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At least 1,333 records · Page 74

Dynamic Behavior of Bound Interlayer Excitons in Interlayer-Doped Cs 3 Bi 2 Br 9 Vacancy-Ordered Perovskite

Interlayer doping of the vacancy-ordered 2D perovskite Cs 3 Bi 2 Br 9 (CBB) enables the formation of bound interlayer excitons (BIEs), a unique charge-transfer excited state within the layered solid. BIEs previously reported with silver (Ag + ) as an interlayer dopant exhibited bright broadband photoluminescence (PL) with prolonged lifetime at room temperature, offering potential applications in efficient white light emission, photocatalysis, and optoelectronics. However, the dynamic behavior of radiation and excited carriers remains poorly understood due to the limitations of ensemble spectroscopic measurements. Here, we investigate the temperature-dependent dynamics of Ag-doped Cs 3 Bi 2 Br 9 (Ag-CBB) using single-particle time-resolved PL spectroscopy and ultrafast transient absorption imaging. Single-particle PL measurements reveal three distinct emission regimes across temperature: (i) BIE-dominant emission at high temperatures, (ii) a mixture of radiation from BIEs and self-trapped excitons (STEs) at intermediate temperatures, and (iii) STE-dominant emission below 100 K. Rapid transient absorption mapping using Parallel Rapid Imaging with Spectroscopic Mapping (PRISM) reveals subpicosecond STE formation in pristine CBB and long-lived photoinduced absorption by BIEs, consistent with electron–hole separation and suppressed STE transfer. The spatial uniformity of these signals confirms homogeneous Ag doping across single crystals. These findings highlight the role of Ag interlayer dopants in governing the BIE dynamics.

bound interlayer exciton↗

Interligand Coupling Drives Fast Triplet Energy Transfer Routes in PbS/Tetracene Quantum Dot Hybrids

The binding of photoactive organic ligands to inorganic quantum dots (QDs) creates a versatile hybrid architecture that allows access to photophysical processes such as efficient triplet exciton generation with near-infrared radiation. Here we report the subnanosecond generation of a hybrid triplet state with mixed ligand-QD character by replacing native oleate ligands on small PbS QDs with 5,12-tetracenepropiolic acid, a bifunctional ligand with two carboxylic acids that tends to lie face-on with the QD surface at low loadings. The face-on geometry engenders a regime of strong electronic coupling that is evident in steady-state absorption and hastens triplet energy flow by several orders of magnitude compared with more typical tetracene-based ligands exhibiting weak coupling. We further determined via Fourier transform infrared (FTIR) and supported by density functional theory (DFT)-based geometry optimizations that high ligand loading causes a shift in QD-ligand mutual disposition toward an edge-on geometry that instigates the formation of intermolecular excited states characterized by triplet excimer-like features in photoluminescence and transient absorption. Our results demonstrate the ability to control strongly coupled ligand-QD systems toward ultrafast generation of photophysically relevant species such as triplets that are valuable for photon upconversion and catalysis.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electrical Switching and Imaging of Antiferromagnetic Spins in Perovskite Epitaxial Thin Films

Electrical control of antiferromagnets is essential for the field of antiferromagnetic spintronics that promises ultrafast speed and terahertz dynamics. However, the large family of complex oxide antiferromagnets such as perovskites have been largely unexplored. Here, we demonstrate electrical switching and detection of Néel vector in LaFeO 3 epitaxial thin films with an epitaxy-enabled biaxial anisotropy, of which the switching behavior is understood by comparing to magnetic field controlled spin Hall magnetoresistance measurements. The electrical switching is corroborated by imaging of antiferromagnetic domains using X-ray Magnetic Linear Dichroism Photoemission Electron Microscopy. Electrical switching of 3-nm and 10-nm LaFeO 3 films was achieved over a wide temperature range of 25 to 300 K. This work offers an attractive platform for exploration of antiferromagnetic spintronics and other emerging phenomena such as potential insulating altermagnetism.

