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.

Size dependence of the surface spin disorder and surface anisotropy constant in ferrite nanoparticles.

The magnetic properties of nanoscale magnets are greatly influenced by surface anisotropy. So far, its quantification is based on the examination of the blocking temperature shift within a series of nanoparticles of varying sizes. In this scenario, the surface anisotropy is assumed to be a particle size-independent quantity. However, there is no solid experimental proof to support this simplified picture. On the contrary, our work unravels the size-dependent magnetic morphology and surface anisotropy in highly uniform magnetic nanoparticles using small-angle polarized neutron scattering. We observed that the surface anisotropy constant does not depend on the nanoparticle's size in the range of 3-9 nm. Furthermore, our results demonstrate that the surface spins are less prone to polarization with increasing nanoparticle size. Our study thus proves the size dependence of the surface spin disorder and the surface anisotropy constant in fine nanomagnets. These findings open new routes in materials based on a controlled surface spin disorder, which is essential for future applications of nanomagnets in biomedicine and magnonics.

Chiral Light Emission from a Hybrid Magnetic Molecule-Monolayer Transition Metal Dichalcogenide Heterostructure.

Hybrid layered materials assembled from atomically thin crystals and small molecules bring great promises in pushing the current information and quantum technologies beyond the frontiers. We demonstrate here a class of layered valley-spin hybrid (VSH) materials composed of a monolayer two-dimensional (2D) semiconductor and double-decker single molecule magnets (SMMs). We have materialized a VSH prototype by thermal evaporation of terbium bis-phthalocyanine onto a MoS2 monolayer and revealed its composition and stability by both microscopic and spectroscopic probes. The interaction of the VSH components gives rise to the intersystem crossing of the photogenerated carriers and moderate p-doping of the MoS2 monolayer, as corroborated by the density functional theory calculations. We further explored the valley contrast by helicity-resolved photoluminescence (PL) microspectroscopy carried out down to liquid helium temperatures and in the presence of the external magnetic field. The most striking feature of the VSH is the enhanced A exciton-related valley emission observed at the out-of-resonance condition at room temperature, which we elucidated by the proposed nonradiative energy drain transfer mechanism. Our study thus demonstrates the experimental feasibility and great promises of the ultrathin VSH materials with chiral light emission, operable by physical fields for emerging opto-spintronic, valleytronic, and quantum information concepts.

Isotope Engineered Fluorinated Single and Bilayer Graphene: Insights into Fluorination Selectivity, Stability, and Defect Passivation.

Tailoring the physicochemical properties of graphene through functionalization remains a major interest for next-generation technological applications. However, defect formation due to functionalization greatly endangers the intrinsic properties of graphene, which remains a serious concern. Despite numerous attempts to address this issue, a comprehensive analysis has not been conducted. This work reports a two-step fluorination process to stabilize the fluorinated graphene and obtain control over the fluorination-induced defects in graphene layers. The structural, electronic and isotope-mass-sensitive spectroscopic characterization unveils several not-yet-resolved facts, such as fluorination sites and CF bond stability in partially-fluorinated graphene (F-SLG). The stability of fluorine has been correlated to fluorine co-shared between two graphene layers in fluorinated-bilayer-graphene (F-BLG). The desorption energy of co-shared fluorine is an order of magnitude higher than the CF bond energy in F-SLG due to the electrostatic interaction and the inhibition of defluorination in the F-BLG. Additionally, F-BLG exhibits enhanced light-matter interaction, which has been utilized to design a proof-of-concept field-effect phototransistor that produces high photocurrent response at a time <200 µs. Thus, the study paves a new avenue for the in-depth understanding and practical utilization of fluorinated graphenic carbon.

Chiral, Magnetic, and Photosensitive Liquid Crystalline Nanocomposites Based on Multifunctional Nanoparticles and Achiral Liquid Crystals.

