Temperature Evolution of Magnon Propagation Length in Tm3Fe5O12 Thin Films: Roles of Magnetic Anisotropy and Gilbert Damping.

The magnon propagation length, ⟨ξ⟩, of a ferro-/ferrimagnet (FM) is one of the key factors that controls the generation and propagation of thermally driven magnonic spin current in FM/heavy metal (HM) bilayer based spincaloritronic devices. For the development of a complete physical picture of thermally driven magnon transport in FM/HM bilayers over a wide temperature range, it is of utmost importance to understand the respective roles of temperature-dependent Gilbert damping (α) and effective magnetic anisotropy (Keff) in controlling the temperature evolution of ⟨ξ⟩. Here, we report a comprehensive investigation of the temperature-dependent longitudinal spin Seebeck effect (LSSE), radio frequency transverse susceptibility, and broad-band ferromagnetic resonance measurements on Tm3Fe5O12 (TmIG)/Pt bilayers grown on different substrates. We observe a significant drop in the LSSE voltage below 200 K independent of TmIG film thickness and substrate choice. This is attributed to the noticeable increases in effective magnetic anisotropy field, HKeff (∝Keff) and α that occur within the same temperature range. From the TmIG thickness dependence of the LSSE voltage, we determined the temperature dependence of ⟨ξ⟩ and highlighted its correlation with the temperature-dependent HKeff and α in TmIG/Pt bilayers, which will be beneficial for the development of rare-earth iron garnet based efficient spincaloritronic nanodevices.

Damping and Interfacial Dzyaloshinskii-Moriya Interaction in Thulium Iron Garnet/Bismuth-Substituted Yttrium Iron Garnet Bilayers.

Thin films of ferrimagnetic iron garnets can exhibit useful magnetic properties, including perpendicular magnetic anisotropy (PMA) and high domain wall velocities. In particular, bismuth-substituted yttrium iron garnet (BiYIG) films grown on garnet substrates have a low Gilbert damping but zero Dzyaloshinskii-Moriya interaction (DMI), whereas thulium iron garnet (TmIG) films have higher damping but a nonzero DMI. We report the damping and DMI of thulium-substituted BiYIG (BiYTmIG) and TmIG|BiYIG bilayer thin films deposited on (111) substituted gadolinium gallium garnet and neodymium gallium garnet (NGG) substrates. The films are epitaxial and exhibit PMA. BiYIG|TmIG bilayers have a damping value that is an order of magnitude lower than that of TmIG, and BiYIG|TmIG|NGG have DMI of 0.0145 ± 0.0011 mJ/m2, similar to that of TmIG|NGG. The bilayer therefore provides a combination of DMI and moderate damping, useful for the development of high-speed spin orbit torque-driven devices.

Directed Self-Assembly of Oxide Nanocomposites by Ion-Beam Lithography.

Vertically aligned self-assembled nanocomposite films have provided a unique platform to study magnetoelectric effects and other forms of coupling between complex oxides. However, the distribution in the locations and sizes of the phase-separated nanostructures limits their utility. In this work, we demonstrate a process to template the locations of the self-assembled structure using ion lithography, which is effective for general insulating substrates. This process was used to produce a nanocomposite consisting of fin-shaped vertical nanostructures of ferroelectric BiFeO3 and ferrimagnetic CoFe2O4 with a feature size of 100 nm on (111)-oriented SrTiO3 substrates. Cross-sectional imaging of the three-phase perovskite-spinel-substrate epitaxial interface reveals the selective nucleation of CoFe2O4 in the trenches of the patterned substrate, and the magnetic domains of CoFe2O4 were manipulated by applying an external magnetic field.

First-principles based Monte Carlo modeling of the magnetization of oxygen-deficient Fe-substituted SrTiO3.

