Understanding Antiferromagnetic Coupling in Lead-Free Halide Double Perovskite Semiconductors.

Solution-processable semiconductors with antiferromagnetic (AFM) order are attractive for future spintronics and information storage technology. Halide perovskites containing magnetic ions have emerged as multifunctional materials, demonstrating a cross-link between structural, optical, electrical, and magnetic properties. However, stable optoelectronic halide perovskites that are antiferromagnetic remain sparse, and the critical design rules to optimize magnetic coupling still must be developed. Here, we combine the complementary magnetometry and electron-spin-resonance experiments, together with first-principles calculations to study the antiferromagnetic coupling in stable Cs2(Ag:Na)FeCl6 bulk semiconductor alloys grown by the hydrothermal method. We show the importance of nonmagnetic monovalence ions at the BI site (Na/Ag) in facilitating the superexchange interaction via orbital hybridization, offering the tunability of the Curie-Weiss parameters between -27 and -210 K, with a potential to promote magnetic frustration via alloying the nonmagnetic BI site (Ag:Na ratio). Combining our experimental evidence with first-principles calculations, we draw a cohesive picture of the material design for B-site-ordered antiferromagnetic halide double perovskites.

Programmable Compartment Networks by Unraveling the Stress-Dependent Deformation of Polymer Vesicles.

Nanocontainers that can sense and respond to environmental stimuli like cells are desirable for next-generation delivery systems. However, it is still a grand challenge for synthetic nanocontainers to mimic or even surpass the shape adaption of cells, which may produce novel compartments for cargo loading. Here, this work reports the engineering of compartment network with a single polymer vesicle by unraveling osmotic stress-dependent deformation. Specifically, by manipulating the way in exerting the stress, sudden increase or gradual increase, polymer vesicles can either undergo deflation into the stomatocyte, a bowl-shaped vesicle enclosing a new compartment, or tubulation into the tubule of varied length. Such stress-dependent deformation inspired us to program the shape transformation of polymer vesicles, including tubulation, deflation, or first tubulation and then deflation. The coupled deformation successfully transforms the polymer vesicle into the stomatocyte with tubular arms and a network of two or three small stomatocytes connected by tubules. To the author's knowledge, these morphologies are still not accessed by synthetic nanocontainers. This work envisions that the network of stomatocytes may enable the loading of different catalysts to construct novel motile systems, and the well-defined morphology of vesicles helps to define the effect of morphology on cellar uptake.

The average magnetic anisotropy of polystyrene in polymersomes self-assembled from poly(ethylene glycol)-b-polystyrene.

Using the diamagnetic anisotropy of polymers for the characterization of polymers and polymer aggregates is a relatively new approach in the field of soft-matter and polymer research. So far, a good and thorough quantitative description of these diamagnetic properties has been lacking. Using a simple equation that links the magnetic properties of an average polymer repeating unit to those of the polymer vesicle of any shape, we measured, using magnetic birefringence, the average diamagnetic anisotropy of a polystyrene (PS) repeating unit, ΔχPS, inside a poly(ethylene glycol)-polystyrene (PEG-PS) polymersome membrane as a function of the PS-length and as a function of the preparation method. All obtained values of ΔχPS have a negative sign which results in polymers tending to align perpendicular to an applied magnetic field. Combined, the same order of magnitude of ΔχPS (10-12 m3 mol-1) for all polymersome shapes proves that the individual polymers are organized similarly regardless of the PS length and polymersome shape. Furthermore, the value found is only a fraction (∼1%) of what it can maximally be due to the random coiling of the polymers. We, therefore, predict that further ordering of the polymers within the membrane could lead to similar responses at much lower magnetic fields, possibly obtainable with permanent magnets, which would be highly advantageous for practical applications.

Impact of Optically Pumped Nonequilibrium Steady States on Luminescence Emission of Atomically Thin Semiconductor Excitons.

