⁺ ion-bombardment and annealing of epitaxial CuGaSe₂ films grown on GaAs(0 0 1) substrates it was possible to obtain flat, well-ordered surfaces showing a clear (4 × 1) reconstruction. The cleanliness and structure were analyzed in situ by AES and LEED. AES data suggest a slight Se-enrichment and Cu-depletion upon surface preparation. Our results demonstrate that (0 0 1) surfaces of the Cu-III-VI₂(0 0 1) material can show stable, unfacetted surfaces.     

Surface termination of the NdGaO3(1 1 0)

Auger electron spectroscopy using excitation via grazing impact of protons was applied to determine the elemental composition of the topmost and near-surface layers of a NdGaO₃(1 1 0) substrate. The preparation conditions of vicinal NdGaO₃ substrates were optimized by varying the annealing temperature, time, and gas atmosphere. Well prepared surfaces show regularly arranged, atomically smooth terraces with single-atomic steps. The surfaces were always NdO terminated with a small amount of Ga (2-4%) atoms on the surface. A Ga and O depletion layer with a thickness of about 4 nm has been detected at optimized preparation conditions.     

Texture of molybdenum thin films on SrTiO3(1 0 0): A RHEED study

The structure of ultrathin Mo films on SrTiO₃(1 0 0) was studied by in situ reflection high-energy electron diffraction (RHEED). A different structure was observed for films less than 20 Å thick than for thicker films. These films were epitaxial and had a metastable structure. Thicker films had the dimensions of equilibrium bcc Mo(1 1 0). Relaxation processes transformed the metastable Mo into bcc Mo, resulting in the following orientation relationships between Mo and SrTiO₃: (1 1 0)[0 0 1]_bcc Mo ∥ (1 0 0)[0 0 1]_SrTiO3 and (1 1 0)[1 1 1]_bcc Mo ∥ (1 0 0)[0 1 1]_SrTiO3. The formation of such specific orientations is related to transformations via the Bain and Needle Path, respectively.     

Atypical grain growth for (2 1 1) CdTe films deposited on surface reconstructed (1 0 0) SrTiO3 substrates

The (1 0 0) SrTiO₃ substrate has emerged as the oxide substrate of choice for the deposition of a wide variety of materials. The substrate's unavoidable miscut leads to a step-terrace morphology when heated to high temperatures. This morphological transition is accompanied by an atomic scale repositioning of the uppermost terrace atoms, the nature of which is strongly dependent on the substrate temperature and ambient atmosphere used. Here, we report the deposition of CdTe films on the as-received and reconstructed surfaces of (1 0 0) SrTiO₃. The as-received substrate gives rise to a [1 1 1] CdTe film with four equally distributed in-plane grain orientations. The surface reconstruction, on the other hand, gives rise to an unprecedented reorientation of the film's grain structure. For this case, a [2 1 1] CdTe film emerges having twelve unevenly distributed in-plane orientations. We attribute the film's grain structure to an atomic scale surface reconstruction, with the anisotropic distribution of grain-types arising from a preferential formation due to the step edges.     

Epitaxial growth of Co(0 0 0 1)hcp/Fe(1 1 0)bcc magnetic bi-layer films on SrTiO3(1 1 1) substrates

Co(0 0 0 1)_hcp/Fe(1 1 0)_bcc epitaxial magnetic bi-layer films were successfully prepared on SrTiO₃(1 1 1) substrates. The crystallographic properties of Co/Fe epitaxial magnetic bi-layer films were investigated. Fe(1 1 0)_bcc soft magnetic layer grew epitaxially on SrTiO₃(1 1 1) substrate with two type variants, Nishiyama–Wasserman and Kurdjumov–Sachs relationships. An hcp-Co single-crystal layer is obtained on Ru(0 0 0 1)_hcp interlayer, while hcp-Co layer formed on Au(1 1 1)_fcc or Ag(1 1 1)_fcc interlayer is strained and may involve fcc-Co phase. It has been shown possible to prepare Co/Fe epitaxial magnetic bi-layer films which can be usable for patterned media application.     

The preparation of c-axis epitaxial Bi-2212 films on STO(1 0 0) by sol-gel method

Bi₂Sr₂Ca₁Cu₂O_8+δ (Bi-2212) films were grown on (1 0 0) oriented SrTiO₃ (STO) substrate using sol-gel spin-coating method. The effects of heat treatment conditions and coating times on the phase formation and surface morphology were investigated using thermal analysis, optical microscope, X-ray diffraction, and scanning electronic microscopy. Mixed phases were formed from 820 to 840 °C, and Bi-2212 single phase was obtained at 830 °C for 3 h. c-axis epitaxial films with smooth surfaces were obtained by drying at 600 °C and coating for 5 times.     