Transition-metal (TM) substituted SrTiO3 has attracted much attention because its magnetism and/or ferroelectricity can be tuned via cation substitution, point defects, strain and/or oxygen deficiency. For example, Goto et al. [Phys. Rev. Applied, 7, 024006 (2017)] reported the magnetization of SrTi1-xFexO3-δ (STF) grown under different oxygen pressures and on various substrates. Here, we use hybrid density functional theory to calculate the effects of different oxygen vacancy (VO) states in STF on the magnetization for a variety of Fe cation arrangements. The magnetic states of the cations associated with the VO ground-states for x = {0.125, 0.25} are used within a Monte Carlo model for collinear magnetism to simulate the spontaneous magnetization. Our model captures several experimental features of STF, i.e., an increase in magnetization for small δ up to a maximum of ∼0.35µB per formula unit at an intermediate number of vacancies, with a slower decrease in magnetization with an increasing number of vacancies. Our approach gives insight into the relation between vacancy concentration and the oxygen pressure required to maximize the magnetization.

Erratum: Large Anomalous Frequency Shift in Perpendicular Standing Spin Wave Modes in BiYIG Films Induced by Thin Metallic Overlayers [Phys. Rev. Lett. 130, 126703 (2023)].

This corrects the article DOI: 10.1103/PhysRevLett.130.126703.

Coherent magnon-induced domain-wall motion in a magnetic insulator channel.

Advancing the development of spin-wave devices requires high-quality low-damping magnetic materials where magnon spin currents can efficiently propagate and effectively interact with local magnetic textures. Here we show that magnetic domain walls can modulate spin-wave transport in perpendicularly magnetized channels of Bi-doped yttrium iron garnet. Conversely, we demonstrate that the magnon spin current can drive domain-wall motion in the Bi-doped yttrium iron garnet channel device by means of magnon spin-transfer torque. The domain wall can be reliably moved over 15-20 µm distances at zero applied magnetic field by a magnon spin current excited by a radio-frequency pulse as short as 1 ns. The required energy for driving the domain-wall motion is orders of magnitude smaller than those reported for metallic systems. These results facilitate low-switching-energy magnonic devices and circuits where magnetic domains can be efficiently reconfigured by magnon spin currents flowing within magnetic channels.

Reversible Morphology Locking via Metal Infiltration in a Block Copolymer.

Metal infiltration from an acid solution of a metal precursor into the poly(2-vinylpyridine) (P2VP) microdomains of a polystyrene-b-P2VP block copolymer is shown to reduce the uptake of solvent vapor during a subsequent solvent annealing process, locking the morphology of the self-assembled microdomains. The amount of metal, here Pt, incorporated into the P2VP increases with both metal precursor [PtCl4]2- and hydrochloric acid concentrations, reaching 0.83 Pt atom per pyridine unit. The metal is then exfiltrated using a KOH + ethylenediaminetetraacetic acid disodium salt dihydrate (Na2EDTA) complexing solution, which restores solvent uptake and unlocks the morphology. The reversibility of the metal infiltration and morphology locking is demonstrated in a multistage annealing process and is confirmed for Fe as well as Pt. Reversible locking and unlocking of block copolymer microdomain morphologies expand their utility for nanofabrication processes by allowing the morphology to be fixed during subsequent process steps.

Large Anomalous Frequency Shift in Perpendicular Standing Spin Wave Modes in BiYIG Films Induced by Thin Metallic Overlayers.

Interface-driven effects on magnon dynamics are studied in magnetic insulator-metal bilayers using Brillouin light scattering. It is found that the Damon-Eshbach modes exhibit a significant frequency shift due to interfacial anisotropy generated by thin metallic overlayers. In addition, an unexpectedly large shift in the perpendicular standing spin wave mode frequencies is also observed, which cannot be explained by anisotropy-induced mode stiffening or surface pinning. Rather, it is suggested that additional confinement may result from spin pumping at the insulator-metal interface, which results in a locally overdamped interface region. These results uncover previously unidentified interface-driven changes in magnetization dynamics that may be exploited to locally control and modulate magnonic properties in thin-film heterostructures.

Revealing Site Occupancy in a Complex Oxide: Terbium Iron Garnet.

