Programmable Interfacial Band Configuration in WS2/Bi2O2Se Heterojunctions.

van der Waals heterojunctions based on transition-metal dichalcogenides (TMDs) offer advanced strategies for manipulating light-emitting and light-harvesting behaviors. A crucial factor determining the light-material interaction is in the band alignment at the heterojunction interface, particularly the distinctions between type-I and type-II alignments. However, altering the band alignment from one type to another without changing the constituent materials is exceptionally difficult. Here, utilizing Bi2O2Se with a thickness-dependent band gap as a bottom layer, we present an innovative strategy for engineering interfacial band configurations in WS2/Bi2O2Se heterojunctions. In particular, we achieve tuning of the band alignment from type-I (Bi2O2Se straddling WS2) to type-II and finally to type-I (WS2 straddling Bi2O2Se) by increasing the thickness of the Bi2O2Se bottom layer from monolayer to multilayer. We verified this band architecture conversion using steady-state and transient spectroscopy as well as density functional theory calculations. Using this material combination, we further design a sophisticated band architecture incorporating both type-I (WS2 straddles Bi2O2Se, fluorescence-quenched) and type-I (Bi2SeO5 straddles WS2, fluorescence-recovered) alignments in one sample through focused laser beam (FLB). By programming the FLB trajectory, we achieve a predesigned localized fluorescence micropattern on WS2 without changing its intrinsic atomic structure. This effective band architecture design strategy represents a significant leap forward in harnessing the potential of TMD heterojunctions for multifunctional photonic applications.

Organic and inorganic sublattice coupling in two-dimensional lead halide perovskites.

Two-dimensional layered organic-inorganic halide perovskites have successfully spread to diverse optoelectronic applications. Nevertheless, there remain gaps in our understanding of the interactions between organic and inorganic sublattices that form the foundation of their remarkable properties. Here, we examine these interactions using pump-probe spectroscopy and ab initio molecular dynamics simulations. Unlike off-resonant pumping, resonant excitation of the organic sublattice alters both the electronic and lattice degrees of freedom within the inorganic sublattice, indicating the existence of electronic coupling. Theoretical simulations verify that the reduced bandgap is likely due to the enhanced distortion index of the inorganic octahedra. Further evidence of the mechanical coupling between these two sublattices is revealed through the slow heat transfer process, where the resultant lattice tensile strain launches coherent longitudinal acoustic phonons. Our findings explicate the intimate electronic and mechanical couplings between the organic and inorganic sublattices, crucial for tailoring the optoelectronic properties of two-dimensional halide perovskites.

Weakly Confined Organic-Inorganic Halide Perovskite Quantum Dots as High-Purity Room-Temperature Single Photon Sources.

Colloidal perovskite quantum dots (PQDs) have emerged as highly promising single photon emitters for quantum information applications. Presently, most strategies have focused on leveraging quantum confinement to increase the nonradiative Auger recombination (AR) rate to enhance single-photon (SP) purity in all-inorganic CsPbBr3 QDs. However, this also increases the fluorescence intermittency. Achieving high SP purity and blinking mitigation simultaneously remains a significant challenge. Here, we transcend this limitation with room-temperature synthesized weakly confined hybrid organic-inorganic perovskite (HOIP) QDs. Superior single photon purity with a low g(2)(0) < 0.07 ± 0.03 and a nearly blinking-free behavior (ON-state fraction >95%) in 11 nm FAPbBr3 QDs are achieved at room temperature, attributed to their long exciton lifetimes (τX) and short biexciton lifetimes (τXX). The significance of the organic A-cation is further validated using the mixed-cation FAxCs1-xPbBr3. Theoretical calculations utilizing a combination of the Bethe-Salpeter (BSE) and k·p approaches point toward the modulation of the dielectric constants by the organic cations. Importantly, our findings provide valuable insights into an additional lever for engineering facile-synthesized room-temperature PQD single photon sources.

Floquet Engineering of Excitons in Two-Dimensional Halide Perovskites via Biexciton States.