36 MATERIALS SCIENCE↗

Carrier Dynamics of Strongly Confined CsPbI 3 Nanowires

Here, we investigate the carrier dynamics of strongly confined cesium lead iodide (CsPbI 3 ) nanowires and compare them with weakly confined quantum dots (QDs) to understand how dimensionality affects recombination processes. Using time-resolved photoluminescence and ultrafast transient absorption spectroscopy, we find that nanowires exhibit a 5× faster recombination rate and more rapid carrier cooling than QDs. These differences are attributed to enhanced carrier interactions with trap states. Although nanowires exhibit slightly enhanced radiative rates as a result of confinement, their photoluminescence quantum yield remains relatively low, 23 ± 8%, due to competition from nonradiative recombination processes that occur at a faster rate. These findings highlight a dimensionality-dependent trade-off between radiative efficiency and nonradiative losses, providing insight into the limitations and opportunities for low-dimensional perovskite nanostructures. Our results establish design principles for tailoring CsPbI 3 nanocrystal dimensionality to optimize optical performance in optoelectronic applications such as LEDs and solar cells.

Oddo, Alexander M. [University of California, Berk↗

Depth-Resolved X-Ray Nanoimaging of Coherent and Incoherent Energy Transport in Silicon Carbide

Understanding lattice dynamics is crucial for optimizing the process of creating functional structures, such as laser writing of color-center defects. However, existing structural probes have difficulty measuring structural dynamics with submicrometer depth sensitivity. Here, in this study, a depth-resolved ultrafast X-ray nanodiffraction technique is developed to track the lattice dynamics of silicon carbide (SiC) in three dimensions. Upon laser excitation of an aluminum layer that acts as a heat and strain transducer, a specular Bragg peak of SiC shows an overall increase in the X-ray diffraction intensity rather than a peak shift. The relaxation dynamics of the increased intensity are significantly different when probed on and off the Bragg peak. The fast subnanosecond relaxation probed at the maximum of the Bragg peak is a result of the propagation of a coherent strain wave along the depth direction, while a slow relaxation probed at the wings of the Bragg peak reflects a localized incoherent lattice heating. To further visualize these processes, spatiotemporal maps were obtained by scanning the relative position and delay between the laser pump and X-ray probe beams, which capture the propagation of the strain wave, as well as a stationary structural distortion close to the aluminum/SiC interface. These depth-resolved structural measurements disentangle energy dissipation mechanisms in laser-excited SiC, and they open opportunities for finer control of, for example, the formation of optically addressable defect complexes central to quantum information applications.

X-ray nanodiffraction↗

Tellurene Photodetector with High Gain and Wide Bandwidth

Two-dimensional (2D) semiconductors have been extensively explored as a new class of materials with great potential. In particular, black phosphorus (BP) has been considered to be a strong candidate for applications such as high-performance infrared photodetectors. However, the scalability of BP thin film is still a challenge, and its poor stability in the air has hampered the progress of the commercialization of BP devices. Herein, we report the use of hydrothermal-synthesized and air-stable 2D tellurene nanoflakes for broadband and ultrasensitive photodetection. The tellurene nanoflakes show high hole mobilities up to 458 cm 2 /V·s at ambient conditions, and the tellurene photodetector presents peak extrinsic responsivity of 383 A/W, 19.2 mA/W, and 18.9 mA/W at 520 nm, 1.55 μm, and 3.39 μm light wavelength, respectively. Because of the photogating effect, high gains up to 1.9 × 10 3 and 3.15 × 10 4 are obtained at 520 nm and 3.39 μm wavelength, respectively. At the communication wavelength of 1.55 μm, the tellurene photodetector exhibits an exceptionally high anisotropic behavior, and a large bandwidth of 37 MHz is obtained. The photodetection performance at different wavelength is further supported by the corresponding quantum molecular dynamics (QMD) simulations. Our approach has demonstrated the air-stable tellurene photodetectors that fully cover the short-wave infrared band with ultrafast photoresponse.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionization-Induced Subcycle Metallization of Nanoparticles in Few-Cycle Pulses

