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Interfacial spin–orbit torques

Spin–orbit torques offer a promising mechanism for electrically controlling magnetization dynamics in nanoscale heterostructures. While spin–orbit torques occur predominately at interfaces, the physical mechanisms underlying these torques can originate in both the bulk layers and at interfaces. Classifying spin–orbit torques based on the region that they originate in provides clues as to how to optimize the effect. While most bulk spin–orbit torque contributions are well studied, many of the interfacial contributions allowed by symmetry have yet to be fully explored theoretically and experimentally. To facilitate progress, we review interfacial spin–orbit torques from a semiclassical viewpoint and relate these contributions to recent experimental results. In this study, we show the relationship between different interface transport parameters within the same model. For charges and spins flowing perpendicular to the interface, interfacial spin–orbit coupling both modifies the mixing conductance of the magnetoelectronic circuit theory and gives rise to spin memory loss. For in-plane electric fields, interfacial spin–orbit coupling gives rise to torques described by spin–orbit filtering, spin swapping, and precession. In addition, these same interfacial processes generate spin currents that flow into the non-magnetic layer. For in-plane electric fields in trilayer structures, the spin currents generated at the interface between one ferromagnetic layer and the non-magnetic spacer layer can propagate through the non-magnetic layer to produce novel torques on the other ferromagnetic layer.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Semiconductor nanocrystal photocatalysis for the production of solar fuels

Colloidal semiconducting nanocrystals (NCs) are powerful elements of a photocatalytic system useful for enabling a variety of chemical transformations owing to their strong light-absorbing properties and high degree of size-, shape-, and composition-tunability. Key to their utility is our understanding of the photoinduced charge transfer processes required for these photochemical transformations. This Perspective will focus on the implementation of semiconductor NCs for photochemical fuel formation. Three general system designs for photocatalytic proton reduction using semiconductor NCs will be reviewed: metal–semiconductor heterostructures, NC photosensitizers with molecular catalysts, and hydrogenase-based systems. Additionally, other relevant reactions toward solar fuel targets, such as CO 2 and N 2 reductions with NCs, will also be highlighted. Illustrating the versatile roles that NCs can play in light-driven chemical reactions, advances made toward NC-catalyzed organic transformations will be discussed. Finally, we will share a few concluding thoughts and perspectives on the future of the field, with a focus on goals toward improving and implementing NC-based technologies for solar fuel development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Introduction to special issue: Colloidal quantum dots

The quantum confinement effect has driven the development and exploration of colloidal semiconductor nanocrystals over approximately the past three decades. These semiconductor nanostructures are typically synthesized as stable colloidal dispersions in solution-phase chemical batch reactions at relatively low temperatures. Researchers have developed a wide range of reaction conditions to produce a variety of shapes, compositions, and structures with well-controlled sizes and low polydispersities. The shape can be controlled to produce confinement in one, two, or all three spatial dimensions, the latter defining a “quantum dot.” Combining two or more semiconductors within the various nanostructures produces additional optical and electronic degrees of freedom. These mixed compositional nanostructures have properties not accessible in bulk semiconductor systems. Further, researchers have fabricated novel nanoheterostructures, such as “dot-in-rods,” quantum wells, core/shell structures, giant-core/shell tetrapods where the core is one material and the arm is another, Janus structures that consist of spherical structures with well-defined internal heterostructures, nano-dumbbells, hollow-core structures, and many other novel and interesting structures. The structural variations are seemingly only limited by the creativity of the various researchers engaged in these endeavors.

36 MATERIALS SCIENCE↗

Ion beam etching dependence of spin-orbit torque memory devices with switching current densities reduced by Hf interlayers

We report on the fabrication of nanoscale, three-terminal in-plane spin–orbit torque switching devices with low switching current densities. Critical parameters in the fabrication process, including the ion beam etching angle and time, were optimized to avoid fabrication defects and improve device yield. Measurements of the magnetic field and current-induced switching behavior of the tunnel junctions demonstrate a sensitivity to the nanopillar aspect ratio, which dictates the nanopillars’ anisotropy and thermal stability. Additionally, we show that the current density required for switching can be reduced and the device thermal stability increased by inserting Hf interlayers into the heterostructure. Micromagnetic simulations are generally consistent with the experimentally observed switching behavior, suggesting an increase in the interfacial perpendicular anisotropy at the CoFeB/MgO interface and the reduction in the Dzyaloshinskii–Moriya interaction at the W/CoFeB interface by the Hf interlayers.