The interplay of the nonequivalent corners in the Brillouin zone of transition metal dichalcogenides (TMDCs) has been investigated extensively. While experimental and theoretical works contributed to a detailed understanding of the relaxation of selective optical excitations and the related relaxation rates, only limited microscopic descriptions of stationary experiments are available so far. Here we present microscopic calculations for the nonequilibrium steady state properties of excitons during continuous wave pumping exemplary for monolayer MoSe_{2}. We find sharp features in photoluminescence excitation spectra and degree of polarization which result from phonon assisted excitonic transitions dominating over exciton recombination and intervalley exchange coupling.

Signature of Ultrafast Formation and Annihilation of Polaronic States in a Layered Ferromagnet.

The strong interaction between charge and lattice vibration gives rise to a polaron, which has a profound effect on optical and transport properties of matters. In magnetic materials, polarons are involved in spin dependent transport, which can be potentially tailored for spintronic and opto-spintronic device applications. Here, we identify the signature of ultrafast formation of polaronic states in CrBr3. The polaronic states are long-lived, having a lifetime on the time scale of nanoseconds to microseconds, which coincides with the emission lifetime of ∼4.3 µs. Transition of the polaronic states is strongly screened by the phonon, generating a redshift of the transition energy ∼0.2 eV. Moreover, energy-dependent localization of polaronic states is discovered followed by transport/annihilation properties. These results shed light on the nature of the polarons and their formation and transport dynamics in layered magnetic materials, which paves the way for the rational design of two-dimensional magnetic devices.

Strain-Induced Exciton Hybridization in WS_{2} Monolayers Unveiled by Zeeman-Splitting Measurements.

Mechanical deformations and ensuing strain are routinely exploited to tune the band gap energy and to enhance the functionalities of two-dimensional crystals. In this Letter, we show that strain leads also to a strong modification of the exciton magnetic moment in WS_{2} monolayers. Zeeman-splitting measurements under magnetic fields up to 28.5 T were performed on single, one-layer-thick WS_{2} microbubbles. The strain of the bubbles causes a hybridization of k-space direct and indirect excitons resulting in a sizable decrease in the modulus of the g factor of the ground-state exciton. These findings indicate that strain may have major effects on the way the valley number of excitons can be used to process binary information in two-dimensional crystals.

Fröhlich interaction dominated by a single phonon mode in CsPbBr3.

The excellent optoelectronic performance of lead halide perovskites has generated great interest in their fundamental properties. The polar nature of the perovskite lattice means that electron-lattice coupling is governed by the Fröhlich interaction. Still, considerable ambiguity exists regarding the phonon modes that participate in this crucial mechanism. Here, we use multiphonon Raman scattering and THz time-domain spectroscopy to investigate Fröhlich coupling in CsPbBr3. We identify a longitudinal optical phonon mode that dominates the interaction, and surmise that this mode effectively defines exciton-phonon scattering in CsPbBr3, and possibly similar materials. It is additionally revealed that the observed strength of the Fröhlich interaction is significantly higher than the expected intrinsic value for CsPbBr3, and is likely enhanced by carrier localization in the colloidal perovskite nanocrystals. Our experiments also unearthed a dipole-related dielectric relaxation mechanism which may impact transport properties.

Direct Observation of Magnon-Phonon Strong Coupling in Two-Dimensional Antiferromagnet at High Magnetic Fields.

We report the direct observation of strong coupling between magnons and phonons in a two-dimensional antiferromagnetic semiconductor FePS_{3}, via magneto-Raman spectroscopy at magnetic fields up to 30 Tesla. A Raman-active magnon at 121 cm^{-1} is identified through Zeeman splitting in an applied magnetic field. At a field-driven resonance with a nearby phonon mode, a hybridized magnon-phonon quasiparticle is formed due to strong coupling between the two modes. We develop a microscopic model of the strong coupling in the two-dimensional magnetic lattice, which enables us to elucidate the nature of the emergent quasiparticle. Our polarized Raman results directly show that the magnons transfer their spin angular momentum to the phonons and generate phonon spin through the strong coupling.

Electrical and optical properties of transition metal dichalcogenides on talc dielectrics.

