Electronic Band Structure Changes across the Antiferromagnetic Phase Transition of Exfoliated MnPS3 Flakes Probed by µ-ARPES.

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 MnPS3 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 MnPS3. The novel access is transferable to other MPX3 materials (M: transition metal, P: phosphorus, X: chalcogenide), providing several antiferromagnetic arrangements.

Optically detected magnetic resonance spectroscopic analyses on the role of magnetic ions in colloidal nanocrystals.

Incorporating magnetic ions into semiconductor nanocrystals has emerged as a prominent research field for manipulating spin-related properties. The magnetic ions within the host semiconductor experience spin-exchange interactions with photogenerated carriers and are often involved in the recombination routes, stimulating special magneto-optical effects. The current account presents a comparative study, emphasizing the impact of engineering nanostructures and selecting magnetic ions in shaping carrier-magnetic ion interactions. Various host materials, including the II-VI group, halide perovskites, and I-III-VI2 in diverse structural configurations such as core/shell quantum dots, seeded nanorods, and nanoplatelets, incorporated with magnetic ions such as Mn2+, Ni2+, and Cu1+/2+ are highlighted. These materials have recently been investigated by us using state-of-the-art steady-state and transient optically detected magnetic resonance (ODMR) spectroscopy to explore individual spin-dynamics between the photogenerated carriers and magnetic ions and their dependence on morphology, location, crystal composition, and type of the magnetic ion. The information extracted from the analyses of the ODMR spectra in those studies exposes fundamental physical parameters, such as g-factors, exchange coupling constants, and hyperfine interactions, together providing insights into the nature of the carrier (electron, hole, dopant), its local surroundings (isotropic/anisotropic), and spin dynamics. The findings illuminate the importance of ODMR spectroscopy in advancing our understanding of the role of magnetic ions in semiconductor nanocrystals and offer valuable knowledge for designing magnetic materials intended for various spin-related technologies.

Temperature dependence of Fano resonances in CrPS4.

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 (CrPS4). 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 Cr3+ center, predominantly the spin-forbidden 2Eg → 4A2g transition with contributions of the broad-band 4T2g → 4A2g 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.

Exfoliated CrPS4 with Promising Photoconductivity.

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 (CrPS4 ) 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. CrPS4 is also liquid exfoliated, and in combination with colloidal graphene, an ink-jet-printed photodetector is created. This all-printed graphene/CrPS4 /graphene heterostructure detector demonstrates a specific detectivity of 8.3 × 108 (D*). This study shows a potential application of both bulk crystal and individual flakes of CrPS4 as active components in light detection, when introduced as ink-printable moieties with a large benefit for manufacturing.

Rashba Effect in a Single Colloidal CsPbBr3 Perovskite Nanocrystal Detected by Magneto-Optical Measurements.

This study depicts the influence of the Rashba effect on the band-edge exciton processes in all-inorganic CsPbBr3 perovskite single colloidal nanocrystal (NC). The study is based on magneto-optical measurements carried out at cryogenic temperatures under various magnetic field strengths in which discrete excitonic transitions were detected by linearly and circularly polarized measurements. Interestingly, the experiments show a nonlinear energy splitting between polarized transitions versus magnetic field strength, indicating a crossover between a Rashba effect (at the lowest fields) to a Zeeman effect at fields above 4 T. We postulate that the Rashba effect emanates from a lattice distortion induced by the Cs+ motion degree of freedom or due to a surface effect in nanoscale NCs. The unusual magneto-optical properties shown here underscore the importance of the Rashba effect in the implementation of such perovskite materials in various optical and spin-based devices.

Biexciton Auger Recombination in CdSe/CdS Core/Shell Semiconductor Nanocrystals.

A theoretical study of the positive and negative trion channels in the nonradiative Auger recombination of band-edge biexcitons (BXs) in CdSe/CdS core/shell nanocrystals (NCs) is presented. The theory takes into account the BX fine-structure produced by NC asymmetry and hole-hole exchange interaction. The calculations show that growth of CdS shell upon CdSe core suppresses the rate of the Auger recombination via negative trion channel, while the more efficient Auger recombination via positive trion channel shows much weaker dependence on the shell thickness. The demonstrated oscillatory dependence of the BX Auger rate on the core and shell sizes is explained qualitatively in terms of overlap of the ground and excited carrier wave functions. The calculations show that raise of temperature accelerates the Auger recombination in CdSe/CdS NCs due to reduction of the bulk energy gaps of CdSe and CdS.