36 MATERIALS SCIENCE↗

Enhanced van der Waals epitaxy of germanium by out-of-plane dipole moment induced from transferred graphene on TiN/AlN multilayers

We report recent advances in 3D/2D heterostructures have opened up tremendous opportunities in building highly flexible and durable optoelectronic devices. However, the inherit lack of interfacial bonding and low surface energy of van der Waals surfaces limit the nucleation and growth of 3D materials. Enhancing wettability by providing a porous buffer is effective in growing compound semiconductors on graphene while van der Waals epitaxy of Ge remains challenging. Here, the nucleation of Ge has been significantly improved from an islanded mode to granular modes by using a TiN/AlN multilayered buffer prior to Ge/graphene integration. Highly textured Ge growth with dominating (111), (220), and (311) peaks are identified by x-ray diffraction. The microstructure of the buffer TiN/AlN demonstrates a polycrystalline quality with clean interfaces between each interlayer and the substrate. Kelvin probe force microscopy measurements along the lateral TiN/AlN interface identify a potential drop corresponding to the AlN phase. This contact potential difference between TiN and AlN is the key in generating the out-of-plane dipole moment that modifies the surface energy of the monolayer graphene, resulting in enhanced wettability of the Ge adatoms nucleated on top. Surface dipole induced nucleation of 3D semiconductor thin films on 2D materials via the proper design of buffer layer is fundamentally important to enhance the 3D/2D growth toward flexible optoelectronic applications.

36 MATERIALS SCIENCE↗

Controlling magnetic configuration in soft–hard bilayers probed by polarized neutron reflectometry

Hard/soft magnetic bilayer thin films have been widely used in data storage technologies and permanent magnet applications. The magnetic configuration and response to temperatures and magnetic fields in these heterostructures are considered to be highly dependent on the interfacial coupling. However, the intrinsic properties of each of the layers, such as the saturation magnetization and layer thickness, also strongly influence the magnetic configuration. Changing these parameters provides an effective method to tailor magnetic properties in composite magnets. Here, we use polarized neutron reflectometry (PNR) to experimentally probe the interfacial magnetic configurations in the hard/soft bilayer thin films: L1 0 -FePt/A1-FePt, [Co/Pd]/CoPd, [Co/Pt]/FeNi, and L1 0 -FePt/Fe, all of which have a perpendicular magnetic anisotropy in the hard layer. These films were designed with different soft and hard layer thicknesses (t soft and t hard ) and saturation magnetization (M$_s^{soft}$ and M$_s^{hard}$). The influences of an in-plane magnetic field (H ip ) and temperature (T) are also studied using a L1 0 -FePt/A1-FePt bilayer sample. Comparing the PNR results to the micromagnetic simulations reveals that the interfacial magnetic configuration is highly dependent on t soft , M$_s^{soft}, and the external factors (H ip and T) and has a relatively weak dependence on t hard and M$_s^{hard}$. Key among these results, for thin t soft , the hard and soft layers are rigidly coupled in the out-of-plane direction and then undergo a transition to relax in-plane. This transition can be delayed to larger t soft by decreasing M$_s^{soft}$. Understanding the influence of these parameters on the magnetic configuration is critical to designing functional composite magnets for applications.

36 MATERIALS SCIENCE↗

Synthesis of La 2–x Sr x CuO 4 films via atomic layer-by-layer molecular beam epitaxy

Atomic layer-by-layer molecular beam epitaxy (ALL-MBE) is a sophisticated technique to synthesize high-temperature superconductor (HTS) materials. ALL-MBE produces single-crystal HTS films with atomically smooth surfaces and interfaces, as well as precise multilayer heterostructures engineered down to a single atomic layer level. This enables the fabrication of tunnel junctions, nanowires, nanorings, and other HTS devices of interest. Our group has focused on ALL-MBE synthesis and materials science of La 2–x Sr x CuO 4 (LSCO), a representative HTS cuprate. In the past two decades, we have synthesized over three thousand LSCO thin films and characterized them by a range of analytical techniques. Here, we present in full detail a systematic process for the synthesis and engineering of atomically perfect LSCO films. The procedure includes the preparation of substrates, calibration of the elemental sources, the recipe for ALL growth of LSCO films without any secondary-phase precipitates, post-growth annealing of the films, and ex situ film characterization. This report should aid replication and dissemination of this technique of synthesizing single-crystal LSCO films for basic research as well as for HTS electronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

