Magneto-optics in a van der Waals magnet tuned by self-hybridized polaritons.

Controlling quantum materials with light is of fundamental and technological importance. By utilizing the strong coupling of light and matter in optical cavities1-3, recent studies were able to modify some of their most defining features4-6. Here we study the magneto-optical properties of a van der Waals magnet that supports strong coupling of photons and excitons even in the absence of external cavity mirrors. In this material-the layered magnetic semiconductor CrSBr-emergent light-matter hybrids called polaritons are shown to substantially increase the spectral bandwidth of correlations between the magnetic, electronic and optical properties, enabling largely tunable optical responses to applied magnetic fields and magnons. Our results highlight the importance of exciton-photon self-hybridization in van der Waals magnets and motivate novel directions for the manipulation of quantum material properties by strong light-matter coupling.

Ultrafast Exciton Dynamics in the Atomically Thin van der Waals Magnet CrSBr.

Among atomically thin semiconductors, CrSBr stands out as both its bulk and monolayer forms host tightly bound, quasi-one-dimensional excitons in a magnetic environment. Despite its pivotal importance for solid-state research, the exciton lifetime has remained unknown. While terahertz polarization probing can directly trace all excitons, independently of interband selection rules, the corresponding large far-field foci substantially exceed the lateral sample dimensions. Here, we combine terahertz polarization spectroscopy with near-field microscopy to reveal a femtosecond decay of paramagnetic excitons in a monolayer of CrSBr, which is 30 times shorter than the bulk lifetime. We unveil low-energy fingerprints of bound and unbound electron-hole pairs in bulk CrSBr and extract the nonequilibrium dielectric function of the monolayer in a model-free manner. Our results demonstrate the first direct access to the ultrafast dielectric response of quasi-one-dimensional excitons in CrSBr, potentially advancing the development of quantum devices based on ultrathin van der Waals magnets.

Ferromagnetic Interlayer Coupling in CrSBr Crystals Irradiated by Ions.

Layered magnetic materials are becoming a major platform for future spin-based applications. Particularly, the air-stable van der Waals compound CrSBr is attracting considerable interest due to its prominent magneto-transport and magneto-optical properties. In this work, we observe a transition from antiferromagnetic to ferromagnetic behavior in CrSBr crystals exposed to high-energy, non-magnetic ions. Already at moderate fluences, ion irradiation induces a remanent magnetization with hysteresis adapting to the easy-axis anisotropy of the pristine magnetic order up to a critical temperature of 110 K. Structure analysis of the irradiated crystals in conjunction with density functional theory calculations suggests that the displacement of constituent atoms due to collisions with ions and the formation of interstitials favors ferromagnetic order between the layers.

Magneto-Optical Sensing of the Pressure Driven Magnetic Ground States in Bulk CrSBr.

Competition between exchange interactions and magnetocrystalline anisotropy may bring new magnetic states that are of great current interest. An applied hydrostatic pressure can further be used to tune their balance. In this work, we investigate the magnetization process of a biaxial antiferromagnet in an external magnetic field applied along the easy axis. We find that the single metamagnetic transition of the Ising type observed in this material under ambient pressure transforms under hydrostatic pressure into two transitions, a first-order spin-flop transition followed by a second-order transition toward a polarized ferromagnetic state near saturation. This reversible tuning into a new magnetic phase is obtained in layered bulk CrSBr at low temperature by varying the interlayer distance using high hydrostatic pressure, which efficiently acts on the interlayer magnetic exchange and is probed by magneto-optical spectroscopy.

Electrostatic co-assembly of FePS3 nanosheets and surface functionalized BCN heterostructures for hydrogen evolution reaction.

Advances in the hydrogen evolution reaction (HER) are intricately connected with addressing the current energy crisis and quest for sustainable energy sources. The necessity of catalysts that are efficient and inexpensive to perform the hydrogen evolution reaction is key to this. Following the ground-breaking discovery of graphene, metal thio/seleno phosphates (MPX3: M - transition metal, P - phosphorus and X - S/Se), two dimensional (2D) materials, exhibit excellent tunable physicochemical, electronic and optical properties, and are expected to be key to the energy industry for years to come. Taking this into account, a facile time-effective electrostatic restacking synthesis procedure has been followed to synthesize a 2D/2D heterostructure (FePS3@BCN) involving FePS3, one of the prominent MPX3 materials, with borocarbonitride (BCN), for hydrogen evolution reaction (HER). The piled up nanosheets of FePS3 and BCN are held together by an electrostatic force, and display extreme robustness under the harsh conditions of HER application. The amalgamated electrocatalyst achieved an overpotential of 187 mV at a current density of 10 mA cm-2 with a shallow Tafel slope of 41 mV dec-1, following the Volmer-Heyrovsky mechanism. The resilience of the electrocatalyst has been examined through chronoamperometric testing for long term stability, and it is stable for more than 14 hours, which shows the excellent electrocatalytic activity for hydrogen evolution reaction owing to the strategic approach to the catalyst design, the use of numerous electrochemically active sites, large surface area and a barrier-free channel for quick ion transfer.