Nonradiative Auger recombination in semiconductor nanocrystals.

We calculate the rate of nonradiative Auger recombination in negatively charged CdSe nanocrystals (NCs). The rate is nonmonotonic, strongly oscillating with NC size, and sensitive to the NC surface. The oscillations result in nonexponential decay of carriers in NC ensembles. Using a standard single-exponential approximation of the decay dynamics, we determine the apparent size dependence of the Auger rate in an ensemble and derive CdSe surface parameters consistent with the experimental dependence on size.

Controlling the size of hot injection made nanocrystals by manipulating the diffusion coefficient of the solute.

We investigate the relation between the chain length of ligands used and the size of the nanocrystals formed in the hot injection synthesis. With two different CdSe nanocrystal syntheses, we consistently find that longer chain carboxylic acids result in smaller nanocrystals with improved size dispersions. By combining a more in-depth experimental investigation with kinetic reaction simulations, we come to the conclusion that this size tuning is due to a change in the diffusion coefficient and the solubility of the solute. The relation between size tuning by the ligand chain length and the coordination of the solute by the ligands is further explored by expanding the study to amines and phosphine oxides. In line with the weak coordination of CdSe nanocrystals by amines, no influence of the chain length on the nanocrystals is found, whereas the size tuning brought about by phosphine oxides can be attributed to a solubility change. We conclude that the ligand chain length provides a practical handle to optimize the outcome of a hot injection synthesis in terms of size and size dispersion and can be used to probe the interaction between ligands and the actual solute.

A spray-based technique for the production of MnS thin films.

A spray-based technique, originally developed for the production of semiconductor nanocrystals, is utilized for the preparation of high-quality nanocrystalline thin films, as demonstrated with manganese sulfide. The films are formed by the use of pneumatic-assisted thermospray or pneumatic nebulizers. Our simple, low-cost, and low-temperature process results in a dense and phase-pure grain structure. The concepts and benefits of this technique are described and discussed. The film characteristics show dependence on the experimental parameters, in particular the rate of solvent vaporization. Three alternative film formation mechanisms are suggested for cases with varied experimental conditions.

Charge transport-induced recoil and dissociation in double quantum dots.

Colloidal quantum dots (CQDs) are free-standing nanostructures with chemically tunable electronic properties. This combination of properties offers intriguing new possibilities for nanoelectromechanical devices that were not explored yet. In this work, we consider a new scanning tunneling microscopy setup for measuring ligand-mediated effective interdot forces and for inducing motion of individual CQDs within an array. Theoretical analysis of a double quantum dot structure within this setup reveals for the first time voltage-induced interdot recoil and dissociation with pronounced changes in the current. Considering realistic microscopic parameters, our approach enables correlating the onset of mechanical motion under bias voltage with the effective ligand-mediated binding forces.

Full spectral and angular characterization of highly directional emission from nanocrystal quantum dots positioned on circular plasmonic lenses.

We design a circular plasmonic lens for collimation of light emission from nanocrystal quantum dots at room temperature in the near IR spectral range. We implement a two-dimensional k-space imaging technique to obtain the full spectral-angular response of the surface plasmon resonance modes of the bare plasmonic lens. This method is also used to map the full spectral-angular emission from nanocrystal quantum dots positioned at the center of the circular plasmonic lens. A narrow directional emitting beam with a divergence angle of only ∼4.5° full width at half-maximum is achieved with a spectrally broad bandwidth of 30 nm. The spectrally resolved k-space imaging method allows us to get a direct comparison between the spectral-angular response of the resonant surface plasmon modes of the lens and the emission pattern of the quantum dots. This comparison gives a clear and detailed picture of the direct role of these resonant surface waves in directing the emission. The directional emission effect agrees well with calculations based on the coupled mode method. These results are a step toward fabricating an efficient room-temperature single photon source based on nanocrystal quantum dots.

Non-Poissonian formation of multiple excitons in photoexcited CdTe colloidal quantum qots by femtosecond nonresonant two-photon absorption.