Layered two-dimensional halide perovskites (2DHPs) exhibit exciting non-equilibrium properties that allow the manipulation of energy levels through coherent light-matter interactions. Under the Floquet picture, novel quantum states manifest through the optical Stark effect (OSE) following intense subresonant photoexcitation. Nevertheless, a detailed understanding of the influence of strong many-body interactions between excitons on the OSE in 2DHPs remains unclear. Herein, we uncover the crucial role of biexcitons in photon-dressed states and demonstrate precise optical control of the excitonic states via the biexcitonic OSE in 2DHPs. With fine step tuning of the driven energy, we fully parametrize the evolution of exciton resonance modulation. The biexcitonic OSE enables Floquet engineering of the exciton resonance with either a blue-shift or a red-shift of the energy levels. Our findings shed new light on the intricate nature of coherent light-matter interactions in 2DHPs and extend the degree of freedom for ultrafast coherent optical control over excitonic states.

Making and Breaking of Exciton Cooling Bottlenecks in Halide Perovskite Nanocrystals.

Harnessing quantum confinement (QC) effects in semiconductors to retard hot carrier cooling (HCC) is an attractive approach for enabling efficient hot carrier extraction to overcome the Shockley-Queisser limit. However, there is a debate about whether halide perovskite nanocrystals (PNCs) can effectively exploit these effects. To address this, we utilized pump-probe and multipulse pump-push-probe spectroscopy to investigate HCC behavior in PNCs of varying sizes and cation compositions. Our results validate the presence of an intrinsic phonon bottleneck with clear manifestations of QC effects in small CsPbBr3 PNCs exhibiting slower HCC rates compared to those of larger PNCs. However, the replacement of inorganic Cs+ with organic cations suppresses this intrinsic bottleneck. Furthermore, PNCs exhibit distinct size-dependent HCC behavior in response to changes in the cold carrier densities. We attribute this to the enhanced exciton-exciton interactions in strongly confined PNCs that facilitate Auger heating. Importantly, our findings dispel the existing controversy and provide valuable insights into design principles for engineering QC effects in PNC hot carrier applications.

Carrier multiplication in perovskite solar cells with internal quantum efficiency exceeding 100.

Carrier multiplication (CM) holds great promise to break the Shockley-Queisser limit of single junction photovoltaic cells. Despite compelling spectroscopic evidence of strong CM effects in halide perovskites, studies in actual perovskite solar cells (PSCs) are lacking. Herein, we reconcile this knowledge gap using the testbed Cs0.05FA0.5MA0.45Pb0.5Sn0.5I3 system exhibiting efficient CM with a low threshold of 2Eg (~500 nm) and high efficiency of 99.4 ± 0.4%. Robust CM enables an unbiased internal quantum efficiency exceeding 110% and reaching as high as 160% in the best devices. Importantly, our findings inject fresh insights into the complex interplay of various factors (optical and parasitic absorption losses, charge recombination and extraction losses, etc.) undermining CM contributions to the overall performance. Surprisingly, CM effects may already exist in mixed Pb-Sn PSCs but are repressed by its present architecture. A comprehensive redesign of the existing device configuration is needed to leverage CM effects for next-generation PSCs.

Unveiling Solvation Dynamics of Excited and Ground States via Ultrafast Pump-Dump-Probe Spectroscopy.

The conventional ultrafast pump-probe spectroscopy has primarily focused on examining the formation and decay of the excited state intermediates, but it is very difficult to detect those intermediates while the formation is slow and dissipation is much fast because of the limited concentration during the intrinsic photocycle. To address this issue, a multipulse ultrafast pump-dump-probe spectroscopy was employed to generate and probe the short-lived ground state intermediates (GSIs) in an electronic push-pull pyrene derivative (EPP). This particular derivative undergoes planarized intramolecular charge transfer (PICT) in the excited state upon initial femtosecond pulse excitation. After applying the dump pulse once the PICT was formed, the blue-shifted transient absorption GSIs with the ground state dynamics of the structure recovery was directly observed. It is found that GSIs undergo slower reorganization than the PICT formation in the excited state of EPP due to the solvation effect with different dipole moments of ground states and excited states. These findings provide a comprehensive understanding of the full photocycle dynamics of both the ground and excited states, shedding light on the presence of hidden ground state behaviors.