Polarization-Resolved Position-Sensitive Self-Powered Binary Photodetection in Multilayer Janus CrSBr.

Recent progress in polarization-resolved photodetection based on low-symmetry 2D materials has formed the basis of cutting-edge optoelectronic devices, including quantum optical communication, 3D image processing, and sensing applications. Here, we report an optical polarization-resolving photodetector (PD) fabricated from multilayer semiconducting CrSBr single crystals with high structural anisotropy. We have demonstrated self-powered photodetection due to the formation of Schottky junctions at the Au-CrSBr interfaces, which also caused the photocurrent to display a position-sensitive and binary nature. The self-biased CrSBr PD showed a photoresponsivity of ∼0.26 mA/W with a detectivity of 3.4 × 108 Jones at 514 nm excitation of fluency (0.42 mW/cm2) under ambient conditions. The optical polarization-induced photoresponse exhibits a large dichroic ratio of 3.4, while the polarization is set along the a- and the b-axes of single-crystalline CrSBr. The PD also showed excellent stability, retaining >95% of the initial photoresponsivity in ambient conditions for more than five months without encapsulation. Thus, we demonstrate CrSBr as a fascinating material for ultralow-powered optical polarization-resolving optoelectronic devices for cutting-edge technology.

Electronic Band Structure and Optical Properties of HgPS3 Crystal and Layers.

Transition metal thiophosphates (MPS3) are of great interest due to their layered structure and magnetic properties. Although HgPS3 may not exhibit magnetic properties, its uniqueness lies in its triclinic crystal structure and in the substantial mass of mercury, rendering it a compelling subject for exploration in terms of fundamental properties. In this work, we present comprehensive experimental and theoretical studies of the electronic band structure and optical properties for the HgPS3 crystal and mechanically exfoliated layers from a solid crystal. Based on absorption, reflectance and photoluminescence measurements supported by theoretical calculations, it is shown that the HgPS3 crystal has an indirect gap of 2.68 eV at room temperature. The direct gap is identified at the Γ point of the Brillouin zone (BZ) ≈ 50 meV above the indirect gap. The optical transition at the Γ point is forbidden due to selection rules, but the oscillator strength near the Γ point increases rapidly and therefore the direct optical transitions are visible in the reflectance spectra approximately at 60-120 meV above the absorption edge, across the temperature range of 40 to 300 K. The indirect nature of the bandgap and the selection rules for Γ point contribute to the absence of near-bandgap emission in HgPS3. Consequently, the photoluminescence spectrum is primarily governed by defect-related emission. The electronic band structure of HgPS3 undergoes significant changes when the crystal thickness is reduced to tri- and bilayers, resulting in a direct bandgap. Interestingly, in the monolayer regime, the fundamental transition is again indirect. The layered structure of the HgPS3 crystal was confirmed by scanning electron microscopy (SEM) and by mechanical exfoliation.

Electrochemical Intercalation and Exfoliation of CrSBr into Ferromagnetic Fibers and Nanoribbons.

Recent studies dedicated to layered van der Waals crystals have attracted significant attention to magnetic atomically thin crystals offering unprecedented opportunities for applications in innovative magnetoelectric, magneto-optic, and spintronic devices. The active search for original platforms for the low-dimensional magnetism study has emphasized the entirely new magnetic properties of two dimensional (2D) semiconductor CrSBr. Herein, for the first time, the electrochemical exfoliation of bulk CrSBr in a non-aqueous environment is demonstrated. Notably, crystal cleavage governed by the structural anisotropy occurred along two directions forming atomically thin and few-layered nanoribbons. The exfoliated material possesses an orthorhombic crystalline structure and strong optical anisotropy, showing the polarization dependencies of Raman signals. The antiferromagnetism exhibited by multilayered CrSBr gives precedence to ferromagnetic ordering in the revealed CrSBr nanostructures. Furthermore, the potential application of CrSBr nanoribbons is pioneered for electrochemical photodetector fabrication and demonstrates its responsivity up to 30 µA cm-2 in the visible spectrum. Moreover, the CrSBr-based anode for lithium-ion batteries exhibited high performance and self-improving abilities. This anticipates that the results will pave the way toward the future study of CrSBr and practical applications in magneto- and optoelectronics.

