Spin-Phonon Coupling in Iron-Doped Ultrathin Bismuth Halide Perovskite Derivatives.

Spin in semiconductors facilitates magnetically controlled optoelectronic and spintronic devices. In metal halide perovskites (MHPs), doping magnetic ions is proven to be a simple and efficient approach to introducing a spin magnetic momentum. In this work, we present a facile metal ion doping protocol through the vapor-phase metal halide insertion reaction to the chemical vapor deposition (CVD)-grown ultrathin Cs3BiBr6 perovskites. The Fe-doped bismuth halide (Fe:CBBr) perovskites demonstrate that the iron spins are successfully incorporated into the lattice, as revealed by the spin-phonon coupling below the critical temperature Tc around 50 K observed through temperature-dependent Raman spectroscopy. Furthermore, the phonons exhibit significant softening under an applied magnetic field, possibly originating from magnetostriction and spin exchange interaction. The spin-phonon coupling in Fe:CBBr potentially provides an efficient way to tune the spin and lattice parameters for halide perovskite-based spintronics.

Spin-orbit exciton-induced phonon chirality in a quantum magnet.

The interplay of charge, spin, lattice, and orbital degrees of freedom in correlated materials often leads to rich and exotic properties. Recent studies have brought new perspectives to bosonic collective excitations in correlated materials. For example, inelastic neutron scattering experiments revealed non-trivial band topology for magnons and spin-orbit excitons (SOEs) in a quantum magnet CoTiO3 (CTO). Here, we report phonon properties resulting from a combination of strong spin-orbit coupling, large crystal field splitting, and trigonal distortion in CTO. Specifically, the interaction between SOEs and phonons endows chirality to two [Formula: see text] phonon modes and leads to large phonon magnetic moments observed in magneto-Raman spectra. The remarkably strong magneto-phononic effect originates from the hybridization of SOEs and phonons due to their close energy proximity. While chiral phonons have been associated with electronic topology in some materials, our work suggests opportunities may arise by exploring chiral phonons coupled to topological bosons.

Revealing intrinsic domains and fluctuations of moiré magnetism by a wide-field quantum microscope.

Moiré magnetism featured by stacking engineered atomic registry and lattice interactions has recently emerged as an appealing quantum state of matter at the forefront of condensed matter physics research. Nanoscale imaging of moiré magnets is highly desirable and serves as a prerequisite to investigate a broad range of intriguing physics underlying the interplay between topology, electronic correlations, and unconventional nanomagnetism. Here we report spin defect-based wide-field imaging of magnetic domains and spin fluctuations in twisted double trilayer (tDT) chromium triiodide CrI3. We explicitly show that intrinsic moiré domains of opposite magnetizations appear over arrays of moiré supercells in low-twist-angle tDT CrI3. In contrast, spin fluctuations measured in tDT CrI3 manifest little spatial variations on the same mesoscopic length scale due to the dominant driving force of intralayer exchange interaction. Our results enrich the current understanding of exotic magnetic phases sustained by moiré magnetism and highlight the opportunities provided by quantum spin sensors in probing microscopic spin related phenomena on two-dimensional flatland.

Evidence for Topological Magnon-Phonon Hybridization in a 2D Antiferromagnet down to the Monolayer Limit.

Topological phonons and magnons potentially enable low-loss, quantum coherent, and chiral transport of information and energy at the atomic scale. Van der Waals magnetic materials are promising to realize such states due to their recently discovered strong interactions among the electronic, spin, and lattice degrees of freedom. Here, we report the first observation of coherent hybridization of magnons and phonons in monolayer antiferromagnet FePSe3 by cavity-enhanced magneto-Raman spectroscopy. The robust magnon-phonon cooperativity in the 2D limit occurs even in zero magnetic field, which enables nontrivial band inversion between longitudinal and transverse optical phonons caused by the strong coupling with magnons. The spin and lattice symmetry theoretically guarantee magnetic-field-controlled topological phase transition, verified by nonzero Chern numbers calculated from the coupled spin-lattice model. The 2D topological magnon-phonon hybridization potentially offers a new route toward quantum phononics and magnonics with an ultrasmall footprint.

Magnetic anisotropy reversal driven by structural symmetry-breaking in monolayer α-RuCl3.

Layered α-RuCl3 is a promising material to potentially realize the long-sought Kitaev quantum spin liquid with fractionalized excitations. While evidence of this state has been reported under a modest in-plane magnetic field, such behaviour is largely inconsistent with theoretical expectations of spin liquid phases emerging only in out-of-plane fields. These predicted field-induced states have been largely out of reach due to the strong easy-plane anisotropy of bulk crystals, however. We use a combination of tunnelling spectroscopy, magnetotransport, electron diffraction and ab initio calculations to study the layer-dependent magnons, magnetic anisotropy, structure and exchange coupling in atomically thin samples. Due to picoscale distortions, the sign of the average off-diagonal exchange changes in monolayer α-RuCl3, leading to a reversal of spin anisotropy to easy-axis anisotropy, while the Kitaev interaction is concomitantly enhanced. Our work opens the door to the possible exploration of Kitaev physics in the true two-dimensional limit.

Theoretical and experimental investigations on rotary ultrasonic surface micro-machining of brittle materials.

Many brittle materials, such as single-crystal materials, amorphous materials, and ceramics, are widely used in many industries such as the energy industry, aerospace industry, and biomedical industry. In recent years, there is an increasing demand for high-precision micro-machining of these brittle materials to produce precision functional parts. Traditional ultra-precision micro-machining can lead to workpiece cracking, low machined surface quality, and reduced tool life. To reduce and further solve these problems, a new micro-machining process is needed. As one of the nontraditional machining processes, rotary ultrasonic machining is an effective method to reduce the issues generated by traditional machining processes of brittle materials. Therefore, rotary ultrasonic micro-machining (RUµM) is investigated to conduct the surface micro-machining of brittle materials. Due to the small diameter cutting tool (<500 µm) and high accuracy requirements, the impact of input parameters in the rotary ultrasonic surface micro-machining (RUSµM) process on tool deformation and cutting quality is extremely different from that in rotary ultrasonic surface machining (RUSM) with relatively large diameter cutting tool (∼10 mm). Up till now, there is still no investigation on the effects of ultrasonic vibration (UV) and input variables (such as tool rotation speed and depth of cut) on cutting force and machined surface quality in RUSµM of brittle materials. To fill this knowledge gap, rotary ultrasonic surface micro-machining of the silicon wafer (one of the most versatile brittle materials) was conducted in this study. The effects of ultrasonic vibration, tool rotation speed, and depth of cut on tool trajectory, material removal rate (MRR), cutting force, cutting surface quality, and residual stress were investigated. Results show that the ultrasonic vibration could reduce the cutting force, improve the cutting surface quality, and suppress the residual compressive stress, especially under conditions with high tool rotation speed.

Structural Monoclinicity and Its Coupling to Layered Magnetism in Few-Layer CrI3.

Using polarization-resolved Raman spectroscopy, we investigate layer number, temperature, and magnetic field dependence of Raman spectra in one- to four-layer CrI3. Layer-number-dependent Raman spectra show that in the paramagnetic phase a doubly degenerated Eg mode of monolayer CrI3 splits into one Ag and one Bg mode in N-layer (N > 1) CrI3 due to the monoclinic stacking. Their energy separation increases in thicker samples until an eventual saturation. Temperature-dependent measurements further show that the split modes tend to merge upon cooling but remain separated until 10 K, indicating a failed attempt of the monoclinic-to-rhombohedral structural phase transition that is present in the bulk crystal. Magnetic-field-dependent measurements reveal an additional monoclinic distortion across the magnetic-field-induced layered antiferromagnetism-to-ferromagnetism phase transition. We propose a structural change that consists of both a lateral sliding toward the rhombohedral stacking and a decrease in the interlayer distance to explain our experimental observations.

Hexagonal Boron Nitride Crystal Growth from Iron, a Single Component Flux.

The highest quality hexagonal boron nitride (hBN) crystals are grown from molten solutions. For hBN crystal growth at atmospheric pressure, typically the solvent is a combination of two metals, one with a high boron solubility and the other to promote nitrogen solubility. In this study, we demonstrate that high-quality hBN crystals can be grown at atmospheric pressure using pure iron as a flux. The ability to produce excellent-quality hBN crystals using pure iron as a solvent is unexpected, given its low solubility for nitrogen. The properties of crystals produced with this flux matched the best values ever reported for hBN: a narrow Raman E2g vibration peak (7.6 cm-1) and strong phonon-assisted peaks in the photoluminescence spectra. To further test their quality, the hBN crytals were used as a substrate for WSe2 epitaxy. WSe2 was deposited with a low nucleation density, indicating the low defect density of the hBN. Lastly, the carrier tunneling through our hBN thin layers (3.5 nm) follows the Fowler-Nordheim model, with a barrier height of 3.7 eV, demonstrating hBN's superior electrical insulating properties. This ability to produce high-quality hBN crystals in such a simple, environmentally friendly and economical process will advance two-dimensional material research by enabling integrated devices.