Advanced van der Waals (vdW) heterostructure devices rely on the incorporation of high quality dielectric materials which need to possess a low defect density as well as being atomically smooth and uniform. In this work we explore the use of talc dielectrics as a potentially clean alternative substrate to hexagonal boron nitride (hBN) for few-layer transition metal dichalcogenide (TMDC) transistors and excitonic TMDC monolayers. We find that talc dielectric transistors show small hysteresis which does not depend strongly on sweep rate and show negligible leakage current for our studied dielectric thicknesses. We also show narrow photoluminescence linewidths down to 10 meV for different TMDC monolayers on talc which highlights that talc is a promising material for future van der Waals devices.

Phase-transition-induced jumping, bending, and wriggling of single crystal nanofibers of coronene.

For decades, it has been reported that some organic crystals suddenly crack, break, or jump when they are heated from room temperature. Recently, such crystals have been intensively studied both in fundamental science and for high-speed mechanical device applications. According to these studies, the sudden crystal motions have been attributed to structural phase transitions induced by heating. Stress created by the phase transition is released through the sudden and rapid motion of the crystals. Here we report that single crystal nanofibers of coronene exhibit a new type of ultrafast motion when they are cooled from room temperature and subsequently heated to room temperature. The nanofibers make centimeter-scale jumps accompanied by surprisingly unique behaviors such as sharp bending and wriggling. We found that the motions are caused by a significantly fast structural phase transition between two polymorphs of coronene. A theoretical investigation revealed that the sudden force generated by the phase transition together with the nanoscale dimensions and elastic properties create dynamical instability in the nanofibers that results in the motions. Our finding demonstrates the novel mechanism that leads to ultrafast, large deformation of organic crystals.

Polarized emission of CdSe nanocrystals in magnetic field: the role of phonon-assisted recombination of the dark exciton.

The recombination dynamics and spin polarization of excitons in CdSe nanocrystals synthesized in a glass matrix are investigated using polarized photoluminescence in high magnetic fields up to 30 Tesla. The dynamics are accelerated by increasing temperature and magnetic field, confirming the dark exciton nature of low-temperature photoluminescence (PL). The circularly polarized PL in magnetic fields reveals several unusual appearances: (i) a spectral dependence of the polarization degree, (ii) its low saturation value, and (iii) a stronger intensity of the Zeeman component which is higher in energy. The latter feature is the most surprising being in contradiction with the thermal population of the exciton spin sublevels. The same contradiction was previously observed in the ensemble of wet-chemically synthesized CdSe nanocrystals but was not understood. We present a theory which explains all the observed features and shows that the inverted ordering of the circularly polarized PL maxima from the ensemble of nanocrystals is a result of competition between the zero phonon (ZPL) and one optical phonon-assisted (1PL) emission of the dark excitons. The essential aspects of the theoretical model are different polarization properties of the dark exciton emission via ZPL and 1PL recombination channels and the inhomogeneous broadening of the PL spectrum from the ensemble of nanocrystals exceeding the optical phonon energy.

Hole and Electron Effective Masses in Single InP Nanowires with a Wurtzite-Zincblende Homojunction.

The formation of wurtzite (WZ) phase in III-V nanowires (NWs) such as GaAs and InP is a complication hindering the growth of pure-phase NWs, but it can also be exploited to form NW homostructures consisting of alternate zincblende (ZB) and WZ segments. This leads to different forms of nanostructures, such as crystal-phase superlattices and quantum dots. Here, we investigate the electronic properties of the simplest, yet challenging, of such homostructures: InP NWs with a single homojunction between pure ZB and WZ segments. Polarization-resolved microphotoluminescence (µ-PL) measurements on single NWs provide a tool to gain insights into the interplay between NW geometry and crystal phase. We also exploit this homostructure to simultaneously measure effective masses of charge carriers and excitons in ZB and WZ InP NWs, reliably. Magneto-µ-PL measurements carried out on individual NWs up to 29 T at 77 K allow us to determine the free exciton reduced masses of the ZB and WZ crystal phases, showing the heavier character of the WZ phase, and to deduce the effective mass of electrons in ZB InP NWs (me= 0.080 m0). Finally, we obtain the reduced mass of light-hole excitons in WZ InP by probing the second optically permitted transition Γ7C ↔ Γ7uV with magneto-µ-PL measurements carried out at room temperature. This information is used to extract the experimental light-hole effective mass in WZ InP, which is found to be mlh = 0.26 m0, a value much smaller than the one of the heavy hole mass. Besides being a valuable test for band structure calculations, the knowledge of carrier masses in WZ and ZB InP is important in view of the optimization of the efficiency of solar cells, which is one of the main applications of InP NWs.

