Epitaxial growth of ultrathin ZrO2(111) films on Pt(111)

Gao, Yan; Zhang, Liang; Yong, Pan; Guo-dong, Wang; Xu, Yang; Zhang, Wenhua; Zhu, Junfa

doi:10.1007/s11434-010-4309-7

Cited by 15 publications

(22 citation statements)

References 21 publications

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“…At first sight it is therefore surprising that a Zr rich surface oxide shows a distinct core level binding energy with respect to that of Zr in PZT. However, the XPS data in the literature shows that the Zr binding energy is (181.4 ±0.1) eV in PZT [10,24,35,32,36,37,38,39,40,41,42,43,44,45,46] and (182.4 ±0.3) eV in ZrO 2 [47,48,49,50,51,52,53,54,55,56], in excellent agreement with the 1 eV shift measured here. Beyond the immediate chemical environment of the Zr emitter, two other effects may influence the BE shift.…”

Section: Discussionsupporting

confidence: 90%

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol–gel films

Gueye

Rhun

Gergaud

et al. 2016

Applied Surface Science

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We present a study of the chemistry of the nanostructured phase at the surface of lead zirconium titanate PbZr 0.52 Ti 0.48 O 3 (PZT) films synthesized by sol-gel method. In sol-gel synthesis, excess lead precursor is used to maintain the target stoichiometry. Surface nanostructures appear at 10% excess lead precursor whereas 30% excess precursor inhibits their formation. Using the surface-sensitive, quantitative X-ray photoelectron spectroscopy and glancing angle X-ray diffraction we have shown that the chemical composition of the nanostructures is ZrO 1.82−1.89 rather than pyrochlore often described in the literature. The presence of a possibly discontinuous layer of wide band gap ZrO 1.82−1.89 could be of importance in determining the electrical properties of PZT-based metal-insulator-metal heterostructures.

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Section: Discussionsupporting

confidence: 90%

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol–gel films

Gueye

Rhun

Gergaud

et al. 2016

Applied Surface Science

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“…By annealing at 900 °C in UHV, the disordered zirconia transformed to an ordered monolayer corresponding to one O-Zr-O trilayer repeat unit of ZrO 2 (111). For ZrO 2 /Pt 3 Zr, the film exhibited the same (√19 × √19)R23.4° superstructure (this rotation angle is equivalent to 36.6°) as found in previous studies of zirconia on Pt(111) [24,26], confirming that this structure on Pt(111) likely corresponded to an ultrathin film. ZrO 2 /Pd 3 Zr formed an O-Zr-O trilayer with an almost identical in-plane lattice constant (0.35 nm) and a large (√217 × √217)R10.16° superstructure cell.…”

Section: Introductionsupporting

confidence: 83%

“…Pt(111) after 3 min of annealing at 680 °C can be attributed to the ZrO 2 films. Submonolayer films exhibited (5 × 5) and (√19 × √19)R36.6° superstructures with respect to Pt(111) [26]; the latter structure also appeared when thicker films were annealed at high temperatures. Possibly those formed at areas where the thicker ZrO 2 film has disappeared.…”

Section: Introductionmentioning

confidence: 97%

Surface structures of ZrO2 films on Rh(111): From two layers to bulk termination

et al. 2019

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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.

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“… 27 , 28 An exact identification of the different oxide components has, however, not yet been achieved. Gao et al 9 applied XPS to study the growth of ZrO 2 film on Pt(111) by vapor deposition of zirconium in an oxygen atmosphere (10 –7 Torr). They also observed a Zr 3d 5/2 binding energy of 182.9 eV corresponding to bulklike ZrO 2 up to ≈5 ML; an additional shift of +0.7 eV at higher thickness (8.3 ML) was attributed to surface charging due to the poor oxide conductivity.…”

Section: Resultsmentioning

confidence: 99%

Growth of an Ultrathin Zirconia Film on Pt₃Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory

Choi²,

Mayr-Schmölzer³

et al. 2015

J. Phys. Chem. C

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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.

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Epitaxial growth of ultrathin ZrO2(111) films on Pt(111)

Cited by 15 publications

References 21 publications

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol–gel films

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol–gel films

Surface structures of ZrO2 films on Rh(111): From two layers to bulk termination

Growth of an Ultrathin Zirconia Film on Pt₃Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory

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Epitaxial growth of ultrathin ZrO2(111) films on Pt(111)

Cited by 15 publications

References 21 publications

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol–gel films

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol–gel films

Surface structures of ZrO2 films on Rh(111): From two layers to bulk termination

Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory

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Growth of an Ultrathin Zirconia Film on Pt₃Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory