MAPbBr3 (MA: CH3NH3+) undergoes surface degradation under dark and vacuum conditions that leads to the formation of surface PbBr2 species.
Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt3Zr(0001) substrate by oxidation in 1 × 10–7 mbar of O2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O–Zr–O) films on the alloy; only a small area fraction (10–15%) is covered by ZrO2 clusters (thickness ∼0.5–10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt3Zr substrate by ZrO2, that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO2 films are between those of metallic Zr and thick (bulklike) ZrO2. Therefore, the assignment of such XPS core level shifts to substoichiometric ZrOx is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO2 films or metal/ZrO2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators.
Despite its importance in many areas of industry, such as catalysis, fuel cell technology and microelectronics, the surface structure and physical properties of ZrO2 are not well understood. Following the successful growth of ultra-thin zirconia on Pt3Zr(0 0 0 1) (Antlanger et al 2012 Phys. Rev. B 86 035451), we report on recent progress into ZrO2 thin films, which were prepared by oxidation of a Pd3Zr(0 0 0 1) crystal. Results from scanning tunneling microscopy (STM), Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS) as well as density-functional theory (DFT) are presented. Many sputter-annealing cycles are required for preparation of the clean Pd3Zr alloy surface, because oxygen easily dissolves in the bulk. By oxidation and post-annealing, a homogeneous ultra-thin ZrO2 film was obtained. This is an O-Zr-O trilayer based on cubic ZrO2(1 1 1). Using STM images corrected for distortion and creep of the piezo scanner the in-plane lattice parameter was determined as (351.2 ± 0.4) pm, slightly contracted with respect to the cubic ZrO2 bulk phase. The oxide forms an overlayer that is either incommensurate or has a very large superstructure cell (a = 8.3 nm); nevertheless its rotational orientation is always the same. In contrast to ultra-thin zirconia on Pt3Zr(0 0 0 1), where the uppermost substrate layer is pure (but reconstructed) Pt, STM and XPS suggest a stoichiometric Pd3Zr below the oxide. The oxide film binds to the substrate mainly via bonds between oxygen and the Zr atoms in the substrate. The ultra-thin oxide shows large buckling in STM, confirmed by DFT calculations, where the buckling of the Zr layer can exceed 100 pm. Compared to the ZrO2 film on Pt3Zr(0 0 0 1), the oxide on Pd3Zr(0 0 0 1) has the advantage that the substrate below does not reconstruct, leading to a homogeneous oxide film.
Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces.
We have studied zirconia films on a Rh(111) substrate with thicknesses in the range of 2-10 monolayers (ML) using scanning tunneling microscopy (STM) and lowenergy electron diffraction (LEED). Zirconia was deposited using a UHV-compatible sputter source, resulting in layer-by-layer growth and good uniformity of the films. For thicknesses of 2-4 ML, a layer-dependent influence of the substrate on the structure of the thin films is observed. Beyond this thickness, films show a (2 × 1) or a distorted (2 × 2) surface structure with respect to cubic ZrO 2 (111); these structures correspond to tetragonal and monoclinic zirconia, respectively. The tetragonal phase occurs for annealing temperatures of up to 730 °C; transformation to the thermodynamically stable monoclinic phase occurs after annealing at 850 °C or above. High-temperature annealing also breaks up the films and exposes the Rh(111) substrate. We argue that the tetragonal films are stabilized by oxygen deficiency, while the monoclinic films are only weakly defective and show band bending at defects and grain boundaries. This observation is in agreement with positive charge being responsible for the grain-boundary blocking effect in zirconia-based solid electrolytes. Our work introduces the tetragonal and monoclinic 5 ML-thick ZrO 2 films on Rh(111) as well-suited model system for surface-science studies on ZrO 2 as they do not exhibit the charging problems of thicker films or the bulk material and show better homogeneity and stability than the previously-studied ZrO 2 /Pt(111) system.
A comprehensive study of water adsorption and desorption on an ultrathin trilayer zirconia film by experimental and computational methods shows good agreement with data for H2O/ZrO2 powder material.
Atomistic characterization of surface termination and the corresponding mechanical properties of single-crystal methylammonium lead tribromide (MAPbBr 3 ) are performed using combined atomic force microscopy (AFM) measurements and density functional theory (DFT) calculations. A clean MAPbBr 3 surface is obtained by in situ cleavage in ultrahigh vacuum at room temperature, and the subsequent AFM measurements of the as-cleaved MAPbBr 3 exhibit the coexistence of two different surface terrace types with step height differences corresponding to about half the thickness of a PbI 6 octahedron layer. Concurrent friction force microscopy measurements show that the two surfaces result in two distinct friction values. Based on DFT calculations, we attribute the higher-friction and lower-friction surfaces to MABrterminated flat and PbBr 2 -terminated vacant surface terminations, respectively. The calculated electronic band structures of the various MABr-and PbBr 2 -terminated surfaces show that the midgap states are absent, revealing the defect-tolerant nature of the ideal single-crystal MAPbBr 3 surfaces.
Modern surface science faces two major challenges, a materials gap and a pressure gap. While studies on single crystal surface in ultrahigh vacuum have uncovered the atomic and electronic structures of the surface, the materials and environmental conditions of commercial catalysis are much more complicated, both in the structure of the materials and in the accessible pressure range of analysis instruments. Model systems and operando surface techniques have been developed to bridge these gaps. In this Review, we highlight the current trends in the development of the surface characterization techniques and methodologies in more realistic environments, with emphasis on recent research efforts at the Korea Advanced Institute of Science and Technology. We show principles and applications of the microscopic and spectroscopic surface techniques at ambient pressure that were used for the characterization of atomic structure, electronic structure, charge transport, and the mechanical properties of catalytic and energy materials. Ambient pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy allow us to observe the surface restructuring that occurs during oxidation, reduction, and catalytic processes. In addition, we introduce the ambient pressure atomic force microscopy that revealed the morphological, mechanical, and charge transport properties that occur during the catalytic and energy conversion processes. Hot electron detection enables the monitoring of catalytic reactions and electronic excitations on the surface. Overall, the information on the nature of catalytic reactions obtained with operando spectroscopic and microscopic techniques may bring breakthroughs in some of the global energy and environmental problems the world is facing.
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