Overcoming Redox Reactions at Perovskite-Nickel Oxide Interfaces to Boost Voltages in Perovskite Solar Cells
Not Available
14 SOLAR ENERGY↗
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Results for “oxide interfaces”
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From weak antilocalization to Kondo scattering in a magnetic complex oxide interface
Quantum corrections to electrical resistance can serve as sensitive probes of the magnetic landscape of a material. For example, interference between time-reversed electron paths gives rise to weak localization effects, which can provide information about the coupling between spins and orbital motion, while the Kondo effect is sensitive to the presence of spin impurities. In this work, we use low-temperature magnetotransport measurements to reveal a gradual transition from weak antilocalization (WAL) to Kondo scattering in the quasi-two-dimensional electron gas formed at the interface between SrTiO 3 and the Mott insulator NdTiO 3 . This transition occurs as the thickness of the NdTiO 3 layer is increased. Analysis of the Kondo scattering and WAL points to the presence of atomic-scale magnetic impurities coexisting with nanoscale magnetic regions that affect transport via a strong magnetic exchange interaction. This leads to distinct magnetoresistance behaviors that can serve as a sensitive probe of magnetic properties in two dimensions.
36 MATERIALS SCIENCE↗
Tunable one-dimensional electron gas carrier densities at nanostructured oxide interfaces
The emergence of two-dimensional metallic states at the LaAlO 3 /SrTiO 3 (LAO/STO) heterostructure interface is known to occur at a critical thickness of four LAO over layers. This insulator-to-metal transition can be explained through the polar catastrophe mechanism arising from the divergence of the electrostatic potential at the LAO surface. Here, we demonstrate that nanostructuring can be effective in reducing or eliminating this critical thickness. Employing a modified polar catastrophe" model, we demonstrate that the nanowire heterostructure electrostatic potential diverges more rapidly as a function of layer thickness than in a regular heterostructure. Our first principles calculations indicate that for nanowire heterostructure geometries a one-dimensional electron gas (1DEG) can be induced, consistent with recent experimental observations of 1D conductivity in LAO/STO steps. Similar to LAO/STO 2DEGs, we predict that the 1D charge density will decay laterally within a few unit cells away from the nanowire; thus providing a mechanism for tuning the carrier behavior between 1D and 2D conductivity. Furthermore, our work provides insight into the creation and manipulation of charge density at an oxide heterostructure interface and therefore may be beneficial for future nanoelectronic devices and for the engineering of novel quantum phases.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt–Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy
A method to modulate the Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. The interfacial chemistries that modulate barrier heights for the Pt/a-IGZO system were investigated using in-situ X-ray photoelectron spectroscopy. A significant reduction of indium, from In 3+ to In 0 , occurs during deposition of Pt on to the a-IGZO surface in ultra-high vacuum. Post-annealing and controlling the background ambient O 2 pressure allows tuning the degree of indium reduction and the corresponding Schottky barrier height between 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metalsemiconductor field-effect transistors.