Nanoparticles serving as a multifunctional and multiaddressable dopant to modify the properties of liquid crystalline matrices are developed by combining cobalt ferrite nanocrystals with organic ligands featuring a robust photosensitive unit and a source of chirality from the natural pool. These nanoparticles provide a stable nanocomposite when dispersed in achiral liquid crystals, giving rise to chiral supramolecular structures that can respond to UV-light illumination, and, at the same time, the formed nanocomposite possesses strong magnetic response. We report on a nanocomposite that shows three additional functionalities (chirality and responsiveness to UV light and magnetic field) upon the introduction of a single dopant into achiral liquid crystals.

Effect of different molecular coatings on the heating properties of maghemite nanoparticles.

In this work, the effect of different molecular coatings on the alternating magnetic field-induced heating properties of 15 nm maghemite nanoparticles (NPs) in water dispersions was studied at different frequencies (159-782 kHz) and field amplitudes (100-400 G). The original hydrophobic oleate coating was replaced with dimercaptosuccinic acid (DMSA) or polyethylene glycol trimethoxysilane (PEGTMS), while cetrimonium bromide (CTAB) or stearic acid-poloxamer 188 (SA-P188) was intercalated or encapsulated, respectively, to transfer the dispersions into water. Surface modification, based on intercalation processes, induced clustering phenomena with the formation of spherical-like assemblies (CTAB and SA-P188), while ligand-exchange strategies kept the particles isolated. The clustering phenomenon has detrimental effects on the heating performances compared with isolated systems, in line with the reduction of Brown relaxation times. Furthermore, broader comprehension of the heating phenomenon in this dynamic system is obtained by following the evolution of SPA and ILP with time and temperature beyond the initial stage.

Self-Limitations of Heat Release in Coupled Core-Shell Spinel Ferrite Nanoparticles: Frequency, Time, and Temperature Dependencies.

We explored a series of highly uniform magnetic nanoparticles (MNPs) with a core-shell nanoarchitecture prepared by an efficient solvothermal approach. In our study, we focused on the water dispersion of MNPs based on two different CoFe2O4 core sizes and the chemical nature of the shell (MnFe2O4 and spinel iron oxide). We performed an uncommon systematic investigation of the time and temperature evolution of the adiabatic heat release at different frequencies of the alternating magnetic field (AMF). Our systematic study elucidates the nontrivial variations in the heating efficiency of core-shell MNPs concerning their structural, magnetic, and morphological properties. In addition, we identified anomalies in the temperature and frequency dependencies of the specific power absorption (SPA). We conclude that after the initial heating phase, the heat release is governed by the competition of the Brown and Néel mechanism. In addition, we demonstrated that a rational parameter sufficiently mirroring the heating ability is the mean magnetic moment per MNP. Our study, thus, paves the road to fine control of the AMF-induced heating by MNPs with fine-tuned structural, chemical, and magnetic parameters. Importantly, we claim that the nontrivial variations of the SPA with the temperature must be considered, e.g., in the emerging concept of MF-assisted catalysis, where the temperature profile influences the undergoing chemical reactions.

Mixed sp2-sp3 Nanocarbon Materials: A Status Quo Review.

Carbon nanomaterials with a different character of the chemical bond-graphene (sp2) and nanodiamond (sp3)-are the building bricks for a new class of all-carbon hybrid nanomaterials, where the two different carbon networks with sp3 and sp2 hybridization coexist, interacting and even transforming into one another. The extraordinary physiochemical properties defined by the unique electronic band structure of the two border nanoallotropes ensure the immense application potential and versatility of these all-carbon nanomaterials. The review summarizes the status quo of sp2 - sp3 nanomaterials, including graphene/graphene-oxide-nanodiamond composites and hybrids, graphene/graphene-oxide-diamond heterojunctions, and other sp2-sp3 nanocarbon hybrids for sensing, electronic, and other emergent applications. Novel sp2-sp3 transitional nanocarbon phases and architectures are also discussed. Furthermore, the two-way sp2 (graphene) to sp3 (diamond surface and nanodiamond) transformations at the nanoscale, essential for innovative fabrication, and stability and chemical reactivity assessment are discussed based on extensive theoretical, computational and experimental studies.

Defect Structures of Magnetic Nanoparticles in Smectic A Liquid Crystals.