High-κ Wide-Gap Layered Dielectric for Two-Dimensional van der Waals Heterostructures.

van der Waals heterostructures of two-dimensional materials have unveiled frontiers in condensed matter physics, unlocking unexplored possibilities in electronic and photonic device applications. However, the investigation of wide-gap, high-κ layered dielectrics for devices based on van der Waals structures has been relatively limited. In this work, we demonstrate an easily reproducible synthesis method for the rare-earth oxyhalide LaOBr, and we exfoliate it as a 2D layered material with a measured static dielectric constant of 9 and a wide bandgap of 5.3 eV. Furthermore, our research demonstrates that LaOBr can be used as a high-κ dielectric in van der Waals field-effect transistors with high performance and low interface defect concentrations. Additionally, it proves to be an attractive choice for electrical gating in excitonic devices based on 2D materials. Our work demonstrates the versatile realization and functionality of 2D systems with wide-gap and high-κ van der Waals dielectric environments.

Doping-control of excitons and magnetism in few-layer CrSBr.

Magnetism in two-dimensional materials reveals phenomena distinct from bulk magnetic crystals, with sensitivity to charge doping and electric fields in monolayer and bilayer van der Waals magnet CrI3. Within the class of layered magnets, semiconducting CrSBr stands out by featuring stability under ambient conditions, correlating excitons with magnetic order and thus providing strong magnon-exciton coupling, and exhibiting peculiar magneto-optics of exciton-polaritons. Here, we demonstrate that both exciton and magnetic transitions in bilayer and trilayer CrSBr are sensitive to voltage-controlled field-effect charging, exhibiting bound exciton-charge complexes and doping-induced metamagnetic transitions. Moreover, we demonstrate how these unique properties enable optical probes of local magnetic order, visualizing magnetic domains of competing phases across metamagnetic transitions induced by magnetic field or electrostatic doping. Our work identifies few-layer CrSBr as a rich platform for exploring collaborative effects of charge, optical excitations, and magnetism.

Anisotropic 2D van der Waals Magnets Hosting 1D Spin Chains.

The exploration of 1D magnetism, frequently portrayed as spin chains, constitutes an actively pursued research field that illuminates fundamental principles in many-body problems and applications in magnonics and spintronics. The inherent reduction in dimensionality often leads to robust spin fluctuations, impacting magnetic ordering and resulting in novel magnetic phenomena. Here, structural, magnetic, and optical properties of highly anisotropic 2D van der Waals antiferromagnets that uniquely host spin chains are explored. First-principle calculations reveal that the weakest interaction is interchain, leading to essentially 1D magnetic behavior in each layer. With the additional degree of freedom arising from its anisotropic structure, the structure is engineered by alloying, varying the 1D spin chain lengths using electron beam irradiation, or twisting for localized patterning, and spin textures are calculated, predicting robust stability of the antiferromagnetic ordering. Comparing with other spin chain magnets, these materials are anticipated to bring fresh perspectives on harvesting low-dimensional magnetism.

An aligned octahedral core in a nanocage: synthesis, plasmonic, and catalytic properties.

Plasmonic metal nanostructures with complex morphologies provide an important route to tunable optical responses and local electric field enhancement at the nanoscale for a variety of applications including sensing, imaging, and catalysis. Here we report a high-concentration synthesis of gold core-cage nanoparticles with a tethered and structurally aligned octahedral core and examine their plasmonic and catalytic properties. The obtained nanostructures exhibit a double band extinction in the visible-near infrared range and a large area electric field enhancement due to the unique structural features, as demonstrated using finite difference time domain (FDTD) simulations and confirmed experimentally using surface enhanced Raman scattering (SERS) tests. In addition, the obtained structures had a photoelectrochemical response useful for catalyzing the CO2 electroreduction reaction. Our work demonstrates the next generation of complex plasmonic nanostructures attainable via bottom-up synthesis and offers a variety of potential applications ranging from sensing to catalysis.