Environmental Molecular Sciences Laboratory↗
Symmetry-dependent interfacial reconstruction to compensate polar discontinuity at perovskite oxide interfaces (LaAlO{sub 3}/SrTiO{sub 3} and LaAlO{sub 3}/CaTiO{sub 3})
We report the crystal symmetry-dependency of the interfacial reconstruction to relieve the polar discontinuity at the complex oxide heterointerfaces. We chose LaAlO{sub 3}/SrTiO{sub 3} and LaAlO{sub 3}/CaTiO{sub 3} interfaces as model systems, where the neutral TiO{sub 2} and the positive LaO{sup +} layers form the polar discontinuity at the interface with TiO{sub 2}-terminated (001) cubic SrTiO{sub 3} and orthorhombic CaTiO{sub 3}. Using scanning transmission electron microscopy, we observed that the interlayer distance abnormally increased at the interface. We performed the first-principles calculations to understand the detailed atomic displacement at the interfaces having no oxygen vacancy and intermixing. Our results show that cations were reconstructed in different ways depending on the crystal symmetry through the octahedral tilts and atomic displacements to compensate the polar discontinuity at the interfaces. Our results imply that the interfacial reconstructions have to be considered along with the ionic compensation (intermixing) and electronic compensation (two dimensional electron gas) to fully understand the interfacial phenomena.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Focus Issue: Understanding Water-Oxide Interfaces to Harness New Processes and Technologies. Introduction
Water interaction with metal oxides plays a fundamentally important role across environmental chemistry, geochemistry, catalysis, and in the control and performance of functional nanocrystalline oxides. Water is found virtually everywhere on Earth, from bulk fluid to trace molecules, and its interaction with natural and engineered materials often defines or at least influences a key part of their chemical and physical behavior. In turn, metal oxides play a dominant role as mineral particles across most natural environments, while comprising a compelling and versatile platform for the development of new functional materials with tailored properties that benefit society. Given the intrinsic correlation of their properties to water interactions, it is a common goal across materials and chemical sciences to develop a comprehensive understanding of water adsorption, water film formation, and water-mediated reactions on metal oxide surfaces. This is certainly true in heterogeneous catalysis and electrocatalysis, where water is omnipresent either as a reactant, a medium, an inhibitor or as a trace component in the feed. The effect of water on the morphological evolution during synthesis, particle assembly, and sintering is also important to the stability and functional properties of oxide nanostructures. Such processes are intimately related to how water molecules interact with their surfaces and affect local physical-chemical conditions.
Rosso, Kevin M.↗
Phenomenology of Intermediate Molecular Dynamics at Metal-Oxide Interfaces
Reaction intermediates buried within a solid-liquid interface are difficult targets for physiochemical measurements. They are inherently molecular and locally dynamic, while their surroundings are extended by a periodic lattice on one side and the solvent dielectric on the other. Challenges compound on a metal-oxide surface of varied sites and especially so at its aqueous interface of many prominent reactions. Recently, phenomenological theory coupled with optical spectroscopy has become a more prominent tool for isolating the intermediates and their molecular dynamics. The following article reviews three examples of the SrTiO3-aqueous interface subject to the oxygen evolution from water: reaction-dependent component analyses of time-resolved intermediates, a Fano resonance of a mode at the metal-oxide–water interface, and reaction isotherms of metastable intermediates. The phenomenology uses parameters to encase what is unknown at a microscopic level to then circumscribe the clear and macroscopically tuned trends seen in the spectroscopic data.
Chemistry↗
Oxide Interfaces: emergent structure and dynamics
This Final Report describes the scientific accomplishments that have been achieved with support from grant DE-FG02-06ER46273 during the period 6/1/2012– 5/31/2016. The overall goals of this program were focused on the behavior of epitaxial oxide heterostructures at atomic length scales (Ångstroms), and correspondingly short time-scales (fs -ns). The results contributed fundamentally to one of the currently most active frontiers in condensed matter physics research, namely to better understand the intricate relationship between charge, lattice, orbital and spin degrees of freedom that are exhibited by complex oxide heterostructures. The findings also contributed towards an important technological goal which was to achieve a better basic understanding of structural and electronic correlations so that the unusual properties of complex oxides can be exploited for energy-critical applications. Specific research directions included: probing the microscopic behavior of epitaxial interfaces and buried layers; novel materials structures that emerge from ionic and electronic reconfiguration at epitaxial interfaces; ultrahigh-resolution mapping of the atomic structure of heterointerfaces using synchrotron-based x-ray surface scattering, including direct methods of phase retrieval; using ultrafast lasers to study the effects of transient strain on coherent manipulation of multi-ferroic order parameters; and investigating structural ordering and relaxation processes in real-time.