Complex oxide films stabilized by epitaxial growth can exhibit large populations of point defects which have important effects on their properties. The site occupancy of pulsed laser-deposited epitaxial terbium iron garnet (TbIG) films with excess terbium (Tb) is analyzed, in which the terbium:iron (Tb:Fe)ratio is 0.86 compared to the stoichiometric value of 0.6. The magnetic properties of the TbIG are sensitive to site occupancy, exhibiting a higher compensation temperature (by 90 K) and a lower Curie temperature (by 40 K) than the bulk Tb3 Fe5 O12 garnet. Data derived from X-ray core-level spectroscopy, magnetometry, and molecular field coefficient modeling are consistent with occupancy of the dodecahedral sites by Tb3+ , the octahedral sites by Fe3+ , Tb3+ and vacancies, and the tetrahedral sites by Fe3+ and vacancies. Energy dispersive X-ray spectroscopy in a scanning transmission electron microscope provides direct evidence of TbFe antisites. A small fraction of Fe2+ is present, and oxygen vacancies are inferred to be present to maintain charge neutrality. Variation of the site occupancies provides a path to considerable manipulation of the magnetic properties of epitaxial iron garnet films and other complex oxides, which readily accommodate stoichiometries not found in their bulk counterparts.

Emergence of layered nanoscale mesh networks through intrinsic molecular confinement self-assembly.

Block copolymer self-assembly is a powerful tool for two-dimensional nanofabrication; however, the extension of this self-assembly concept to complex three-dimensional network structures is limited. Here we report a simple method to experimentally generate three-dimensional layered mesh morphologies through intrinsic molecular confinement self-assembly. We designed triblock bottlebrush polymers with two Janus domains: one perpendicular and one parallel to the polymer backbone. The former enforces a lamellar superstructure that intrinsically confines the intralayer self-assembly of the latter, giving rise to a mesh-like monoclinic (54°) M15 network substructure with excellent long-range order, as well as a tetragonal (90°) T131 mesh. Numerical simulations show that the spatial constraints exerted on the polymer backbone drive the assembly of M15 and yield T131 in the strong segregation regime. This work demonstrates that intrinsic molecular confinement is a viable path to bottom-up assembly of new geometrical phases of soft matter, extending the capabilities of block copolymer nanofabrication.

Experimental and Computational Evaluation of Self-Assembled Morphologies in Diblock Janus Bottlebrush Copolymers.

Diblock Janus-type "A-branch-B" bottlebrush copolymers (di-JBBCPs) consist of a backbone with alternating A and B side chains, in contrast to the side chain arrangement of conventional bottlebrush copolymers. As a result, A and B blocks of di-JBBCPs can microphase-separate perpendicular to the backbone, which is located at the interface between the two blocks. A reparametrized dissipative particle dynamics (DPD) model is used to theoretically investigate the self-assembly of di-JBBCPs and to compare with the experimental results of a range of polystyrene-branch-polydimethylsiloxane di-JBBCPs. The experimentally formed cylinder, gyroid, and lamellar morphologies showed good correspondence with the model phase diagram, and the effect of changing volume fraction and backbone length is revealed. The DPD model predicts a bulk-stable perforated lamella morphology together with two unconventional spherical phases, the Frank-Kasper A15 spheres and the hexagonally close-packed spheres, indicating the diversity of morphologies available from complex BCP molecular architectures.

Selective sequential infiltration synthesis of ZnO in the liquid crystalline phase of silicon-containing rod-coil block copolymers.

The combination of block copolymer (BCP) thin film self-assembly and selective infiltration synthesis of inorganic materials into one BCP block provides access to various organic-inorganic hybrids. Here, we apply sequential infiltration synthesis, a vapor-phase hybridization technique, to selectively introduce ZnO into the organic microdomains of silicon-containing rod-coil diblock copolymers and a triblock terpolymer, polydimethylsiloxane (PDMS)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS) and PDMS-b-polystyrene-b-PMPCS (PDMS-b-PS-b-PMPCS), in which the PMPCS rod block is a liquid crystalline polymer. The in-plane cylindrical PDMS-b-PMPCS and core-shell cylindrical and hexagonally perforated lamellar PDMS-b-PS-b-PMPCS films were infiltrated with ZnO with high selectivity to the PMPCS. The etching contrast between PDMS, PS and the ZnO-infused PMPCS enables the fabrication of ZnO/SiOx binary composites by plasma etching and reveals the core-shell morphology of the triblock terpolymer.

