Lattice Symmetry-Guided Charge Transport in 2D Supramolecular Polymers Promotes Triplet Formation.

Singlet-to-triplet intersystem crossing (ISC) in organic molecules is intimately connected with their geometries: by modifying the molecular shape, symmetry selection rules pertaining to spin-orbit coupling can be partially relieved, leading to extra matrix elements for increased ISC. As an analog to this molecular design concept, the study finds that the lattice symmetry of supramolecular polymers also defines their triplet formation efficiencies. A supramolecular polymer self-assembled from weakly interacting molecules is considered. Its 2D oblique unit cell effectively renders it as a coplanar array of 1D molecular columns weakly bound to each other. Using momentum-resolved photoluminescence imaging in combination with Monte Carlo simulations, the study found that photogenerated charge carriers in the supramolecular polymer predominantly recombine as spin-uncorrelated carrier pairs through inter-column charge transfer states. This lattice-defined recombination pathway leads to a substantial triplet formation efficiency (≈60%) in the supramolecular polymer. These findings suggest that lattice symmetry of micro-/macroscopic structures relying on intermolecular interactions can be strategized for controlled triplet formation.

Raman Shifts in Two-Dimensional van der Waals Magnets Reveal Magnetic Texture Evolution.

Two-dimensional (2D) van der Waals magnets comprise rich physics that can be exploited for spintronic applications. We investigate the interplay between spin-phonon coupling and spin textures in a 2D van der Waals magnet by combining magneto-Raman spectroscopy with cryogenic Lorentz transmission electron microscopy. We find that when stable skyrmion bubbles are formed in the 2D magnet, a field-dependent Raman shift can be observed, and this shift is absent for the 2D magnet prepared in its ferromagnetic state. Correlating these observations with numerical simulations that take into account field-dependent magnetic textures and spin--phonon coupling in the 2D magnet, we associate the Raman shift to field-induced modulations of the skyrmion bubbles and derive the existence of inhomogeneity in the skyrmion textures over the film thickness.

Photoluminescence, Reflection Contrast, Raman, and Second Harmonic Generation Spectroscopies Spatially Resolve Strain, Alloying, Defects, and Electronic Characteristics of Lateral MX2 Heterostructures.

Lateral heterostructures of two-dimensional (2D) transition metal dichalcogenides offer promise as platforms for a wide variety of applications from exotic physics to environmental control. Further development and study of these heterostructures require characterization methods that assess the quality of the heterostructures. Here, we extend current characterization strategies to create photoluminescence (PL), Raman, reflection contrast, and second harmonic generation (SHG) maps of individual monolayer core-shell WS2-MoS2 lateral heterostructures that were synthesized via water vapor assisted chemical vapor transport. Together, these methods provide the correlations required to resolve the effects of excitons, trions, lattice defects, strain, and alloying. The comparisons show substantial differences, especially in the regions near and at the narrow heterointerface. Comparisons between the different spectral maps show the importance of metal alloying for understanding the electronic and spatial structures of heterostructures. The results are compared to previous work on similar lateral heterostructures created by different methods.

Encapsulating Semiconductor Quantum Dots in Supramolecular Cages Enables Ultrafast Guest-Host Electron and Vibrational Energy Transfer.

In the field of supramolecular chemistry, host-guest systems have been extensively explored to encapsulate a wide range of substrates, owing to emerging functionalities in nanoconfined space that cannot be achieved in dilute solutions. However, host-guest chemistry is still limited to encapsulation of small guests. Herein, we construct a water-soluble metallo-supramolecular hexagonal prism with a large hydrophobic cavity by anchoring multiple polyethylene glycol chains onto the building blocks. Then, assembled prisms are able to encapsulate quantum dots (QDs) with diameters of less than 5.0 nm. Furthermore, we find that the supramolecular cage around each QD strongly modifies the photophysics of the QD by universally increasing the rates of QD relaxation processes via ultrafast electron and vibrational energy transfer. Taken together, these efforts expand the scope of substrates in host-guest systems and provide a new approach to tune the optical properties of QDs.

Room Temperature Lasing from Semiconducting Single-Walled Carbon Nanotubes.

Miniaturized near-infrared semiconductor lasers that are able to generate coherent light with low energy consumption have widespread applications in fields such as optical interconnects, neuromorphic computing, and deep-tissue optogenetics. With optical transitions at near-infrared wavelengths, diameter-tunable electronic structures, and superlative optoelectronic properties, semiconducting single-walled carbon nanotubes (SWCNTs) are promising candidates for nanolaser applications. However, despite significant efforts in this direction and recent progress toward enhancing spontaneous emission from SWCNTs through Purcell effects, SWCNT-based excitonic lasers have not yet been demonstrated. Leveraging an optimized cavity-emitter integration scheme enabled by a self-assembly process, here we couple SWCNT emission to the whispering gallery modes supported by polymer microspheres, resulting in room temperature excitonic lasing with an average lasing threshold of 4.5 kW/cm2. The high photostability of SWCNTs allows stable lasing for prolonged duration with minimal degradation. This experimental realization of excitonic lasing from SWCNTs, combined with their versatile electronic and optical properties that can be further controlled by chemical modification, offers far-reaching opportunities for tunable near-infrared nanolasers that are applicable for optical signal processing, in vivo biosensing, and optoelectronic devices.