36 MATERIALS SCIENCE↗
Transmission electron microscopy examinations of metal-oxide interface of zirconium-based alloys irradiated in Halden reactor-IFA-638 - 2016-0039
This paper provides the results of investigations by transmission electron microscopy (TEM) on the selected materials from in-reactor oxidation tests in the Halden test reactor (Reference No. IFA-638) from 1998 to 2006. The objective of the IFA-638 test was to study the corrosion behavior of modern zirconium-based claddings to high burnup in pressurized water reactor water chemistry and thermal hydraulic conditions. The aim of this paper is to report on the microstructure of selected materials (ZIRLO{sup R}, E635, and Alloy A) after the irradiation to different burnup levels to determine the modifications induced by irradiation and to correlate results to their oxidation behavior. The TEM examinations revealed the nature of secondary phase particles (SPPs) and their modification under irradiation. Four types of SPPs were observed, namely β-niobium precipitates, Zr{sub 0.5}Nb{sub 0.3}Fe{sub 0.2} (mainly in the ZIRLO alloy), Zr(Fe,Nb){sub 2} (in E635), and (Cr,Fe){sub 2}Zr,Nb with varying niobium content (present in Alloy A: Zr-0.58Sn-0.31Nb-0.36Fe-0.26Cr). TEM observations showed that all three materials contained still several precipitates after irradiation and in the case of the ZIRLO alloy even after high burnups. Furthermore, the analysis of the metal side of the interface and its comparison with the oxide side led to the conclusion that all types of precipitates dissolved to some extent under irradiation and that their alloying element content decreased. The dissolution was intensified in the oxide. However, a more detailed examination showed that the β-niobium precipitates dissolved at a slower rate, or knowing that their composition was much richer in niobium, the time needed for the precipitates to become fully depleted from niobium was longer. Regarding the amorphization under irradiation, the b-niobium- and chromium-containing precipitates did not amorphize in the metal part of the interface. This was not the case for the other types of precipitates. Furthermore, these two types of SPP both showed delayed oxidation and due to this behavior the typical crack above the SPP in the oxide was also observed. These results are discussed to gain an improved understanding of the oxidation behavior of materials studied as a function of irradiation and residence time. (authors)
36 MATERIALS SCIENCE↗
Electronic structure evolution and energy level alignment at C{sub 60}/4,4′-cyclohexylidenebis[N,N-bis(4-methylphenyl) benzenamine]/MoO{sub x}/indium tin oxide interfaces
The electronic structure evolution and energy level alignment have been investigated at interfaces comprising fullerene (C{sub 60})/4,4′-cyclohexylidenebis[N,N-bis(4-methylphenyl) benzenamine] (TAPC)/ molybdenum oxide (MoO{sub x})/ indium tin oxide with ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. With deposition of TAPC upon MoO{sub x}, a dipole of 1.58 eV was formed at the TAPC/MoO{sub x} interface due to electron transfer from TAPC to MoO{sub x}. The highest occupied molecular orbital (HOMO) onset of TAPC was pinned closed to the Fermi level, leading to a p-doped region and thus increasing the carrier concentration at the very interface. The downward band bending and the resulting built-in field in TAPC were favorable for the hole transfer toward the TAPC/MoO{sub x} interface. The rigid downward shift of energy levels of TAPC indicated no significant interface chemistry at the interface. With subsequent deposition of C{sub 60} on TAPC, a dipole of 0.27 eV was observed at the C{sub 60}/TAPC heterojunction due to the electron transfer from TAPC to C{sub 60}. This led to a drop of the HOMO of TAPC near the C{sub 60}/TAPC interface, and hence further enhanced the band bending in TAPC. The band bending behavior was also observed in C{sub 60}, similarly creating a built-in field in C{sub 60} film and improving the electron transfer away from the C{sub 60}/TAPC interface. It can be deduced from the interface analysis that a promising maximum open circuit voltage of 1.5 eV is achievable in C{sub 60}/TAPC-based organic photovoltaic cells.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
The silicon/zinc oxide interface in amorphous silicon-based thin-film solar cells: Understanding an empirically optimized contact
The electronic structure of the interface between the boron-doped oxygenated amorphous silicon 'window layer' (a-SiO{sub x}:H(B)) and aluminum-doped zinc oxide (ZnO:Al) was investigated using hard x-ray photoelectron spectroscopy and compared to that of the boron-doped microcrystalline silicon ({mu}c-Si:H(B))/ZnO:Al interface. The corresponding valence band offsets have been determined to be (-2.87 {+-} 0.27) eV and (-3.37 {+-} 0.27) eV, respectively. A lower tunnel junction barrier height at the {mu}c-Si:H(B)/ZnO:Al interface compared to that at the a-SiO{sub x}:H(B)/ZnO:Al interface is found and linked to the higher device performances in cells where a {mu}c-Si:H(B) buffer between the a-Si:H p-i-n absorber stack and the ZnO:Al contact is employed.