Bright Exciton Fine-Structure in Two-Dimensional Lead Halide Perovskites.

The fast-growing field of atomically thin semiconductors urges a new understanding of two-dimensional excitons, which entirely determine their optical responses. Here, taking layered lead halide perovskites as an example of unconventional two-dimensional semiconductors, by means of versatile optical spectroscopy measurements, we resolve fine-structure splitting of bright excitons of up to ∼2 meV, which is among the largest values in two-dimensional semiconducting systems. The large fine-structure splitting is attributed to the strong electron-hole exchange interaction in layered perovskites, which is proven by the optical emission in high magnetic fields of up to 30 T. Furthermore, we determine the g-factors for these bright excitons as ∼+1.8. Our findings suggest layered lead halide perovskites are an ideal platform for studying exciton spin-physics in atomically thin semiconductors that will pave the way toward exciton manipulation for novel device applications.

Fine Structure and Spin Dynamics of Linearly Polarized Indirect Excitons in Two-Dimensional CdSe/CdTe Colloidal Heterostructures.

Heterostructured two-dimensional colloidal nanoplatelets are a class of material that has attracted great interest for optoelectronic applications due to their high photoluminescence yield, atomically tunable thickness, and ultralow lasing thresholds. Of particular interest are laterally heterostructured core-crown nanoplatelets with a type-II band alignment, where the in-plane spatial separation of carriers leads to indirect (or charge transfer) excitons with long lifetimes and bright, highly Stokes shifted emission. Despite this, little is known about the nature of the lowest energy exciton states responsible for emission in these materials. Here, using polarization-controlled, steady-state, and time-resolved photoluminescence measurements, at temperatures down to 1.6 K and magnetic fields up to 30 T, we study the exciton fine structure and spin dynamics of archetypal type-II CdSe/CdTe core-crown nanoplatelets. Complemented by theoretical modeling and zero-field quantum beat measurements, we find the bright-exciton fine structure consists of two linearly polarized states with a fine structure splitting ∼50 µeV and an indirect exciton Landé g-factor of 0.7. In addition, we show the exciton spin lifetime to be in the microsecond range with an unusual B-3 magnetic field dependence. The discovery of linearly polarized exciton states and emission highlights the potential for use of such materials in display and imaging applications without polarization filters. Furthermore, the small exciton fine structure splitting and a long spin lifetime are fundamental advantages when envisaging CdSe/CdTe nanoplatelets as elementary bricks for the next generation of quantum devices, particularly given their ease of fabrication.

Hyperfine Interactions and Slow Spin Dynamics in Quasi-isotropic InP-based Core/Shell Colloidal Nanocrystals.

Colloidal InP core nanocrystals are taking over CdSe-based nanocrystals, notably in optoelectronic applications. Despite their use in commercial devices, such as display screens, the optical properties of InP nanocrystals and especially their relation to the exciton fine structures remain poorly understood. In this work, we show that the ensemble magneto-optical properties of InP-based core/shell nanocrystals investigated in strong magnetic fields up to 30 T are strikingly different from other colloidal nanostructures. Notably, the mixing of the lowest spin-forbidden dark exciton state with the nearest spin-allowed bright state does not occur up to the highest magnetic fields applied. This lack of mixing in an ensemble of nanocrystals suggests an anisotropy tolerance of InP nanocrystals. This striking property allowed us to unveil the slow spin dynamics between Zeeman sublevels (up to 400 ns at 15 T). Furthermore, we show that the unexpected magnetic-field-induced lengthening of the dark exciton lifetime results from the hyperfine interaction between the spin of the electron in the dark exciton with the nuclear magnetic moments. Our results demonstrate the richness of the spin physics in InP quantum dots and stress the large potential of InP nanostructures for spin-based applications.

Fine Structure of Nearly Isotropic Bright Excitons in InP/ZnSe Colloidal Quantum Dots.