Strong-field laser-matter interactions in nanoscale targets offer unique avenues for the generation and detailed characterization of matter under extreme conditions. Field-driven, sub-cycle ionization-induced metallization of nanoscale solids in intense laser fields has been predicted (Peltz et al. Time-Resolved X-ray Imaging of Anisotropic Nano-plasma Expansion. Phys. Rev. Lett. 2014, 113, 133401), but its observation was hampered by a lack of a smoking gun. Here, we report the ultrafast metallization of isolated dielectric and semiconducting nanoparticles under intense few-cycle laser pulses. The highest-energy electron emission is found to be a decisive proof that shows a characteristic cutoff modification to a metallic limit for intensities high enough to ignite carrier avalanching in the volume of the particles. Furthermore, semiclassical Mean-field Mie Monte-Carlo transport simulations reveal the underlying dynamics and explain the observed evolution by near-field driven electron backscattering from the metallizing target.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamically Tunable Terahertz Emission Enabled by Anomalous Optical Phonon Responses in Lead Telluride

Lead telluride (PbTe), a narrow bandgap semiconductor commonly used in infrared detectors, exhibits anomalous vibrational and structural properties, making it appealing for thermoelectrics. Despite significant fundamental interest in the microscopic origins of its unusual vibrational properties, the optical functionalities stemming from phonons and electron–phonon coupling in PbTe have not been closely investigated. This work reports measurements of terahertz (THz) radiation from a PbTe single crystal following ultrafast optical excitation and investigates IR-active phonon responses as a function of excitation fluence and temperature. We uncover a spectrally tunable THz emission peak enabled by an epsilon-near-zero response of the coupled plasmon–longitudinal optical phonon mode that can be dynamically shifted via tuning photocarrier density. Spectral tunability (Δω/ω = 25%) is significant and beyond what has been achieved by any other THz emitter. In addition, the emitted THz fields reveal signatures of a zone center transverse optical phonon anomaly and unveil a new mode at 0.3 THz that diminishes in amplitude under increasing photocarrier density. Temperature-dependent measurements suggest that the transverse-like modes at 1 and 1.5 THz are possibly of different origins. These results indicate that the unusual phononic properties in PbTe are tunable via photoexcitation and enable new optical functionalities in THz applications, such as spectrally tunable emitters and all-optical modulators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strong-Field Control of Plasmonic Properties in Core–Shell Nanoparticles

Utilization of the plasmonic response in nanosystems is a key component of nanophotonics that is typically altered by varying the incident optical frequency or the material configuration. However, in this work we demonstrate that employing intense, femtosecond laser fields unlock nonlinear light–matter interactions such that precise control of the optical response is achieved solely by adjusting the incident intensity. The plasmonic properties of Au/SiO 2 nanoshells are manipulated by exploiting the nonlinear index of refraction of gold and experimentally observed by employing photoelectrons emitted during the interaction as a sensitive, sub-wavelength probe. A striking transition seen in the photoelectron energy spectrum between the weak and strong-field regime is verified by a modified Mie theory simulation that incorporates the nonlinear dielectric nanoshell response. The exhibited intensity-dependent optical control of the plasmonic response in prototypical core–shell nanoparticles paves the way toward ultrafast switching and opto-electronic signal modulation with more complex nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Attosecond Transient Grating Spectroscopy with Near-Infrared Grating Pulses and an Extreme Ultraviolet Diffracted Probe

Transient grating spectroscopy has become a mainstay among metal and semiconductor characterization techniques. Here, we extend the technique toward the shortest achievable time scales by using tabletop high-harmonic generation of attosecond extreme ultraviolet (XUV) pulses that diffract from transient gratings generated with sub-5 fs near-infrared (NIR) pulses. We demonstrate the power of attosecond transient grating spectroscopy (ATGS) by investigating the ultrafast photoexcited dynamics in an Sb semimetal thin film. ATGS provides an element-specific, background-free signal unfettered by spectral congestion, in contrast to transient absorption spectroscopy. With ATGS measurements in Sb polycrystalline thin films, we observe the generation of coherent phonons and investigate the lattice and carrier dynamics. Among the latter processes, we extract carrier thermalization, hot carrier cooling, and electron-hole recombination, which are on the order of 20 fs, 50 fs, and 2 ps time scales, respectively. Furthermore, the simultaneous collection of transient absorption and transient grating data allows us to extract the total complex dielectric constant in the sample dynamics with a single measurement, including the real-valued refractive index, from which we are also able to investigate carrier-phonon interactions and longer-lived phonon dynamics. The outlined experimental technique expands the capabilities of transient grating spectroscopy and attosecond spectroscopies by providing a wealth of information concerning carrier and lattice dynamics with an element-selective technique at the shortest achievable time scales.