High-Performance Semi-Transparent Perovskite Solar Cells with over 22% Visible Transparency: Pushing the Limit through MXene Interface Engineering.

Semi-transparent perovskite solar cells (ST-PSCs) have attracted enormous attention recently due to their potential in building-integrated photovoltaic. To obtain adequate average visible transmittance (AVT), a thin perovskite is commonly employed in ST-PSCs. While the thinner perovskite layer has higher transparency, its light absorption efficiency is reduced, and the device shows lower power conversion efficiency (PCE). In this work, a combination of high-quality transparent conducting layers and surface engineering using 2D-MXene results in a superior PCE. In situ high-temperature X-ray diffraction provides direct evidence that the MXene interlayer retards the perovskite crystallization process and leads to larger perovskite grains with fewer grain boundaries, which are favorable for carrier transport. The interfacial carrier recombination is decreased due to fewer defects in the perovskite. Consequently, the current density of the devices with MXene increased significantly. Also, optimized indium tin oxide provides appreciable transparency and conductivity as the top electrode. The semi-transparent device with a PCE of 14.78% and AVT of over 26.7% (400-800 nm) was successfully obtained, outperforming most reported ST-PSCs. The unencapsulated device maintained 85.58% of its original efficiency after over 1000 h under ambient conditions. This work provides a new strategy to prepare high-efficiency ST-PSCs with remarkable AVT and extended stability.

Insights to Carrier-Phonon Interactions in Lead Halide Perovskites via Multi-Pulse Manipulation.

A fundamental understanding of the hot-carrier dynamics in halide perovskites is crucial for unlocking their prospects for next generation photovoltaics. Presently, a coherent picture of the hot carrier cooling process remains patchy due to temporally overlapping contributions from many-body interactions, multi-bands, band gap renormalization, Burstein-Moss shift etc. Pump-push-probe (PPP) spectroscopy recently emerges as a powerful tool complementing the ubiquitous pump-probe (PP) spectroscopy in the study of hot-carrier dynamics. However, limited information from PPP on the initial excitation density and carrier temperature curtails its full potential. Herein, this work bridges this gap in PPP with a unified model that retrieves these essential hot carrier metrics like initial carrier density and carrier temperature under the push conditions, thus permitting direct comparison with traditional PP spectroscopy. These results are well-fitted by the phonon bottleneck model, from which the longitudinal optical phonon scattering time τLO , for MAPbBr3 and MAPbI3 halide perovskite thin film samples are determined to be 240 ± 10 and 370 ± 10 fs, respectively.

Zero-field quantum beats and spin decoherence mechanisms in CsPbBr3 perovskite nanocrystals.

Coherent optical manipulation of exciton states provides a fascinating approach for quantum gating and ultrafast switching. However, their coherence time for incumbent semiconductors is highly susceptible to thermal decoherence and inhomogeneous broadening effects. Here, we uncover zero-field exciton quantum beating and anomalous temperature dependence of the exciton spin lifetimes in CsPbBr3 perovskite nanocrystals (NCs) ensembles. The quantum beating between two exciton fine-structure splitting (FSS) levels enables coherent ultrafast optical control of the excitonic degree of freedom. From the anomalous temperature dependence, we identify and fully parametrize all the regimes of exciton spin depolarization, finding that approaching room temperature, it is dominated by a motional narrowing process governed by the exciton multilevel coherence. Importantly, our results present an unambiguous full physical picture of the complex interplay of the underlying spin decoherence mechanisms. These intrinsic exciton FSS states in perovskite NCs present fresh opportunities for spin-based photonic quantum technologies.

Intrinsic Carrier Diffusion in Perovskite Thin Films Uncovered by Transient Reflectance Spectroscopy.