Driving force for the WO3(0 0 1) surface relaxation

The optimized structure of the WO₃(0 0 1) surface with various types of termination ((1 × 1)O, (1 × 1)WO₂, and c(2 × 2)O) has been simulated using density functional theory with the Perdew-Wang 91 gradient corrected exchange-correlation functional. While the energy of bulk WO₃ depends weakly on the distortions and tilting of the WO₆ octahedra, relaxation of the (0 0 1) surface results in a significant decrease of surface energy (from 10.2 × 10⁻² eV/Ų for the cubic ReO₃-like, c(2 × 2)O-terminated surface to 2.2 × 10⁻² eV/Ų for the relaxed surface). This feature illustrates a potential role of surface relaxation in formation of crystalline nano-size clusters of WO₃. The surface relaxation is accompanied by a dramatic redistribution of the density of states near the Fermi level, in particular a transformation of surface electronic states. This redistribution is responsible for the decrease of electronic energy and therefore is suggested to be the driving force for surface relaxation of the WO₃(0 0 1) surface and, presumably, similar surfaces of other transition metal oxides.     

SrTiO3(0 0 1) reconstructions: the (2 × 2) to c(4 × 4) transition

Scanning tunneling microscopy (STM) is used to investigate the (0 0 1) surface structure of Nb doped SrTiO₃ single crystals annealed in ultra high vacuum (UHV). Atomically resolved images of the (2 × 2) reconstructed surface are obtained after annealing a chemically etched sample. With further annealing dotted row domains appear, which coexist with the (2 × 2) reconstruction. The expansion of these domains with further annealing gives rise to the formation of a TiO₂ enriched c(4 × 4) reconstruction.     

First-principles study of the (0 0 1) surface of cubic SrZrO3

Density functional calculations have been used to investigate the (0 0 1) surface of cubic SrZrO₃ with both SrO and ZrO₂ termination. Surface structure and electronic structure have been obtained. The SrO surface is found to be similar to its counterpart in SrTiO₃, while there are marked differences between the ZrO₂ and TiO₂ terminations in SrZrO₃ and SrTiO₃, respectively, concerning surface relaxation and rumpling. For the ZrO₂-terminated surface of SrZrO₃, the covalency of the interaction between the outmost Zr and the O beneath is enhanced as a result of their bond contraction. The band gap reduction and the presence of the surface states are also discussed in relation with the behavior of the electrostatic potential.     

Electron surface states in short-period superlattices: (GaAs)2/(AlAs)2(1 0 0)-c(4 × 4)

The electronic structure of (GaAs)₂/(AlAs)₂(1 0 0)-c(4 × 4) superlattice surfaces was studied by means of angular-resolved photoelectron spectroscopy (ARUPS) in the photon energy range 20-38 eV. Four samples with different surface termination layers were grown and As-capped by molecular beam epitaxy (MBE). ARUPS measurements were performed on decapped samples with perfect c(4 × 4) reconstructed surfaces. An intensive surface state was, for the first time, observed below the top of the valence band. This surface state was found to shift with superlattices’ different surface termination in agreement with theoretical predictions.     

Comparative investigation of the c(2 × 2)-Si/Cu(0 1 1) and (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloys using DFT

The electronic structure of the c(2 × 2)-Si/Cu(0 1 1) surface alloy has been investigated and compared to the structures seen in the three phases of the (√3 × √3)R30°Cu₂Si/Cu(1 1 1) system, using LCAO-DFT. The weighted surface energy increase between the alloyed Cu(0 1 1) and Cu(1 1 1) surfaces is 126.7 meV/Si atom. This increase in energy for the (0 1 1) system when compared to the (1 1 1) system is assigned to the transition from a hexagonal to a rectangular local bonding environment for the Si ion cores, with the hexagonal environment being energetically more favorable. The Si 3s state is shown to interact covalently with the Cu 4s and 4p states whereas the Si 3p state, and to a lesser extent the Si 3d state, forms a mixture of covalent and metallic bonds with the Cu states. The Cu 4s and 4p states are shown to be altered by approximately the same amount by both the removal of Cu ion cores and the inclusion of Si ion cores during the alloying of the Cu(0 1 1) surface. However, the Cu 3d states in the surface and second layers of the alloy are shown to be more significantly altered during the alloying process by the removal of Cu ion cores from the surface layer rather than by the addition of Si ion cores. This is compared to the behavior of the Cu 3d states in the surface and second layers of the each phase of the (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) alloy and consequently the loss of Cu-Cu periodicity during alloying of the Cu(0 1 1) surface is conjectured as the driving force for changes to the Cu 3d states. The accompanying changes to the Cu 4s and 4p states in both the c(2 × 2)-Si/Cu(0 1 1) and (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) alloys are quantified and compared. The study concludes with a brief quantitative study of changes in the bond order of the Cu-Cu bonds during alloying of both Cu(0 1 1) and Cu(1 1 1) surfaces.     