Brightening of Dark States in CsPbBr3 Quantum Dots Caused by Light-Induced Magnetism.

Lead halide perovskite quantum dots (QDs) have shown great potential for optoelectronic and quantum photonic applications. Although controversy remains about the electronic fine structures of bulk perovskites due to the strong spin-orbit coupling affecting the conduction bands, compelling evidence indicates that the ground states of perovskite QDs remain dark, limiting their applications in optoelectronic devices. Here, it is demonstrated that photoexcitation can induce large intrinsic magnetic fields in Mn-doped CsPbBr3 perovskite QDs. Equivalent to applying an external magnetic field, the light-induced field causes giant Zeeman splitting to the bright triplet states and brightens the dark singlet ground state, thus effectively rendering a partially bright ground state in the doped QDs. These findings here may contribute to the understanding of the electronic fine structures in perovskite QDs and demonstrate a potential approach for creating semiconductor nanostructures that can serve as bright light sources.

Deterministic fabrication of arbitrary vertical heterostructures of two-dimensional Ruddlesden-Popper halide perovskites.

Ruddlesden-Popper lead halide perovskites have emerged as a new class of two-dimensional semiconductors with tunable optoelectronic properties, potentially offering unlimited heterostructure configurations for exploration. However, the practical realization of such heterostructures is challenging because of the difficulty in achieving controllable direct synthesis or van der Waals integration of halide perovskites due to their mobile and fragile crystal lattices. Here we report direct growth of large-area nanosheets of diverse phase-pure Ruddlesden-Popper perovskites with thicknesses down to one monolayer at the solution-air interface and a reliable approach for gently transferring and stacking these nanosheets. These advances enable the deterministic fabrication of arbitrary vertical heterostructures and multi-heterostructures of Ruddlesden-Popper perovskites with greater structural degrees of freedom that define the electronic structures of the heterojunctions. Such rationally designed heterostructures exhibit interesting interlayer properties, such as interlayer carrier transfer and reduction of the photoluminescence linewidth, and could enable the exploration of exciton physics and optoelectronic applications.

Disentangling Second Harmonic Generation from Multiphoton Photoluminescence in Halide Perovskites using Multidimensional Harmonic Generation.

Layered two-dimensional Ruddlesden-Popper (RP) halide perovskites are an intriguing class of semiconductors being explored for their linear and nonlinear optical and ferroelectric properties. Second harmonic generation (SHG) is commonly used to screen for noncentrosymmetric and ferroelectric materials. However, SHG measurements of perovskites can be obscured by their intense multiphoton photoluminescence (mPL). Here, we apply multidimensional harmonic generation as a method to eliminate the complications from mPL. By scanning and correlating both excitation and emission frequencies, we unambiguously assess whether a material supports SHG by examining if an emission feature scales as twice the excitation frequency. Measurements of a series of n = 2, 3 RP perovskites reveal that, contrary to previous belief, n-butylammonium (BA) RP perovskites are not SHG-active and thus centrosymmetric, but RP perovskites with phenylethylammonium (PEA) and 2-thiophenemethylammonium (TPMA) spacer cations display SHG. This work establishes multidimensional harmonic generation as a definitive method to measure SHG in halide perovskites.

Communication: Multidimensional triple sum-frequency spectroscopy of MoS2 and comparisons with absorption and second harmonic generation spectroscopies.

Triple sum-frequency (TSF) spectroscopy is a recently developed methodology that enables collection of multidimensional spectra by resonantly exciting multiple quantum coherences of vibrational and electronic states. This work reports the first application of TSF to the electronic states of semiconductors. Two independently tunable ultrafast pulses excite the A, B, and C features of a MoS2 thin film. The measured TSF spectrum differs markedly from absorption and second harmonic generation spectra. The differences arise because of the relative importance of transition moments and the joint density of states (JDOS). We develop a simple model and globally fit the absorption and harmonic generation spectra to extract the JDOS and the transition moments from these spectra. Our results validate previous assignments of the C feature to a large JDOS created by band nesting.

Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO3).

High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcoming the limitation of island-forming Volmer-Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (104 cm s-1), and low defect density of 1012 cm-3, which are comparable to those of CsPbBr3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. The high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.