III-Nitride p-down green (520 nm) light emitting diodes with near-ideal voltage drop

We demonstrate p-down green emitting LEDs with low turn-on voltage enabled by efficient tunnel junctions. Due to the polarization field alignment in the (In,Ga)N/GaN interface with the p-down orientation, the electrostatic depletion barrier for electron and hole injection is reduced when compared with the conventional p-up LEDs. A single (In,Ga)N/GaN heterostructure quantum well active region with a GaN homojunction tunnel junction exhibited very low forward operating voltage of 2.42 V at 20 A/cm 2 with a peak electroluminescence emission wavelength of 520 nm for current densities above 100 A/cm 2 . Furthermore, the bottom tunnel junction with minimal voltage drop enabled excellent hole injection into the bottom p-GaN layer.

36 MATERIALS SCIENCE↗

Selective amorphization of SiGe in Si/SiGe nanostructures via high energy Si+ implant

Here, the selective amorphization of SiGe in Si/SiGe nanostructures via a 1 MeV Si + implant was investigated, resulting in single-crystal Si nanowires (NWs) and quantum dots (QDs) encapsulated in amorphous SiGe fins and pillars, respectively. The Si NWs and QDs are formed during high-temperature dry oxidation of single-crystal Si/SiGe heterostructure fins and pillars, during which Ge diffuses along the nanostructure sidewalls and encapsulates the Si layers. The fins and pillars were then subjected to a 3 × 10 15 ions/cm 2 1 MeV Si + implant, resulting in the amorphization of SiGe, while leaving the encapsulated Si crystalline for larger, 65-nm wide NWs and QDs. Interestingly, the 26-nm diameter Si QDs amorphize, while the 28-nm wide NWs remain crystalline during the same high energy ion implant. This result suggests that the Si/SiGe pillars have a lower threshold for Si-induced amorphization compared to their Si/SiGe fin counterparts. However, Monte Carlo simulations of ion implantation into the Si/SiGe nanostructures reveal similar predicted levels of displacements per cm 3 . Molecular dynamics simulations suggest that the total stress magnitude in Si QDs encapsulated in crystalline SiGe is higher than the total stress magnitude in Si NWs, which may lead to greater crystalline instability in the QDs during ion implant. The potential lower amorphization threshold of QDs compared to NWs is of special importance to applications that require robust QD devices in a variety of radiation environments.

36 MATERIALS SCIENCE↗

Transport properties of polarization-induced 2D electron gases in epitaxial AlScN/GaN heterojunctions

AlScN is attractive as a lattice-matched epitaxial barrier layer for incorporation in GaN high electron mobility transistors due to its large dielectric constant and polarization. The transport properties of polarization-induced two-dimensional (2D) electron gas of densities of ∼2×10 13 /cm 2 formed at the AlScN–GaN interface is studied by Hall-effect measurements down to cryogenic temperatures. The 2D electron gas densities exhibit mobilities limited to ∼300 cm 2 /V s down to 10 K at AlScN/GaN heterojunctions. The insertion of a ∼2 nm AlN interlayer boosts the room temperature mobility by more than five times from ∼300 cm 2 /V s to ∼1573 cm 2 /V s, and the 10 K mobility by more than 20 times to ∼6980 cm 2 /V s at 10 K. These measurements provide guidelines to the limits of electron conductivities of these highly polar heterostructures.