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 small unit cell reconstructions of SrTiO3(1 1 1)

We analyze the basic structural units of simple reconstructions of the (1 1 1) surface of SrTiO₃ using density functional calculations. The prime focus is to answer three questions: what is the most appropriate functional to use; how accurate are the energies; what are the dominant low-energy structures and where do they lie on the surface phase diagram. Using test calculations of representative small molecules we compare conventional PBE-GGA with higher-order methods such as the TPSS meta-GGA and on-site hybrid methods PBE0 and TPSSh, the later being the most accurate. There are large effects due to reduction of the metal d oxygen sp hybridization when using the hybrid methods which are equivalent to a dynamical GGA + U, which leads to rather substantial improvements in the atomization energies of simple calibration molecules, even though the d-electron density for titanium compounds is rather small. By comparing the errors of the different methods we are able to generate an estimate of the theoretical error, which is about 0.25 eV per 1 × 1 unit cell, with changes of 0.5-1.0 eV per 1 × 1 cell with the more accurate method relative to conventional GGA. An analysis of the plausible structures reveals a new low-energy TiO₂-rich configuration with octahedral co-ordination. This structure can act as a template for layers of either TiO or Ti₂O₃, consistent with experimental results. The results also suggest that both the fracture surface and the stoichiometric SrTiO₃(1 1 1) surface should spontaneously disproportionate into SrO and TiO₂ rich domains.     

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.     

Probing the properties of the (1 1 1) and (1 0 0) surfaces of LaB6 through infrared spectroscopy of adsorbed CO

The adsorption of carbon monoxide on the LaB₆(1 0 0) and LaB₆(1 1 1) surfaces was studied experimentally with the techniques of reflection absorption infrared spectroscopy and X-ray photoelectron spectroscopy. The interaction of CO with the two surfaces was also studied with density functional theory. Both surfaces adsorb CO molecularly at low temperatures but in markedly different forms. On the LaB₆(1 1 1) surface CO initially adsorbs at 90 K in a form that yields a CO stretching mode at 1502-1512 cm⁻¹. With gentle annealing to 120 K, the CO switches to a bonding environment characterized by multiple CO stretch values from 1980 to 2080 cm⁻¹, assigned to one, two, or three CO molecules terminally bonded to the B atoms of a triangular B₃ unit at the (1 1 1) surface. In contrast, on the LaB₆(1 0 0) surface only a single CO stretch is observed at 2094 cm⁻¹, which is assigned to an atop CO molecule bonded to a La atom. The maximum intensity of the CO stretch vibration on the (1 0 0) surface is higher than on the (1 1 1) surface by a factor of 5. This difference is related to the different orientations of the CO molecules on the two surfaces and to reduced screening of the CO dynamic dipole moment on the (1 0 0) surface, where the bonding occurs further from the surface plane. On LaB₆(1 0 0), XPS measurements indicate that CO dissociates on the surface at temperatures above 400 K.     

Band offsets at the epitaxial anatase TiO2/n-SrTiO3(0 0 1) interface

We have used high-energy resolution X-ray photoelectron spectroscopy to measure valence band offsets at the epitaxial anatase TiO₂(0 0 1)/n-SrTiO₃(0 0 1) heterojunction prepared by molecular beam epitaxy. The valence band offsets range between −0.06 ± 0.05 and +0.16 ± 0.05 eV for anatase thicknesses between 1 and 8 monolayers and three different methods of substrate surface preparation, with no systematic dependence on film thickness. The conduction band offset (CBO) varies over a comparable range by virtue of the fact that anatase and SrTiO₃ exhibit the same bandgap (∼3.2 eV). In contrast, density functional theory predicts the VBO to be +0.55 eV. The lack of agreement between theory and experiment suggests that either some unknown factor in the interface structure or composition excluded from the modeling is influencing the band offset, or that density functional theory cannot accurately calculate band offsets in these oxide materials. The small experimental band offsets have important implications for the use of this interface for fundamental investigations of surface photocatalysis. Neither electrons nor holes are likely to become trapped in the substrate and thus be unable to participate in surface photocatalytic processes.     

Facetting and (n × 1) reconstructions of SrTiO3(1 1 0) surfaces

(n × 1) reconstructions and facetting of the (1 1 0) polar surface of SrTiO₃ are studied by means of a combination of shell model and density functional calculations. The polarity compensation can be achieved through the formation of {1 0 0} nano-facets, which play a crucial role in the reconstruction process. The behaviors of various possible terminations (Sr, Ti, and O) are analyzed, as well as their atomic structure and energetics. Their stability in different chemical environments is discussed, with respect to previous formulations and experimental results. The Sr-terminated surface tends to expose large facets, while the TiO and O terminations are marginally stabilized or even destabilized by (n × 1) reconstructions, respectively. Trend to facetting results from a subtle competition between the thermodynamic stability of the ideal non stoichiometric (n × 1) surfaces, and huge atomic relaxations that contribute to the lowering of the surface energy differently for each termination.