Metallic Nanomeshes Fabricated by Multimechanism Directed Self-Assembly.

The directed self-assembly of block copolymers (BCPs) is a powerful motif for the continued scaling of feature sizes for nanoscale devices. A multimechanism directed self-assembly (MMDSA) method is described that generates orthogonal meshes from a polystyrene-b-poly-2-vinylpyridine BCP that is subsequently metallized with Pt. The MMDSA process takes advantage of three different mechanisms, trench wall guidance, edge nucleation, and underlayer guidance, to align the mesh with respect to substrate features. The mechanisms and their interactions are investigated via both experiments and dissipative particle dynamics simulations. MMDSA is applied to produce well-aligned conductive nanomeshes and then is extended to fabricate multicomponent metallic structures with 2D/3D hybrid morphologies.

Selective Deposition of Copper on Self-Assembled Block Copolymer Surfaces via Physical Vapor Deposition.

Block copolymer (BCP) self-assembly produces chemically and topographically patterned surfaces which are used to guide the formation of Cu nanostructures by exploiting differences in the mobility of vapor-deposited species on each microdomain. Cu metal films a few nm thick were deposited on three different BCP surfaces self-assembled from poly(styrene-b-methyl methacrylate) (PS-b-PMMA) and polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP). For PS-b-PMMA, the effects of chemical heterogeneity dominate over the effects of the 2 nm peak-to-valley topography, and sputtered Cu preferentially wets the PS block. PS-b-P2VP has greater chemical and topographical contrast and shows a wider process window for selective deposition. Cu grown by evaporation has less surface mobility, and shadowing effects are believed to dominate pattern formation. The hierarchical self-assembly process of thin metal films on BCP surfaces provides a route to fabricating heterogeneous metallic nanostructures.

An antisite defect mechanism for room temperature ferroelectricity in orthoferrites.

Single-phase multiferroic materials that allow the coexistence of ferroelectric and magnetic ordering above room temperature are highly desirable, motivating an ongoing search for mechanisms for unconventional ferroelectricity in magnetic oxides. Here, we report an antisite defect mechanism for room temperature ferroelectricity in epitaxial thin films of yttrium orthoferrite, YFeO3, a perovskite-structured canted antiferromagnet. A combination of piezoresponse force microscopy, atomically resolved elemental mapping with aberration corrected scanning transmission electron microscopy and density functional theory calculations reveals that the presence of YFe antisite defects facilitates a non-centrosymmetric distortion promoting ferroelectricity. This mechanism is predicted to work analogously for other rare earth orthoferrites, with a dependence of the polarization on the radius of the rare earth cation. Our work uncovers the distinctive role of antisite defects in providing a mechanism for ferroelectricity in a range of magnetic orthoferrites and further augments the functionality of this family of complex oxides for multiferroic applications.

Bending Behavior and Directed Self-Assembly of Rod-Coil Block Copolymers.

The formation of zigzags, chevrons, Y-junctions, and line segments is demonstrated in thin films formed from cylindrical morphology silicon-containing conformationally asymmetric rod-coil diblock copolymers and triblock terpolymers under solvent annealing. Directed self-assembly of the block copolymers within trenches yields well-ordered cylindrical microdomains oriented either parallel or transverse to the sidewalls depending on the chemical functionalization of the sidewalls, and the location and structure of concentric bends in the cylinders is determined by the shape of the trenches. The innate etching contrast, the spontaneous sharp bends and junctions, and the range of demonstrated periodicity and line/space ratios make these conformationally asymmetric rod-coil polymers attractive for nanoscale pattern generation.

Relativistic kinematics of a magnetic soliton.