The fine structure of exciton states in colloidal quantum dots (QDs) results from the compound effect of anisotropy and electron-hole exchange. By means of single-dot photoluminescence spectroscopy, we show that the emission of photoexcited InP/ZnSe QDs originates from radiative recombination of such fine structure exciton states. Depending on the excitation power, we identify a bright exciton doublet, a trion singlet, and a biexciton doublet line that all show pronounced polarization. Fluorescence line narrowing spectra of an ensemble of InP/ZnSe QDs in magnetic fields demonstrate that the bright exciton effectively consists of three states. The Zeeman splitting of these states is well described by an isotropic exciton model, where the fine structure is dominated by electron-hole exchange and shape anisotropy leads to only a minor splitting of the F = 1 triplet. We argue that excitons in InP-based QDs are nearly isotropic because the particular ratio of light and heavy hole masses in InP makes the exciton fine structure insensitive to shape anisotropy.

Exciton Fine Structure and Lattice Dynamics in InP/ZnSe Core/Shell Quantum Dots.

Nanocrystalline InP quantum dots (QDs) hold promise for heavy-metal-free optoelectronic applications due to their bright and size-tunable emission in the visible range. Photochemical stability and high photoluminescence (PL) quantum yield are obtained by a diversity of epitaxial shells around the InP core. To understand and optimize the emission line shapes, the exciton fine structure of InP core/shell QD systems needs be investigated. Here, we study the exciton fine structure of InP/ZnSe core/shell QDs with core diameters ranging from 2.9 to 3.6 nm (PL peak from 2.3 to 1.95 eV at 4 K). PL decay measurements as a function of temperature in the 10 mK to 300 K range show that the lowest exciton fine structure state is a dark state, from which radiative recombination is assisted by coupling to confined acoustic phonons with energies ranging from 4 to 7 meV, depending on the core diameter. Circularly polarized fluorescence line-narrowing (FLN) spectroscopy at 4 K under high magnetic fields (up to 30 T) demonstrates that radiative recombination from the dark F = ±2 state involves acoustic and optical phonons, from both the InP core and the ZnSe shell. Our data indicate that the highest intensity FLN peak is an acoustic phonon replica rather than a zero-phonon line, implying that the energy separation observed between the F = ±1 state and the highest intensity peak in the FLN spectra (6 to 16 meV, depending on the InP core size) is larger than the splitting between the dark and bright fine structure exciton states.

Zeeman Splitting and Inverted Polarization of Biexciton Emission in Monolayer WS_{2}.

Atomically thin semiconductors provide an ideal testbed to investigate the physics of Coulomb-bound many-body states. We shed light on the intricate structure of such complexes by studying the magnetic-field-induced splitting of biexcitons in monolayer WS_{2} using polarization-resolved photoluminescence spectroscopy in out-of-plane magnetic fields up to 30 T. The observed g factor of the biexciton amounts to about -3.9, closely matching the g factor of the neutral exciton. The biexciton emission shows an inverted circular field-induced polarization upon linearly polarized excitation; i.e., it exhibits preferential emission from the high-energy peak in a magnetic field. This phenomenon is explained by taking into account the hybrid configuration of the biexciton constituents in momentum space and their respective energetic behavior in magnetic fields. Our findings reveal the critical role of dark excitons in the composition of this many-body state.

Intervalley Scattering of Interlayer Excitons in a MoS2/MoSe2/MoS2 Heterostructure in High Magnetic Field.

Degenerate extrema in the energy dispersion of charge carriers in solids, also referred to as valleys, can be regarded as a binary quantum degree of freedom, which can potentially be used to implement valleytronic concepts in van der Waals heterostructures based on transition metal dichalcogenides. Using magneto-photoluminescence spectroscopy, we achieve a deeper insight into the valley polarization and depolarization mechanisms of interlayer excitons formed across a MoS2/MoSe2/MoS2 heterostructure. We account for the nontrivial behavior of the valley polarization as a function of the magnetic field by considering the interplay between exchange interaction and phonon-mediated intervalley scattering in a system consisting of Zeeman-split energy levels. Our results represent a crucial step toward the understanding of the properties of interlayer excitons with strong implications for the implementation of atomically thin valleytronic devices.