36 MATERIALS SCIENCE↗
Electronic Structure of the Perylene–Zinc Oxide Interface: Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects
The electronic properties of dye-sensitized semiconductor surfaces consisting of perylene chromophores chemisorbed on zinc oxide via different spacer-anchor groups have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Crude-Oil-Repellent Membranes by Atomic Layer Deposition: Oxide Interface Engineering
Crude oil fouling on membrane surfaces is a persistent, crippling challenge in oil spill remediation and oilfield wastewater treatment. In this research, we present how a nanosized oxide coating can profoundly affect the anti crude-oil property of membrane materials. Select oxide coatings with a thickness of similar to 10 nm are deposited conformally on common polymer membrane surfaces by atomic layer deposition to significantly mitigate fouling during filtration processes. TiO 2 - and SnO 2 -coated membranes exhibited far greater anti-crude-oil performance than ZnO- and Al 2 O 3 -coated ones. Tightly bound hydration layers play a crucial role in protecting the surface from crude oil adhesion, as revealed by molecular dynamics simulations. Furthermore, this work provides a facile strategy to fabricate crude oil-resistant membranes with negligible impact on membrane structure, and also demonstrates that, contrary to common belief, excellent crude oil resistance can be achieved easily without implementation of sophisticated, hierarchical structures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
On the Nature of the Increase in the Electron Mobility in the Inversion Channel at the Silicon–Oxide Interface after the Field Effect
The conduction characteristics of the inversion channel of Si-transistor structures after the ionic polarization and depolarization of samples are measured in (0–5)-T transverse magnetic fields at temperatures from 100 to 200 K. After ionic polarization in a strong electric field at 420 K, no less than 6 × 10{sup 13} cm{sup –2} ions flowed through the oxide. The previously found tenfold increase in the conductivity in the source–drain circuit after the polarization of insulating layers is explained by the formation of a new electron transport path along the surface impurity band, related to delocalized D{sup –} states; these states are generated by neutralized ions located in the insulating layer at its interface with the semiconductor.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Polarity‐Driven Atomic Displacements at the 2D Mg 2 TiO 4 ‐MgO (001) Oxide Interface for Hosting Potential Interlayer Excitons
Abstract Interlayer excitons in solid‐state systems have emerged as candidates for realizing novel platforms ranging from excitonic transistors and optical qubits to exciton condensates. Interlayer excitons have been discovered in 2D transition metal dichalcogenides, with large exciton binding energies and the ability to form various van der Waals heterostructures. Here, an oxide system consisting of a single unit cell of Mg 2 TiO 4 on MgO (001) is proposed as a platform for hosting interlayer excitons. Using a combination of density functional theory (DFT) calculations, molecular beam epitaxy growth, and in situ crystal truncation rod measurements, it is shown that the Mg 2 TiO 4 ‐MgO interface can be precisely controlled to yield an internal electric field suitable for hosting interlayer excitons. The atoms in the polar Mg 2 TiO 4 layers are observed to be displaced to reduce polarity at the interface with the non‐polar MgO (001) surface. Such polarity‐driven atomic displacements strongly affect electrostatics of the film and the interface, resulting in localization of filled and empty band‐edge states in different layers of the Mg 2 TiO 4 film. The DFT calculations suggest that the electronic structure is favorable for localization of photoexcited electrons in the bottom layer and holes in the top layer, which may bind to form interlayer exciton states.