A tenet of special relativity is that no particle can exceed the speed of light. In certain magnetic materials, the maximum magnon group velocity serves as an analogous relativistic limit for the speed of magnetic solitons. Here, we drive domain walls to this limit in a low-dissipation magnetic insulator using pure spin currents from the spin Hall effect. We achieve record current-driven velocities in excess of 4300 meters per second-within ~10% of the relativistic limit-and we observe key signatures of relativistic motion associated with Lorentz contraction, which leads to velocity saturation. The experimental results are well explained through analytical and atomistic modeling. These observations provide critical insight into the fundamental limits of the dynamics of magnetic solitons and establish a readily accessible experimental framework to study relativistic solitonic physics.

Machine Learning Predictions of Block Copolymer Self-Assembly.

Directed self-assembly of block copolymers is a key enabler for nanofabrication of devices with sub-10 nm feature sizes, allowing patterning far below the resolution limit of conventional photolithography. Among all the process steps involved in block copolymer self-assembly, solvent annealing plays a dominant role in determining the film morphology and pattern quality, yet the interplay of the multiple parameters during solvent annealing, including the initial thickness, swelling, time, and solvent ratio, makes it difficult to predict and control the resultant self-assembled pattern. Here, machine learning tools are applied to analyze the solvent annealing process and predict the effect of process parameters on morphology and defectivity. Two neural networks are constructed and trained, yielding accurate prediction of the final morphology in agreement with experimental data. A ridge regression model is constructed to identify the critical parameters that determine the quality of line/space patterns. These results illustrate the potential of machine learning to inform nanomanufacturing processes.

Self-Directed Self-Assembly of 3D Tailored Block Copolymer Nanostructures.

Directed self-assembly (DSA) of block copolymers (BCPs) provides a powerful tool to fabricate various 2D nanostructures. However, it still remains a challenge to extend DSA to make uniform and complex 3D nanostructures through BCP self-assembly. In this paper, we introduce a method to fabricate various nanostructures in 3D and test it using simulations. In particular, we employ dissipative particle dynamics (DPD) simulation to demonstrate that uniform multilayer nanostructures can be achieved by alternating the stacking of two "orthogonal" BCPs films, AB copolymer film and AC copolymer film, without the need to cross-link or etch any of the components. The assembly of a new layer occurs on top of the previous bottom layer, and thus the structural information from the substrate is propagated upward in the film, a process we refer to as self-directed self-assembly (SDSA). If this process is repeated many times, one can have tailored multilayer nanostructures. Furthermore, the natural (bulk) phases of the block copolymers in each layer do not need to be the same, so one can achieve complex 3D assemblies that are not possible with a single-phase 3D system. This method in conjunction with grapho (or chemo) epitaxy is able to evolve a surface pattern into a 3D nanostructure. Here we show several examples of nanostructures fabricated by this process, which include aligned cylinders, spheres on top of cylinders, and orthogonal nanomeshes. Our work should be useful for creating complex 3D nanostructures using self-assembly.

Tough and Strong: Cross-Lamella Design Imparts Multifunctionality to Biomimetic Nacre.

The creation of structural composites with combined strength, toughness, low density, and biocompatibility remains a long-standing challenge. On the other hand, bivalve marine shells-Clinocardiumspp.-exhibit strength, stiffness, and toughness that surpass even that of the nacre that is the most widely mimicked model for structural composites. The superior mechanical properties of Clinocardiumspp. shells originate from their cross-lamella design, comprising CaCO3 mineral platelets arranged in an "interlocked" herringbone fashion. Reproduction of such hierarchical designs could offer multifunctionality, potentially combining strength and toughness at low densities, and the capability for seamless integration with biological systems. Here, we demonstrate manufacturing of the cross-lamella design by biomineralizing aragonite films with sawtooth patterns and assembling them in a chitosan/fibroin matrix to generate a composite with interlocked mineral layers. The resultant composite, with a similar constitution to that of the biological counterpart, nearly doubles the strength of previous nacre-mimetic composites while improving the tensile toughness and simultaneously exhibiting stiffness and biocompatibility.