Quintero-Bermudez, Rafael↗

3 d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications

Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni( t-Bu bpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV–Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3 d-d rather than 3 MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1 H NMR techniques, supporting that this 3 d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the 3 d-d state was determined to lie ~0.5 eV (12 kcal/mol) above the ground state. Because the 3 d-d state features a weak Ni–aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported experimentally. Thus, photoinduced Ni–aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Perspectives on Dye Sensitization of Nanocrystalline Mesoporous Thin Films

Recent advances in our mechanistic understanding of dye-sensitized electron transfer reactions occurring at metal oxide interfaces are described. These advances were enabled by the advent of mesoporous thin films, comprised of anatase TiO 2 nanocrystallites, that are amenable to spectroscopic and electrochemical characterization in unprecedented molecular-level detail. The metal-to-ligand charge transfer (MLCT) excited states of Ru polypyridyl compounds serve as the dye sensitizers. Excited-state injection often occurs on ultrafast time scales with yields that can be tuned from unity to near zero through modification of the sensitizer or the electrolyte composition. Transport of the injected electron and the oxidized sensitizer (hole hopping) are both operative in the composite mechanism for charge recombination between the injected electron and the oxidized sensitizer. Sensitizers that contain a pendant electron donor, as well as core/shell SnO 2 /TiO 2 nanostructures, often prolong the lifetime of the injected electron and provide fundamental insights into adiabatic and nonadiabatic electron transfer mechanisms. Regeneration of the oxidized sensitizer by iodide is enhanced through halogen bonding, orbital pathways, and ion pairing. A substantial ~10 MV cm –1 electric field is created by electron injection into TiO 2 nanocrystallites that induces ion migration, reports on the sensitizer dipole orientation, and (in some cases) reorients or flips the sensitizer. Dye-sensitized conductive oxides also promote long-lived charge separation with bias dependent kinetics that provide insights into the reorganization energies associated with electron and proton-coupled electron transfer in the electric double layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronically Coupled 2D Polymer/MoS 2 Heterostructures

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS 2 heterostructures. In this work, control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS 2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distance Dependence of Förster Resonance Energy Transfer Rates in 2D Perovskite Quantum Wells via Control of Organic Spacer Length

Two-dimensional (2D) semiconductors are attractive candidates for a variety of optoelectronic applications owing to the unique electronic properties that arise from quantum confinement along a single dimension. Incorporating nonradiative mechanisms that enable directed migration of bound charge carriers, such as Forster resonance energy transfer (FRET), could boost device efficiencies provided that FRET rates outpace undesired relaxation pathways. However, predictive models for FRET between distinct 2D states are lacking, particularly with respect to the distance d between a donor and acceptor. We approach FRET in systems with binary mixtures of donor and acceptor 2D perovskite quantum wells (PQWs), and we synthetically tune distances between donor and acceptor by varying alkylammonium spacer cation lengths. FRET rates are monitored using transient absorption spectroscopy and ultrafast photoluminescence, revealing rapid picosecond lifetimes that scale with spacer cation length. We theoretically model these binary mixtures of PQWs, describing the emitters as classical oscillating dipoles. Finally, we find agreement with our empirical lifetimes and then determine the effects of lateral extent and layer thickness, establishing fundamental principles for FRET in 2D materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-Evolving Chirality Loss in Molecular Photodissociation Monitored by X-ray Circular Dichroism Spectroscopy

