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1. Electrically Coupling Multifunctional Oxides to Semiconductors: A Route to Novel Material Functionalities

   https://doi.org/https://doi.org/10.1557/adv.2016.101  

   Ngai, J. H. ; Ahmadi-Majlan, K. ; Moghadam, J. ; Chrysler, M. ; Kumah, D.P. ; Ahn, C.H. ; Walker, F.J. ; Droubay, T. ; Bowden, M. ; Chambers, S. A. ; et al ( February 2016 , MRS Advances)

   Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling oxides to semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Key to electrically coupling oxides to semiconductors is controlling the physical and electronic structure of semiconductor – crystalline oxide heterostructures. Here we discuss how composition of the oxide can be manipulated to control physical and electronic structure in Ba1-xSrxTiO3/ Ge and SrZrxTi1-xO3/Ge heterostructures. In the case of the former we discuss how strain can be engineered through composition to enable the re-orientable ferroelectric polarization to be coupled to carriers in the semiconductor. In the case of the latter we discuss how composition can be exploited to control the band offset at the semiconductor - oxide interface. The ability to control the band offset, i.e. band-gap engineering, provides a pathway to electrically couple crystalline oxides to semiconductors to realize a host of functionalities. 

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2. Epitaxial Oxides on Semiconductors: From Fundamentals to New Devices

   https://doi.org/10.1002/adfm.201901597  

   Kumah, Divine P. ; Ngai, Joseph H. ; Kornblum, Lior ( July 2019 , Advanced Functional Materials)

   Functional oxides are an untapped resource for futuristic devices and functionalities. These functionalities can range from high temperature superconductivity to multiferroicity and novel catalytic schemes. The most prominent route for transforming these ideas from a single device in the lab to practical technologies is by integration with semiconductors. Moreover, coupling oxides with semiconductors can herald new and unexpected functionalities that exist in neither of the individual materials. Therefore, oxide epitaxy on semiconductors provides a materials platform for novel device technologies. As oxides and semiconductors exhibit properties that are complementary to one another, epitaxial heterostructures comprised of the two are uniquely poised to deliver rich functionalities. This review discusses recent advancements in the growth of epitaxial oxides on semiconductors, and the electronic and physical structure of their interfaces. Leaning on these fundamentals and practicalities, the material behavior and functionality of semiconductor–oxide heterostructures is discussed, and their potential as device building blocks is highlighted. The culmination of this discussion is a review of recent advances in the development of prototype devices based on semiconductor–oxide heterostructures, in areas ranging from silicon photonics to photocatalysis. This overview is intended to stimulate ideas for new concepts of functional devices and lay the groundwork for their realization.

    

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3. Extreme Ultraviolet Reflection-Absorption (XUV-RA) Spectroscopy: Probing Dynamics at Surfaces from a Molecular Perspective

   https://doi.org/https://doi.org/10.1021/acs.accounts.1c00765  

   Biswas, Somnath ; Baker, L. Robert ( March 2022 , Accounts of chemical research)