Carrier diffusion and surface recombination are key processes influencing the performance of conventional semiconductor devices. However, the interplay of photon recycling together with these processes in halide perovskites obfuscates our understanding. Herein, we discern these inherent processes in a thin FAPbBr3 perovskite single crystal (PSC) utilizing a unique transient reflectance technique that allows accurate diffusion modeling with clear boundary conditions. Temperature-dependent measurements reveal the coexistence of shallow and deep traps at the surface. The inverse quadratic dependence of temperature on carrier mobility µ suggests an underlying scattering mechanism arising from the anharmonic deformation of the PbBr6 cage. Our findings ascertain the fundamental limits of the intrinsic surface recombination velocity (S) and carrier diffusion coefficient (D) in PSC samples. Importantly, these insights will help resolve the ongoing debate and clarify the ambiguity surrounding the contributions of photon recycling and carrier diffusion in perovskite optoelectronics.

Electric Field Modulation of 2D Perovskite Excitonics.

Multiquantum-well (MQW) perovskite is one of the forerunners in high-efficiency perovskite LED (PeLEDs) research. Despite the rapid inroads, PeLEDs suffer from the pertinent issue of efficiency decrease with increasing brightness, commonly known as "efficiency roll-off". The underlying mechanisms are presently an open question. Herein, we explicate the E-field effects on the exciton states in the archetypal MQW perovskite (C6H5C2H4NH3)2PbI4, or PEPI, in a device-like architecture using field-assisted transient spectroscopy and theoretical modeling. The applied E-field results in a complex interplay of spectral blueshifts and enhancement/quenching of the different exciton modes. The former originates from the DC Stark shift, while the latter is attributed to the E-field modulation of the transfer rates between bright/dark exciton modes. Importantly, our findings uncover crucial insights into the photophysical processes under E-field modulation contributing to efficiency roll-off in MQW PeLEDs. Electrical modulation of exciton properties presents exciting possibilities for signal processing devices.

COVID-19 Pandemic Increased Anxiety Among Patients with Inflammatory Bowel Disease: A Patient Survey in a Tertiary Referral Center.

BACKGROUND: COVID-19 is the first global pandemic in more than 100 years, and at its onset, the effects were largely unknown. Immunocompromised patients, including IBD, were presumed to have higher risk. AIMS: We hypothesized patients with IBD would have higher-than-baseline anxiety, high perceived vulnerability and significant lifestyle impacts as a result of the pandemic. We sought to assess the impact of these changes on disease and management. METHODS: A cross-sectional study of patients with Crohn's disease, ulcerative colitis and IBD-unspecified was conducted. Patients were invited to participate by email in an IRB-approved brief, voluntary survey. Survey questions focused on disease characteristics, healthcare access and self-reported psychological well-being. RESULTS: Responses from 492 (CD = 337, UC = 141,IC = 14) patients were included in the analysis. The majority of patients with IBD had increased anxiety since the pandemic, which correlated with an increase in GI symptoms. This risk of symptoms was mitigated by communication with their provider. Many patients had lifestyle changes including requesting time off work due to perceived vulnerability and changes in eating habits. CONCLUSIONS: Our findings support an increase in illness-associated anxiety and perceived vulnerability among patients with IBD during the COVID-19 pandemic. Open communication with providers is important to maintain adequate control of disease and reduce symptoms of flares triggered by ongoing stress.

Controllable Solution-Phase Epitaxial Growth of Q1D Sb2 (S,Se)3 /CdS Heterojunction Solar Cell with 9.2% Efficiency.

Antimony sulfoselenide (Sb2 (S,Se)3 ) is a promising photoabsorber for stable and high efficiency thin film photovoltaics (PV). The unique quasi-1D (Q1D) crystal structure gives Sb2 (S,Se)3 intriguing anisotropic optoelectronic properties, which intrinsically require the optimization of crystal growth orientation, especially for electronic devices with vertical charge transport such as solar cells. Although the efficiency of Sb2 (S,Se)3 solar cells has been improved greatly through optimizing the material quality, the fundamental issue of crystal orientation control in polycrystalline films remains unsolved, resulting in charge carrier recombination losses in the device. Herein, the epitaxial growth of vertically-oriented Sb2 (S,Se)3 film on hexagonal CdS is successfully realized via a solution-based synergistic crystal growth process. The crystallographic orientation relationship between Sb2 (S,Se)3 light absorber and the CdS substrate has been rigorously investigated. The best performing Sb2 (S,Se)3 solar cell shows a high power conversion efficiency of 9.2% owing to the faster charge transport in the bulk and the efficient charge extraction across the heterojunction. This study points to a new direction to control the crystal growth of mixed-anion Sb2 (S,Se)3 , which is crucial to achieve high efficiency solar cells based on antimony chalcogenides with low dimensionality.