Topological defects in anisotropic fluids like liquid crystals serve as a playground for the research of various effects. In this study, we concentrated on a hybrid system of chiral rod-like molecules doped by magnetic nanoparticles. In textures of the smectic A phase, we observed linear defects and found that clusters of nanoparticles promote nucleation of smectic layer defects just at the phase transition from the isotropic to the smectic A (SmA) phase. In different geometries, we studied and analysed creation of defects which can be explained by attractive elastic forces between nanoparticles in the SmA phase. On cooling the studied hybrid system, clusters grow up to the critical dimension, and the smectic texture is stabilised. The presented effects are theoretically described and explained if we consider the elastic interaction of two point defects and stabilisation of prismatic dislocation loops due to the presence of nanoparticles.

Thermal Traits of MNPs under High-Frequency Magnetic Fields: Disentangling the Effect of Size and Coating.

We investigated the heating abilities of magnetic nanoparticles (MNPs) in a high-frequency magnetic field (MF) as a function of surface coating and size. The cobalt ferrite MNPs were obtained by a hydrothermal method in a water-oleic acid-ethanol system, yielding MNPs with mean diameter of about 5 nm, functionalized with the oleic acid. By applying another cycle of hydrothermal synthesis, we obtained MNPs with about one nm larger diameter. In the next step, the oleic acid was exchanged for 11-maleimidoundecanoic acid or 11-(furfurylureido)undecanoic acid. For the heating experiments, all samples were dispersed in the same solvent (dichloroethane) in the same concentration and the heating performance was studied in a broad interval of MF frequencies (346-782 kHz). The obtained results enabled us to disentangle the impact of the hydrodynamic, structural, and magnetic parameters on the overall heating capabilities. We also demonstrated that the specific power absorption does not show a monotonous trend within the series in the investigated interval of temperatures, pointing to temperature-dependent competition of the Brownian and Néel contributions in heat release.

Anomalous Freezing of Low-Dimensional Water Confined in Graphene Nanowrinkles.

Various properties of water are affected by confinement as the space-filling of the water molecules is very different from bulk water. In our study, we challenged the creation of a stable system in which water molecules are permanently locked in nanodimensional graphene traps. For that purpose, we developed a technique, nitrocellulose-assisted transfer of graphene grown by chemical vapor deposition, which enables capturing of the water molecules below an atomically thin graphene membrane structured into a net of regular wrinkles with a lateral dimension of about 4 nm. After successfully confining water molecules below a graphene monolayer, we employed cryogenic Raman spectroscopy to monitor the phase changes of the confined water as a function of the temperature. In our experiment system, the graphene monolayer structured into a net of fine wrinkles plays a dual role: (i) it enables water confinement and (ii) serves as an extremely sensitive probe for phase transitions involving water via graphene-based spectroscopic monitoring of the underlying water structure. Experimental findings were supported with classical and path integral molecular dynamics simulations carried out on our experimental system. Results of simulations show that surface premelting of the ice confined within the wrinkles starts at ∼200 K and the melting process is complete at ∼240 K, which is far below the melting temperature of bulk water ice. The processes correspond to changes in the doping and strain in the graphene tracked by Raman spectroscopy. We conclude that water can be confined between graphene structured into nanowrinkles and silica substrate and its phase transitions can be tracked via Raman spectral feature of the encapsulating graphene. Our study also demonstrated that peculiar behavior of liquids under spatial confinement can be inspected via the optical response of atomically thin graphene sensors.

Recent Advances of Graphene-Derived Nanocomposites in Water-Based Drilling Fluids.

Nanocomposite materials have distinctive potential for various types of captivating usage in drilling fluids as a well-designed solution for the petroleum industry. Owing to the improvement of drilling fluids, it is of great importance to fabricate unique nanocomposites and advance their functionalities for amplification in base fluids. There is a rising interest in assembling nanocomposites for the progress of rheological and filtration properties. A series of drilling fluid formulations have been reported for graphene-derived nanocomposites as additives. Over the years, the emergence of these graphene-derived nanocomposites has been employed as a paradigm to formulate water-based drilling fluids (WBDF). Herein, we provide an overview of nanocomposites evolution as engineered materials for enhanced rheological attributes in drilling operations. We also demonstrate the state-of-the-art potential graphene-derived nanocomposites for enriched rheology and other significant properties in WBDF. This review could conceivably deliver the inspiration and pathways to produce novel fabrication of nanocomposites and the production of other graphenaceous materials grafted nanocomposites for the variety of drilling fluids.

