Search

Magnetic 2D materials enable interesting tuning options of magnetism. As an example, the van der Waals material FePS 3 , a zig-zag-type intralayer antiferromagnet, exhibits very strong magnetoelastic coupling due to the different bond lengths along different ferromagnetic and antiferromagnetic coupling directions enabling elastic tuning of magnetic properties. The likely cause of the length change is the intricate competition between direct exchange of the Fe atoms and superexchange via the S and P atoms. To elucidate this interplay, we study the band structure of exfoliated FePS 3 by μm scale ARPES (angular resolved photoelectron spectroscopy), both, above and below the Néel temperature T N . We found three characteristic changes across T N . They involve S 3 p -type bands, Fe 3 d -type bands and P 3 p -type bands, respectively, as attributed by comparison with density functional theory calculations (DFT + U). This highlights the involvement of all the atoms in the magnetic phase transition providing independent evidence for the intricate exchange paths.

Exfoliated magnetic 2D materials enable versatile tuning of magnetization, e.g., by gating or providing proximity-induced exchange interaction. However, their electronic band structure after exfoliation has not been probed, presumably due to their photochemical sensitivity. Here, we provide micrometer-scale angle-resolved photoelectron spectroscopy of the exfoliated intralayer antiferromagnet MnPS 3 above and below the Néel temperature down to one monolayer. Favorable comparison with density functional theory calculations enables identifying the orbital character of the observed bands. Consistently, we find pronounced changes across the Néel temperature for bands consisting of Mn 3d and 3p levels of adjacent S atoms. The deduced orbital mixture indicates that the superexchange is relevant for the magnetic interaction. There are only minor changes between monolayer and thicker films, demonstrating the predominant 2D character of MnPS 3 . The novel access is transferable to other MPX 3 materials (M: transition metal, P: phosphorus, X: chalcogenide), providing several antiferromagnetic arrangements.

A Fano resonance, as often observed in scattering, absorption, or transmission experiments, arises from quantum interference between a discrete optical transition and a continuous background. Here, we present a temperature-dependent study on Fano resonances observed in photoluminescence from flakes of the layered semiconductor antiferromagnet chromium thiophosphate (CrPS 4 ). Two Fano resonances with a distinctly different temperature dependence were identified. The continuous background that is responsible for the Fano resonances is attributed to the d-d transition of the optically active Cr 3+ center, predominantly the spin-forbidden 2 E g → 4 A 2g transition with contributions of the broad-band 4 T 2g → 4 A 2g transition. The discrete states that interfere with this continuous background are suggested to arise from localized atomic phosphorus. A model idea for explaining the individual temperature dependence of the Fano resonances is presented.

Branched nanostructures have attracted considerable interest due to their large surface-to-volume ratio with benefits in photocatalysis and photovoltaic applications. Here we discuss the tailoring of branched structures with a shape of a star based on PbS semiconductor. It exposes the reaction mechanism and the controlling factors that template their morphology. For this purpose, we varied the primary lead precursors, types of surfactant, lead-to-surfactant molar ratio, temperature and duration of the reaction. Furthermore, intermediate products in a growth reaction were thoroughly examined using X-ray diffraction, transmission electron microscopy, Raman scattering, optical absorbance and Fourier transform infrared spectroscopy. The results designated a primary formation of truncated octahedral seeds with terminating {100} and {111} facets, followed by the selective fast growth of pods along the 〈100〉 directions toward the development of a star-like shape. The examined intermediates possess a cubic rock salt structure. The observations indicated that small surfactant molecules ( e.g. acetate) evolve the branching process, while long-chain surfactants ( e.g. oleate) stabilize the long pods as well as mitigate the aggregation process. This study conveys fundamental knowledge for the design of other branched structures, that are attractive for practical use in catalysis, electrochemistry and light-harvesting., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Controlling the spin degrees of freedom of photogenerated species in semiconductor nanostructures via magnetic doping is an emerging scientific field that may play an important role in the development of new spin-based technologies. The current work explores spin properties in colloidal CdSe/CdS:Mn seeded-nanorod structures doped with a dilute concentration of Mn 2+ ions across the rods. The spin properties were determined using continuous-wave optically detected magnetic resonance (ODMR) spectroscopy recorded under variable microwave chopping frequencies. These experiments enabled the deconvolution of a few different radiative recombination processes: band-to-band, trap-to-band, and trap-to-trap emission. The results uncovered the major role of carrier trapping on the spin properties of elongated structures. The magnetic parameters, determined through spin-Hamiltonian simulation of the steady-state ODMR spectra, reflect anisotropy associated with carrier trapping at the seed/rod interface. These observations unveiled changes in the carriers' g -factors and spin-exchange coupling constants as well as extension of radiative and spin-lattice relaxation times due to magnetic coupling between interface carriers and neighboring Mn 2+ ions. Overall, this work highlights that the spin degrees of freedom in seeded nanorods are governed by interfacial trapping and can be further manipulated by magnetic doping. These results provide insights into anisotropic nanostructure spin properties relevant to future spin-based technologies.

Layered semiconductors have attracted significant attention due to their diverse physical properties controlled by composition and the number of stacked layers. Herein, large crystals of the ternary layered semiconductor chromium thiophosphate (CrPS 4 ) are prepared by a vapor transport synthesis. Optical properties are determined using photoconduction, absorption, photoreflectance, and photoacoustic spectroscopy exposing the semiconducting properties of the material. A simple, one-step protocol for mechanical exfoliation onto a transmission electron microscope grid is developed, and multiple layers are characterized by advanced electron microscopy methods, including atomic resolution elemental mapping confirming the structure by directly showing the positions of the columns of different elements' atoms. CrPS 4 is also liquid exfoliated, and in combination with colloidal graphene, an ink-jet-printed photodetector is created. This all-printed graphene/CrPS 4 /graphene heterostructure detector demonstrates a specific detectivity of 8.3 × 10 8 (D*). This study shows a potential application of both bulk crystal and individual flakes of CrPS 4 as active components in light detection, when introduced as ink-printable moieties with a large benefit for manufacturing., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Semiconductor colloidal quantum dots (CQDs) have attracted vast scientific and technological interest throughout the past three decades, due to the unique tuneability of their optoelectronic properties by variation of size and composition. However, the nanoscale size brings about a large surface-to-bulk volume ratio, where exterior surfaces have a pronounced influence on the chemical stability and on the physical properties of the semiconductor. Therefore, numerous approaches have been developed to gain efficient surface passivation, including a coverage by organic or inorganic molecular surfactants as well as the formation of core/shell heterostructures (a semiconductor core epitaxially covered by another semiconductor shell). This review focuses on special designs of core/shell heterostructures from the IV-VI and II-VI semiconductor compounds, and on synthetic approaches and characterization of the optical properties. Experimental observations revealed the formation of core/shell structures with type-I or quasi-type-II band alignment between the core and shell constituents. Theoretical calculations of the electronic band structures, which were also confirmed by experimental work, exposed surplus electronic tuning (beyond the radial diameter) with adaptation of the composition and control of the interface properties. The studies also considered strain effects that are created between two different semiconductors. It was disclosed experimentally and theoretically that the strain can be released via the formation of alloys at the core-shell interface. Overall, the core/shell and core/alloyed-shell heterostructures showed enhancement in luminescence quantum efficiency with respect to that of pure cores, extended lifetime, uniformity in size and in many cases good chemical sustainability under ambient conditions.