   Extreme ultraviolet (XUV) light sources based on high harmonic generation are enabling the development of novel spectroscopic methods to help advance the frontiers of ultrafast science and technology. In this account we discuss the development of XUV-RA spectroscopy at near grazing incident reflection geometry and highlight recent applications of this method to study ultrafast electron dynamics at surfaces. Measuring core-to-valence transitions with broadband, femtosecond pulses of XUV light extends the benefits of x-ray absorption spectroscopy to a laboratory tabletop by providing a chemical fingerprint of materials, including the ability to resolve individual elements with sensitivity to oxidation state, spin state, carrier polarity, and coordination geometry. Combining this chemical state sensitivity with femtosecond time resolution provides new insight into the material properties that govern charge carrier dynamics in complex materials. It is well known that surface dynamics differ significantly from equivalent processes in bulk materials, and that charge separation, trapping, transport, and recombination occurring uniquely at surfaces governs the efficiency of numerous technologically relevant processes spanning photocatalysis, photovoltaics, and information storage and processing. Importantly, XUV-RA spectroscopy at near grazing angle is also surface sensitive with a probe depth of 3 nm, providing a new window into electronic and structural dynamics at surfaces and interfaces. Here we highlight the unique capabilities and recent applications of XUVRA spectroscopy to study photo-induced surface dynamics in metal oxide semiconductors, including photocatalytic oxides (Fe2O3, Co3O4 NiO, and CuFeO2) as well as photoswitchable magnetic oxide (CoFe2O4). We first compare the ultrafast electron self-trapping rates via small polaron formation at the surface and bulk of Fe2O3 where we note that the energetics and kinetics of this process differ significantly at the surface. Additionally, we demonstrate the ability to systematically tune this kinetics by molecular functionalization, thereby, providing a route to control carrier transport at surfaces. We also measure the spectral signatures of charge transfer excitons with site specific localization of both electrons and holes in a series of transition metal oxide semiconductors (Fe2O3, NiO, Co3O4). The presence of valence band holes probed at the oxygen L1-edge confirms a direct relationship between the metal-oxygen bond covalency and water oxidation efficiency. For a mixed metal oxide CuFeO2 in the layered delafossite structure, XUV-RA reveals that the sub-picosecond hole thermalization from O 2p to Cu 3d states of CuFeO2 leads to the spatial separation of electrons and holes, resulting in exceptional photocatalytic performance for H2 evolution and CO2 reduction of this material. Finally, we provide an example to show the ability of XUV-RA to probe spin state specific dynamics in a the photo-switchable ferrimagnet, cobalt ferrite (CoFe2O4). This study provides a detailed understating of ultrafast spin switching in a complex magnetic material with site-specific resolution. In summary, the applications of XUV-RA spectroscopy demonstrated here illustrate the current abilities and future promise of this method to extend molecule-level understanding from well-defined photochemical complexes to complex materials so that charge and spin dynamics at surfaces can be tuned with the precision of molecular photochemistry. 

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4. Perspective on functional metal-oxide plasmonic metastructures

   https://doi.org/10.1063/5.0134141  

   Sadeghi, Seyed M. ; Wing, Waylin J. ; Gutha, Rithvik R. ( February 2023 , Journal of Applied Physics)

   Plasmonic nanostructures and metasurfaces are appealing hosts for investigation of novel optical devices and exploration of new frontiers in physical/optical processes and materials research. Recent studies have shown that these structures hold the promise of greater control over the optical and electronic properties of quantum emitters, offering a unique horizon for ultra-fast spin-controlled optical devices, quantum computation, laser systems, and sensitive photodetectors. In this Perspective, we discuss how heterostructures consisting of metal oxides, metallic nanoantennas, and dielectrics can offer a material platform wherein one can use the decay of plasmons and their near fields to passivate the defect sites of semiconductor quantum dots while enhancing their radiative decay rates. Such a platform, called functional metal-oxide plasmonic metasubstrates (FMOPs), relies on formation of two junctions at very close vicinity of each other. These include an Au/Si Schottky junction and an Si/Al oxide charge barrier. Such a double junction allows one to use hot electrons to generate a field-passivation effect, preventing migration of photo-excited electrons from quantum dots to the defect sites. Prospects of FMOP, including impact of enhancement exciton–plasmon coupling, collective transport of excitation energy, and suppression of quantum dot fluorescence blinking, are discussed.

    

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5. Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena, Hybrid Materials, and Novel Functionalities

   https://doi.org/10.1002/smll.202105424  

   Prakash, Divya J. ; Chen, Yajin ; Debasu, Mengistie L. ; Savage, Donald E. ; Tangpatjaroen, Chaiyapat ; Deneke, Christoph ; Malachias, Angelo ; Alfieri, Adam D. ; Elleuch, Omar ; Lekhal, Kaddour ; et al ( November 2021 , Small)

   Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO₃layer on a Si:B/Si_1−xGe_x:B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si_1−xGe_x:B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO₃at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si_1−xGe_x:B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO₃. The control of stresses via post‐deposition processing provides a new route to the assembly of complex‐oxide‐based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large‐area semiconductor substrates.

    

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