Understanding Magnetization Dynamics of a Magnetic Nanoparticle with a Disordered Shell Using Micromagnetic Simulations.

Spin disorder effects influence magnetization dynamics and equilibrium magnetic properties of real nanoparticles (NPs). In this work, we use micromagnetic simulations to try to better understand these effects, in particular, on how the magnetization reversal is projected in the character of the hysteresis loops at different temperatures. In our simulation study, we consider a prototype NP adopting a magnetic core-shell model, with magnetically coherent core and somewhat disordered shell, as it is one of the common spin architectures in real NPs. The size of the core is fixed to 5.5 nm in diameter and the shell thickness ranges from 0.5 nm to 3 nm. As a starting point in the simulations, we used typical experimental values obtained for a cobalt ferrite NP of a comparable size investigated previously. The simulations enabled us to study systematically the macrospin dynamics of the prototype NP and to address the interplay between the magnetic anisotropies of the core and the shell, respectively. We also demonstrate how the computational time step, run time, damping parameter, and thermal field influence the simulation results. In agreement with experimental studies, we observed that the direction and magnitude of the shell anisotropy influences the effective magnetic size of the core in the applied magnetic field. We conclude that micromagnetic simulations, in spite of being designed for much larger scales are a useful toolbox for understanding the magnetization processes within a single domain NP with an ordered spin structure in the core and partially disordered spins in the shell.

Coexistence of Van Hove singularities and pseudomagnetic fields in modulated graphene bilayer.

The stacking and bending of graphene are trivial but extremely powerful agents of control over graphene's manifold physics. By changing the twist angle, one can drive the system over a plethora of exotic states via strong electron correlation, thanks to the moiré superlattice potentials, while the periodic or triaxial strains induce discretization of the band structure into Landau levels without the need for an external magnetic field. We fabricated a hybrid system comprising both the stacking and bending tuning knobs. We have grown the graphene monolayers by chemical vapor deposition, using 12C and 13C precursors, which enabled us to individually address the layers through Raman spectroscopy mapping. We achieved the long-range spatial modulation by sculpturing the top layer (13C) over uniform magnetic nanoparticles (NPs) deposited on the bottom layer (12C). An atomic force microscopy study revealed that the top layer tends to relax into pyramidal corrugations with C3 axial symmetry at the position of the NPs, which have been widely reported as a source of large pseudomagnetic fields (PMFs) in graphene monolayers. The modulated graphene bilayer (MGBL) also contains a few micrometer large domains, with the twist angle ∼10°, which were identified via extreme enhancement of the Raman intensity of the G-mode due to formation of van Hove singularities (VHSs). We thereby conclude that the twist-induced VHSs coexist with the PMFs generated in the strained pyramidal objects without mutual disturbance. The graphene bilayer modulated with magnetic NPs is a non-trivial hybrid system that accommodates features of twist-induced VHSs and PMFs in environs of giant classical spins.

Formation of gadolinium-ferritin from clinical magnetic resonance contrast agents.

Gadolinium deposition in the brain following administration of gadolinium-based contrast agents (GBCAs) has led to health concerns. We show that some clinical GBCAs form Gd3+-ferritin nanoparticles at (sub)nanomolar concentrations of Gd3+ under physiological conditions. We describe their structure at atomic resolution and discuss potential relevance for clinical MRI.

Coupled hard-soft spinel ferrite-based core-shell nanoarchitectures: magnetic properties and heating abilities.

Bi-magnetic core-shell spinel ferrite-based nanoparticles with different CoFe2O4 core size, chemical nature of the shell (MnFe2O4 and spinel iron oxide), and shell thickness were prepared using an efficient solvothermal approach to exploit the magnetic coupling between a hard and a soft ferrimagnetic phase for magnetic heat induction. The magnetic behavior, together with morphology, stoichiometry, cation distribution, and spin canting, were investigated to identify the key parameters affecting the heat release. General trends in the heating abilities, as a function of the core size, the nature and the thickness of the shell, were hypothesized based on this systematic fundamental study and confirmed by experiments conducted on the water-based ferrofluids.