Observation of the polaronic character of excitons in a two-dimensional semiconducting magnet CrI3.

Exciton dynamics can be strongly affected by lattice vibrations through electron-phonon coupling. This is rarely explored in two-dimensional magnetic semiconductors. Focusing on bilayer CrI3, we first show the presence of strong electron-phonon coupling through temperature-dependent photoluminescence and absorption spectroscopy. We then report the observation of periodic broad modes up to the 8th order in Raman spectra, attributed to the polaronic character of excitons. We establish that this polaronic character is dominated by the coupling between the charge-transfer exciton at 1.96 eV and a longitudinal optical phonon at 120.6 cm-1. We further show that the emergence of long-range magnetic order enhances the electron-phonon coupling strength by ~50% and that the transition from layered antiferromagnetic to ferromagnetic order tunes the spectral intensity of the periodic broad modes, suggesting a strong coupling among the lattice, charge and spin in two-dimensional CrI3. Our study opens opportunities for tailoring light-matter interactions in two-dimensional magnetic semiconductors.

Tunable layered-magnetism-assisted magneto-Raman effect in a two-dimensional magnet CrI3.

We used a combination of polarized Raman spectroscopy experiment and model magnetism-phonon coupling calculations to study the rich magneto-Raman effect in the two-dimensional (2D) magnet CrI3 We reveal a layered-magnetism-assisted phonon scattering mechanism below the magnetic onset temperature, whose Raman excitation breaks time-reversal symmetry, has an antisymmetric Raman tensor, and follows the magnetic phase transitions across critical magnetic fields, on top of the presence of the conventional phonon scattering with symmetric Raman tensors in N-layer CrI3 We resolve in data and by calculations that the first-order A g phonon of the monolayer splits into an N-fold multiplet in N-layer CrI3 due to the interlayer coupling [Formula: see text] and that the phonons within the multiplet show distinct magnetic field dependence because of their different layered-magnetism-phonon coupling. We further find that such a layered-magnetism-phonon coupled Raman scattering mechanism extends beyond first-order to higher-order multiphonon scattering processes. Our results on the magneto-Raman effect of the first-order phonons in the multiplet and the higher-order multiphonons in N-layer CrI3 demonstrate the rich and strong behavior of emergent magneto-optical effects in 2D magnets and underline the unique opportunities of spin-phonon physics in van der Waals layered magnets.

V2O5: A 2D van der Waals Oxide with Strong In-Plane Electrical and Optical Anisotropy.

V2O5 with a layered van der Waals (vdW) structure has been widely studied because of the material's potential in applications such as battery electrodes. In this work, microelectronic devices were fabricated to study the electrical and optical properties of mechanically exfoliated multilayered V2O5 flakes. Raman spectroscopy was used to determine the crystal structure axes of the nanoflakes and revealed that the intensities of the Raman modes depend strongly on the relative orientation between the crystal axes and the polarization directions of incident/scattered light. Angular dependence of four-probe resistance measured in the van der Pauw (vdP) configuration revealed an in-plane anisotropic resistance ratio of ∼100 between the a and b crystal axes, the largest in-plane transport anisotropy effect experimentally reported for two-dimensional (2D) materials to date. This very large resistance anisotropic ratio is explained by the nonuniform current flow in the vdP measurement and an intrinsic mobility anisotropy ratio of 10 between the a and b crystal axes. Room-temperature electron Hall mobility up to 7 cm2/(V s) along the high-mobility direction was obtained. This work demonstrates V2O5 as a layered 2D vdW oxide material with strongly anisotropic optical and electronic properties for novel applications.

Coupling and Stacking Order of ReS2 Atomic Layers Revealed by Ultralow-Frequency Raman Spectroscopy.

We investigate the ultralow-frequency Raman response of atomically thin ReS2, a special type of two-dimensional (2D) semiconductors with unique distorted 1T structure. Bilayer and few-layer ReS2 exhibit rich Raman spectra at frequencies below 50 cm(-1), where a panoply of interlayer shear and breathing modes are observed. The emergence of these interlayer phonon modes indicate that the ReS2 layers are coupled and orderly stacked. Whereas the interlayer breathing modes behave similarly to those in other 2D layered crystals, the shear modes exhibit distinctive behavior due to the in-plane lattice distortion. In particular, the two shear modes in bilayer ReS2 are nondegenerate and clearly resolved in the Raman spectrum, in contrast to the doubly degenerate shear modes in other 2D materials. By carrying out comprehensive first-principles calculations, we can account for the frequency and Raman intensity of the interlayer modes and determine the stacking order in bilayer ReS2.