Using direct multiexcitonic spectroscopy, we experimentally observe for the first time the non-Poissonian formation of multiple excitons by femtosecond nonresonant two-photon absorption process in semiconductor colloidal quantum dots (QDs). Each of the multiple excitons is individually generated via the absorption of a pair of photons during the femtosecond pulse irradiation. The non-Poissonian distribution of the generated excitons is reflected as a non-quadratic dependence on the pulse intensity of the average number of excitons per QD. This is the main observation of the present work. It is explained by a multiexcitonic formation model that is based on the phenomenon of intrapulse state filling of the few quantum electronic states accessed by the two-photon transitions. The experiments are conducted with 3.9-nm CdTe QDs in room-temperature hexane solution using the femtosecond pump-probe transient absorption technique, where an intense pump pulse generates the excitons and a weak probe pulse measures their number via intraband one-photon absorption.

Colloidal Control of Branching in Metal Chalcogenide Semiconductor Nanostructures.

Colloidal syntheses of metal chalcogenides yield nanostructures of various 1D, 2D, and 3D nanocrystals (NCs), including branched nanostructures (BNSs) of nanoflowers, tetrapods, octopods, nanourchins, and more. Efforts are continuously being made to understand the branching mechanism in colloidally prepared metal chalcogenides for tailor-making them into various morphologies for dedicated applications in solar cells, light-emitting diodes, stress sensor devices, and near-infrared photodetectors. The vital role of precursors and ligands has widely been recognized in directing nanocrystal morphology during the colloidal synthesis of metal chalcogenide nanostructures. Moreover, a few basic branching mechanisms in nanocrystals have also been derived from decades-long observations of branching in NCs. This Perspective (a) accounts for the mediation of branching in In2S3, PbS, MoSe2, WSe2, and WS2; (b) analyzes the underlying mechanisms; and (c) gives a future perspective toward better controlling the BNSs' morphologies and their impact on applications.

Uncovering Multiple Intrinsic Chiral Phases in (PEA)2PbI4 Halide Perovskites.

Two-dimensional (2D) halide perovskites offer a unique platform for investigating the ground state of materials possessing significant anharmonicity. In contrast to three-dimensional perovskites, their 2D counterparts offer substantially fewer degrees of freedom, resulting in multiple well-defined crystal structures. In this work, we thoroughly investigate the anharmonic ground state of the benchmark (PEA)2PbI4 compound, using complementary information from low-temperature X-ray diffraction (XRD) and photoluminescence spectroscopy, supported by density functional theory calculations. We extrapolate four crystallographic configurations from low-temperature XRD. These configurations imply that the ground state has an intrinsic disorder stemming from two coexisting chiral sublattices, each with a bioriented organic spacer molecule. We further show evidence that these chiral structures form unevenly populated ground states, portraying uneven anharmonicity, where the state population may be tuned by surface effects. Our results uncover a disordered ground state that may induce intrinsic grain boundaries, which cannot be ignored in practical applications.

Ultrafast Coherent Delocalization Revealed in Multilayer QDs under a Chiral Potential.

In recent years, it was found that current passing through chiral molecules exhibits spin preference, an effect known as Chiral Induced Spin Selectivity (CISS). The effect also enables the reduction of scattering and therefore enhances delocalization. As a result, the delocalization of an exciton generated in the dots is not symmetric and relates to the electronic and hole excited spins. In this work utilizing fast spectroscopy on hybrid multilayered QDs with a chiral polypeptide linker system, we probed the interdot chiral coupling on a short time scale. Surprisingly, we found strong coherent coupling and delocalization despite having long 4-nm chiral linkers. We ascribe the results to asymmetric delocalization that is controlled by the electron spin. The effect is not measured when using shorter nonchiral linkers. As the system mimics light-harvesting antennas, the results may shed light on a mechanism of fast and efficient energy transfer in these systems.

Fluorescence of colloidal PbSe/PbS QDs in NIR luminescent solar concentrators.

For applications in luminescent solar concentrators harvesting subgap photons, either via direct irradiation of solar cells with optimized band gap or via sensitization of an up-conversion process, exact knowledge and tunability of both the spectral shape and the intensity of the emission are of paramount importance. In this work, we investigate theoretically the photoluminescence spectra of colloidal core-shell PbSe/PbS QDs with type II alignments in the valence band. The method builds on a steady-state formulation of the non-equilibrium Greens function theory for a microscopic system of coupled electrons, photons and phonons interfaced with electronic structure calculations based on a k·p model for PbSe/PbS core-shell QDs. The resulting output spectral density of photons in a realistic QD ensemble is obtained via the renormalization of the incident spectrum according to the polarization of the system.