42 ENGINEERING↗

Element-specific first order reversal curves measured by magnetic transmission x-ray microscopy

The first-order reversal curve (FORC) method is a macroscopic measurement technique that can be used to extract quantitative and microscopic properties of hysteretic systems. Using magnetic transmission x-ray microscopy (MTXM), local element-specific FORC measurements are performed on a 20 nm thick film of CoTb. The FORCs measured with microscopy reveal a step-by-step domain evolution under the magnetic field cycling protocol and provide a direct visualization of the mechanistic interpretation of FORC diagrams. They are compared with magnetometry FORCs and show good quantitative agreement. Furthermore, the high spatial resolution and element-specific sensitivity of MTXM provide new capabilities to measure FORCs in small regions or specific phases within multicomponent systems, including buried layers in heterostructures. The ability to perform FORCs on very small features is demonstrated with the MTXM-FORC measurement of a rectangular microstructure with vortex-like Landau structures. This work demonstrates the confluence of two uniquely powerful techniques to achieve quantitative insight into nanoscale magnetic behavior.

36 MATERIALS SCIENCE↗

Multiscale electric-field imaging of polarization vortex structures in PbTiO 3 /SrTiO 3 superlattices

In ferroelectric heterostructures, the interaction between intrinsic polarization and the electric field generates a rich set of localized electrical properties. The local electric field is determined by several connected factors, including the charge distribution of individual unit cells, the interfacial electromechanical boundary conditions, and chemical composition of the interfaces. However, especially in ferroelectric perovskites, a complete description of the local electric field across micro-, nano-, and atomic-length scales is missing. Here, by applying four-dimensional scanning transmission electron microscopy (4D STEM) with multiple probe sizes matching the size of structural features, we directly image the electric field of polarization vortices in (PbTiO 3 ) 16 /(SrTiO 3 ) 16 superlattices and reveal different electric field configurations corresponding to the atomic scale electronic ordering and the nanoscale boundary conditions. The separability of two different fields probed by 4D STEM offers the possibility to reveal how each contributes to the electronic properties of the film.

36 MATERIALS SCIENCE↗

Detecting driving potentials at the buried SiO 2 nanolayers in solar cells by chemical-selective nonlinear x-ray spectroscopy

We present an approach to selectively examine an asymmetric potential in the buried layer of solar cell devices by means of nonlinear x-ray spectroscopy. Detecting second harmonic generation signals while resonant to the SiO 2 core level, we directly observe existence of the band bending effect in the SiO 2 nanolayer, buried in the heterostructures of Al/LiF/SiO 2 /Si, TiO 2 /SiO 2 /Si, and Al 2 O 3 /SiO 2 /Si. Furthermore, the results demonstrate high sensitivity of the method to the asymmetric potential that determines performance of functional materials for photovoltaics or other optoelectronic devices.

14 SOLAR ENERGY↗

Two-level systems in nucleated and non-nucleated epitaxial alpha-tantalum films

Building usefully coherent superconducting quantum processors depends on reducing losses in their constituent materials. Tantalum, like niobium, has proven utility as the primary superconducting layer within highly coherent qubits. However, unlike Nb, high temperatures are typically used to stabilize the desirable body-centered-cubic phase, α-Ta, during thin film deposition. It has long been known that a thin Nb layer permits the room-temperature nucleation of α-Ta, but here we observe the epitaxial process and present few-photon microwave loss measurements in Nb-nucleated Ta films. We compare resonators patterned from Ta films grown at high temperature (500 °C) and films nucleated at room temperature, in order to understand the impact of the crystalline order on quantum coherence. In both cases, films grew with Al 2 O 3 (001) ∥ Ta (110), indicating that the epitaxial orientation is independent of temperature and is preserved across the Nb/Ta interface. We use conventional low-power spectroscopy to measure two level system (TLS) loss as well as an electric-field bias technique to measure the effective dipole moments of TLS in the surfaces of resonators. In our measurements, Nb-nucleated Ta resonators had greater loss tangent (1.5 ± 0.1 × 10 -5 ) than non-nucleated (5 ± 1× 10 -6 ) in approximate proportion to defect densities as characterized by x-ray diffraction (0.27° vs 0.18° [110] reflection width) and electron microscopy (30 vs 70 nm domain size). Furthermore, the dependence of the loss tangent on domain size indicates that the development of more ordered Ta films is likely to lead to improvements in qubit coherence times. Moreover, low-temperature α-Ta epitaxy may enable the growth of microstate-free heterostructures, which would not withstand high temperature processing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantum sensing effect of electron tunneling in DQD/analyte complex