In this work, the ultrafast photoinduced chirality loss of 2-iodobutane is studied theoretically by time- and frequency-resolved X-ray circular dichroism (TRXCD) spectroscopy. Following an optical excitation, the iodine atom dissociates from the chiral center, which we capture by quantum non-adiabatic molecular dynamics simulations. At variable time delays after the pump, the resonant X-ray pulse selectively probes the iodine and carbon atom involved in the chiral dissociation through a selected core-to-valence transition. The TRXCD signal at the iodine L 1 edge accurately captures the timing of C–I photodissociation and thereby chirality loss, c.a 70 fs. The strong electric dipole–electric quadrupole (ED–EQ) response makes this signal particularly sensitive to vibronic coherence at the high X-ray regime. At the carbon K-edges, the signals monitor the molecular chirality of the 2-butyl radical photoproduct and the spin state of the iodine atom. The ED–EQ response is masked under the strong electric dipole-magnetic dipole response, making this signal intuitive for the electronic population. The evolution of the core electronic states and its chiral sensitivity is discussed. Overall, the element-specific TRXCD signal provides a detailed picture of molecular dynamics and offers a unique sensitive window into the time-dependent chirality of molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum Sensing of Electric Fields Using Spin-Correlated Radical Ion Pairs

Quantum sensing affords the possibility of using quantum entanglement to probe electromagnetic fields with exquisite sensitivity. In this work, we show that a photogenerated spin-correlated radical ion pair (SCRP) can be used to sense an electric field change created at one radical ion of the pair using molecular recognition. The SCRP is generated within a covalent donor–chromophore–acceptor system PXX–PMI–NDI, 1, where PXX = peri-xanthenoxanthene, PMI = 1,6-bis(p-t-butylphenoxy)perylene-3,4-dicarboximide, and NDI = naphthalene-1,8:4,5-bis(dicarboximide). The electron-rich PXX donor in 1 acts as a guest molecule that can be encapsulated selectively by a tetracationic cyclophane ExBox4+ host to give a supramolecular complex 1 ⊂ ExBox 4+ . Selective photoexcitation of the PMI chromophore results in ultrafast generation of the PXX •+ –PMI–NDI •– SCRP. When PXX is encapsulated by ExBox 4+ , the cyclophane generates an electric field that repels the positive charge on PXX •+ within PXX •+ –PMI–NDI •– , reducing the SCRP distance, i.e., the distance between the centers-of-charge on the donor and acceptor. Pulse-EPR measurements are used to measure the coherent oscillations created primarily by the electron–electron dipolar coupling in the SCRP, which yields the distance between the two charges (spins) of PXX •+ –PMI–NDI •– . Here, the experimental results show that the distance between PXX •+ and NDI •– decreases when ExBox 4+ encapsulates PXX •+ , which demonstrates that the SCRP can function as a quantum sensor to detect electric field changes in the vicinity of the radical ions.

Anions↗

Type-I CdS/ZnS Core/Shell Quantum Dot-Gold Heterostructural Nanocrystals for Enhanced Photocatalytic Hydrogen Generation

Developing Type-I core/shell quantum dots is of great importance toward fabricating stable and sustainable photocatalysts. However, the application of Type-I systems has been limited due to the strongly confined photogenerated charges by the energy barrier originating from the wide-bandgap shell material. In this project, we found that through the decoration of Au satellite-type domains on the surface of Type-I CdS/ZnS core/shell quantum dots, such an energy barrier can be effectively overcome and an over 400-fold enhancement of photocatalytic H(2) evolution rate was achieved compared to bare CdS/ZnS quantum dots. Transient absorption spectroscopic studies indicated that the charges can be effectively extracted and subsequently transferred to surrounding molecular substrates in a subpicosecond time scale in such hybrid nanocrystals. Based on density functional theory calculations, the ultrafast charge separation rates were ascribed to the formation of intermediate Au2S layer at the semiconductor-metal interface, which can successfully offset the energy confinement introduced by the ZnS shell. In conclusion, our findings not only provide insightful understandings on charge carrier dynamics in semiconductor-metal heterostructural materials but also pave the way for the future design of quantum dot-based hybrid photocatalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO 2 Photoreduction

Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO 2 reduction performance after incorporating a Re(bpy)(CO) 3 Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF). These interactions ultimately lead the Re-f-COF isomer to function as an efficient CO 2 reduction photocatalyst, while the Re-r-COF isomer shows minimal photocatalytic activity. Furthermore, these findings not only reveal the essential role linker chemistry plays in COF photophysical and photocatalytic properties but also offer a unique opportunity to design photosensitizers that can selectively direct charges.

14 SOLAR ENERGY↗