Anomalous independence of multiple exciton generation on different group IV-VI quantum dot architectures.

Multiple exciton generation (MEG) in PbSe quantum dots (QDs), PbSe(x)S(1-x) alloy QDs, PbSe/PbS core/shell QDs, and PbSe/PbSe(y)S(1-y) core/alloy-shell QDs was studied with time-resolved optical pump and probe spectroscopy. The optical absorption exhibits a red-shift upon the introduction of a shell around a PbSe core, which increases with the thickness of the shell. According to electronic structure calculations this can be attributed to charge delocalization into the shell. Remarkably, the measured quantum yield of MEG, the hot exciton cooling rate, and the Auger recombination rate of biexcitons are similar for pure PbSe QDs and core/shell QDs with the same core size and varying shell thickness. The higher density of states in the alloy and core/shell QDs provide a faster exciton cooling channel that likely competes with the fast MEG process due to a higher biexciton density of states. Calculations reveal only a minor asymmetric delocalization of holes and electrons over the entire core/shell volume, which may partially explain why the Auger recombination rate does not depend on the presence of a shell.

Optically Detected Magnetic Resonance Spectroscopy of Cu-Doped CdSe/CdS and CuInS2 Colloidal Quantum Dots.

Copper-doped II-VI and copper-based I-III-VI2 colloidal quantum dots (CQDs) have been at the forefront of interest in nanocrystals over the past decade, attributable to their optically activated copper states. However, the related recombination mechanisms are still unclear. The current work elaborates on recombination processes in such materials by following the spin properties of copper-doped CdSe/CdS (Cu@CdSe/CdS) and of CuInS2 and CuInS2/(CdS, ZnS) core/shell CQDs using continuous-wave and time-resolved optically detected magnetic resonance (ODMR) spectroscopy. The Cu@CdSe/CdS ODMR showed two distinct resonances with different g factors and spin relaxation times. The best fit by a spin Hamiltonian simulation suggests that emission comes from recombination of a delocalized electron at the conduction band edge with a hole trapped in a Cu2+ site with a weak exchange coupling between the two spins. The ODMR spectra of CuInS2 CQDs (with and without shells) differ significantly from those of the copper-doped II-VI CQDs. They are comprised of a primary resonance accompanied by another resonance at half-field, with a strong correlation between the two, indicating the involvement of a triplet exciton and hence stronger electron-hole exchange coupling than in the doped core/shell CQDs. The spin Hamiltonian simulation shows that the hole is again associated with a photogenerated Cu2+ site. The electron resides near this Cu2+ site, and its ODMR spectrum shows contributions from superhyperfine coupling to neighboring indium atoms. These observations are consistent with the occurrence of a self-trapped exciton associated with the copper site. The results presented here support models under debate for over a decade and help define the magneto-optical properties of these important materials.

Star-shaped colloidal PbS nanocrystals: structural evolution and growth mechanism.

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.

Testing the fate of nascent holes in CdSe nanocrystals with sub-10 fs pump-probe spectroscopy.

Numerous studies have reported that transient absorption spectra in core CdSe nanocrystals do not register state filling in 1Sh, an absence which has profound consequences in light-emitting applications. It has been assigned alternatively to rapid hole trapping, or to distribution over a dense degenerate valence band manifold which includes dark states. Here we attempt to observe early contributions of nascent holes to the bleaching of the band edge exciton transition by conducting 1Se1Sh pump-1Se1Sh probe spectroscopy with <10 fs laser pulses on organic ligand passivated CdSe crystals. The results show no rapidly hole-state filling effects in transient absorption measurements even at the earliest delay, despite the use of pulses which are capable of resolving all dissipation mechanisms reflected in the homogeneous 1Se1Sh bandwidth. This proves that neither hole trapping nor rapid redistribution of the nascent hole over energetically available valence band states can explain the absence of hole contributions to band edge bleaching, calling for a mechanistic review of this phenomenon.