We investigate electron tunneling between quantum dots and molecules to propose a quantum sensor. This sensor consists of double quantum dots (DQD) with energy levels specifically tailored to mirror those of the target analyte. By analyzing the spectral distribution of electron localizations in the DQD system, we can delineate the analyte’s spectrum and deduce its composition by comparing it with a reference sample. To understand electron tunneling dynamics within the DQD/analyte complex, we performed three-dimensional computational modeling applying the effective potential approach to the InAs/GaAs heterostructure. In this modeling, we mimicked the analyte spectrum by utilizing a quantum well characterized by a quasi-discrete spectrum. Our calculations reveal the inherent potential of utilizing this method as a highly sensitive and selective sensor.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of fabrication processes on BaTiO 3 capacitor properties

There is an increasing desire to utilize complex functional electronic materials such as ferroelectrics in next-generation microelectronics. As new materials are considered or introduced in this capacity, an understanding of how we can process these materials into those devices must be developed. Here, the effect of different fabrication processes on the ferroelectric and related properties of prototypical metal oxide (SrRuO 3 )/ferroelectric (BaTiO 3 )/metal oxide (SrRuO 3 ) heterostructures is explored. Two different types of etching processes are studied, namely, wet etching of the top SrRuO 3 using a NaIO 4 solution and dry etching using an Ar + -ion beam (i.e., ion milling). Polarization-electric-field hysteresis loops for capacitors produced using both methods are compared. For the ion-milling process, it is found that the Ar + beam can introduce defects into the SrRuO 3 /BaTiO 3 /SrRuO 3 devices and that the milling depth strongly influences the defect level and can induce a voltage imprint on the function. Realizing that such processing approaches may be necessary, work is performed to ameliorate the imprint of the hysteresis loops via ex situ “healing” of the process-induced defects by annealing the ferroelectric material in a barium-and-oxygen-rich environment via a chemical-vapor-deposition-style process. This work provides a pathway for the nanoscale fabrication of these candidate materials for next-generation memory and logic applications.

36 MATERIALS SCIENCE↗

Uncovering the three-dimensional structure of upconverting core–shell nanoparticles with multislice electron ptychography

In photon upconverting core–shell nanoparticles, structure strongly dictates performance. Typical imaging in scanning transmission electron microscopy has sufficient resolution to probe the atomic structure of these nanoparticles, but contrast, dose, and projection limitations make conventional methods insufficient for fully characterizing these structures. Phase retrieval techniques provide a promising alternative imaging mode, and, in particular, multislice electron ptychography can recover depth-dependent information. Here, we study beam-sensitive photon upconverting core–shell nanoparticles with a multislice ptychography approach using a low electron dose to avoid damage. Large strain fields arise in these heterostructures due to the mismatch in lattice parameter between the core and the shell. We reconstruct both a nanoparticle that appears defect-free and one that has a large break in the side and map the distribution of strain in 3D by computing distortion fields from high-resolution potential images of each slice. In the defect-free nanoparticle, we observe twisting of the shell, while in the broken nanoparticle, we measure the 3D position of the crack, the core, and dislocations. These results highlight the advantage of multislice electron ptychography to recover 3D information from a single scan, even under strict electron dose requirements from beam-sensitive samples.

74 ATOMIC AND MOLECULAR PHYSICS↗

Influence of excess silicon on polytype selection during metal-mediated epitaxy of GaN nanowires

For this work, we have examined the origins of polytype selection during metal-mediated molecular-beam epitaxy of GaN nanowires (NWs). High-angle annular dark-field scanning transmission electron microscopy reveals [111]-oriented zinc blende (ZB) NWs and [0001]-oriented wurtzite (WZ) NWs, with SixNy at the interface between individual NWs and the Si (001) substrate. Quantitative energy dispersive x-ray spectroscopy reveals a notably higher Si concentration of 7.0% ± 2.3% in zinc blende (ZB) NWs than 2.3% ± 1.2% in wurtzite (WZ) NWs. Meanwhile, density functional theory calculations show that incorporation of 8 at. % Si on the Ga sublattice inverts the difference in formation energies between WZ and ZB GaN, such that the ZB polytype of GaN is stabilized. This identification of Si and other ZB polytype stabilizers will enable the development of polytype heterostructures in a wide variety of WZ-preferring compounds.

77 NANOSCIENCE AND NANOTECHNOLOGY↗