36 MATERIALS SCIENCE↗
Simultaneous Activation of CH4 and CO2 for Concerted C-C Coupling at the Oxide-Oxide Interfaces
Catalytic conversion of CO2 and CH4 to value-added platform chemicals via the direct C-C coupling provides one of the most effective routes that not only address global climate change but also alleviate the dependency on traditional fossil fuels. Herein, three oxide-on-oxide catalysts that can realize direct C-C coupling on the basis of simultaneous activation of CH4 and CO2 were investigated using density functional theory (DFT) calculations. With the formation of oxide-on-oxide interfacial sites between the substrate (In2O3) and dispersed oxides ((ZnO)3, (ZrO2)3, or Ga2O3), it is found that CO2 can be activated at the defective site of In2O3 while the C-H bond of CH4 can be simultaneously activated at the M-O pair of the supported metal oxide. In contrast to the Eley-Rideal mechanism that C-C coupling of CO2 and CH3 stabilized on Zn-doped ceria follows, the formation of a Zn-C-C-O transition state at the active centers originates from a Langmuir-Hinshelwood mechanism where the activated CO2 also enhances the dissociative adsorption of CH4. There is a linear relationship between the C-C coupling reaction energy/activation barrier and CH4 dissociation energy. The results indicate that dissociative adsorption of CH4 plays a dominant role in the direct C-C coupling, whereas the adsorption/activation of CO2 is less significant. DFT calculation results of CH4 and CO2 to acetic acid on the (ZnO)3/In2O3 catalyst surface indicates that the C-C coupling step is the kinetically most relevant step. Compared with Ga2O3/In2O3 and (ZrO2)3/In2O3 catalyst surfaces, (ZnO)3/In2O3(110) is more active for the acetic acid formation. The present work provides new mechanistic insights into the direct C-C coupling of CH4 and CO2, which would be useful to design more efficient catalyst.
CH4 activation, C-C coupling, supported oxides, In↗
Prototypical Organic–Oxide Interface: Intramolecular Resolution of Sexiphenyl on In 2 O 3 (111)
Not Available
36 MATERIALS SCIENCE↗
Alkali-induced catalytic tuning at metal and metal oxide interfaces
Alkali metals have been recognized as effective promoters in heterogeneous catalysis, capable of enhancing catalytic activity and tuning product distributions. Over the past few decades, significant efforts have been made aiming to reveal the mechanisms underlying the promoting effect of alkalis. However, the roles that alkali metals play in the catalytic process remain elusive due to challenges in capturing their catalytic behaviours upon exposure to reactive environments. This review summarizes recent surface science and theoretical studies of alkali (potassium, cesium)-decorated metal and metal oxide model catalysts, revealing the crucial tuning by alkalis of activity and selectivity for CO 2 hydrogenation. The analysis of electronic structures identifies the selective binding mechanism of the positively charged alkali ions on the surface, being able to reduce the surface work function and lead to strong electron polarization on the surfaces. Depending on the alkali–support interaction, the deposition of alkalis can selectively modify the bindings of reaction intermediates involved in CO 2 hydrogenation via the interplay among the ionic, covalent and electrostatic tunings. As a result, CO 2 can be effectively activated and converted into diverse products at the alkali–support interface, ranging from formic acid to methanol and ethanol. The identified selective bond-tuning advances the application of alkalis in promoting catalytic activity and controlling catalytic selectivity at alkali–support interfaces.
03 NATURAL GAS↗