Towards the evaluation of defects in MoS2 using cryogenic photoluminescence spectroscopy.

Characterization of the type and density of defects in two-dimensional (2D) transition metal dichalcogenides (TMDs) is important as the nature of these defects strongly influences the electronic and optical properties of the material, especially its photoluminescence (PL). Defect characterization is not as straightforward as it is for graphene films, where the D and D' Raman scattering modes easily indicate the density and type of defects in the graphene layer. Thus, in addition to the Raman scattering analysis, other spectroscopic techniques are necessary to perform detailed characterization of atomically thin TMD layers. We demonstrate that PL spectroscopy performed at liquid helium temperatures reveals the key fingerprints of defects in TMDs and hence provides valuable information about their origin and concentration. In our study, we address defects in chemical vapor deposition (CVD)-grown MoS2 monolayers. A significant difference is observed between the as-grown monolayers compared with the CVD-grown monolayers transferred onto a Si/SiO2 substrate, which contain extra defects due to the transfer process. We demonstrate that the temperature-dependent Raman and PL micro-spectroscopy techniques enable disentangling the contributions and locations of various defect types in TMD systems.

Thermoreversible magnetic nanochains.

The reversible organization of nanomagnets into highly anisotropic assemblies is of considerable interest for many applications, including theragnostic strategies in vivo. The current preparation strategies lead to structures that are not stable without the permanent presence of an applied magnetic field (MF); otherwise, irreversible assemblies are produced with moderate shape anisotropy at nanoscales. Here, we present a new approach based on the thermoreversible Diels-Alder reaction in the presence of an external MF that enables the assembly of single-domain nanomagnets into narrow chains with lengths of several micrometers. The MF-assisted click chemistry approach included (i) the synthesis of nanoparticles through a modified hydrothermal method, (ii) their functionalization via ligand exchange, (iii) the MF-assisted formation of chains, and (iv) the linkage of the nanomagnets in the presence of the magnetic field. Moreover, the chains can be again disassembled at elevated temperatures through a retro-Diels-Alder reaction. We thus demonstrated for the first time that MF-assisted click chemistry is a convenient method for large-scale preparation of highly anisotropic assemblies of nanosized magnets that can be reversibly decomposed by thermal treatment.

Superlattice in collapsed graphene wrinkles.

Topographic corrugations, such as wrinkles, are known to introduce diverse physical phenomena that can significantly modify the electrical, optical and chemical properties of two-dimensional materials. This range of assets can be expanded even further when the crystal lattices of the walls of the wrinkle are aligned and form a superlattice, thereby creating a high aspect ratio analogue of a twisted bilayer or multilayer - the so-called twisted wrinkle. Here we present an experimental proof that such twisted wrinkles exist in graphene monolayers on the scale of several micrometres. Combining atomic force microscopy and Raman spectral mapping using a wide range of visible excitation energies, we show that the wrinkles are extremely narrow and their Raman spectra exhibit all the characteristic features of twisted bilayer or multilayer graphene. In light of a recent breakthrough - the superconductivity of a magic-angle graphene bilayer, the collapsed wrinkles represent naturally occurring systems with tuneable collective regimes.

Introducing Well-Defined Nanowrinkles in CVD Grown Graphene.

The control of graphene's topography at the nanoscale level opens up the possibility to greatly improve the surface functionalization, change the doping level or create nanoscale reservoirs. However, the ability to control the modification of the topography of graphene on a wafer scale is still rather challenging. Here we present an approach to create well-defined nanowrinkles on a wafer scale using nitrocellulose as the polymer to transfer chemical vapor deposition grown graphene from the copper foil to a substrate. During the transfer process, the complex tertiary nitrocellulose structure is imprinted into the graphene area layer. When the graphene layer is put onto a substrate this will result in a well-defined nanowrinkle pattern, which can be subsequently further processed. Using atomic force and Raman microscopy, we characterized the generated nanowrinkles in graphene.