Effect of alloying on the dynamics of coherent acoustic phonons in bismuth double perovskite single crystals.

The bismuth double perovskite Cs2AgBiBr6 has been regarded as a potential candidate for lead-free perovskite photovoltaics. A detailed study on the coherent acoustic phonon dynamics in the pure, Sb- and Tl-alloyed Cs2AgBiBr6 single crystals is performed to understand the effects of alloying on the phonon dynamics and band edge characteristics. The coherent acoustic phonon frequencies are found to be independent of the alloying, while the damping rates are highly dependent on the alloying. Based on the mechanism of coherent acoustic phonon damping, a technique has been successfully developed that can accurately extract the absorption spectra near the indirect band gap for these single crystals with coefficients on the order of 102 cm-1.

Strong self-trapping by deformation potential limits photovoltaic performance in bismuth double perovskite.

Bismuth-based double perovskite Cs2AgBiBr6 is regarded as a potential candidate for low-toxicity, high-stability perovskite solar cells. However, its performance is far from satisfactory. Albeit being an indirect bandgap semiconductor, we observe bright emission with large bimolecular recombination coefficient (reaching 4.5 ± 0.1 × 10-11 cm3 s-1) and low charge carrier mobility (around 0.05 cm2 s-1 V-1). Besides intermediate Fröhlich couplings present in both Pb-based perovskites and Cs2AgBiBr6, we uncover evidence of strong deformation potential by acoustic phonons in the latter through transient reflection, time-resolved terahertz measurements, and density functional theory calculations. The Fröhlich and deformation potentials synergistically lead to ultrafast self-trapping of free carriers forming polarons highly localized on a few units of the lattice within a few picoseconds, which also breaks down the electronic band picture, leading to efficient radiative recombination. The strong self-trapping in Cs2AgBiBr6 could impose intrinsic limitations for its application in photovoltaics.

Hot Carriers in Halide Perovskites: How Hot Truly?

Slow hot carrier cooling in halide perovskites holds the key to the development of hot carrier (HC) perovskite solar cells. For accurate modeling and pragmatic design of HC materials and devices, it is essential that HC temperatures are reliably determined. A common approach involves fitting the high-energy tail of the main photobleaching peak in a transient absorption spectrum with a Maxwell-Boltzmann distribution. However, this approach is problematic because of complications from the overlap of several photophysical phenomena and a lack of consensus in the community on the fitting procedures. Herein, we propose a simple approach that circumvents these challenges. Through tracking the broadband spectral evolution and accounting for bandgap renormalization and spectral line width broadening effects, our method extracts not only accurate and consistent carrier temperatures but also other important parameters such as the quasi-Fermi levels, bandgap renormalization constant, etc. Establishing a reliable method for the carrier temperature determination is a step forward in the study of HCs for next-generation perovskite optoelectronics.

Linear and Nonlinear Infrared Spectroscopies Reveal Detailed Solute-Solvent Dynamic Interactions of a Nitrosyl Ruthenium Complex in Solution.

In this work, the solvation of a nitrosyl ruthenium complex, [(CH3)4N][RuCl3(qn)(NO)] (with qn = deprotonated 8-hydroxyquinoline), which is a potential NO-releasing molecule in the bio-environment, was studied in two bio-friendly solvents, namely deuterated dimethyl sulfoxide (dDMSO) and water (D2O). A blue-shifted NO stretching frequency was observed in water with respect to that in dDMSO, which was believed to be due to ligand-solvent hydrogen-bonding interactions, one N═O···D and particularly three Ru-Cl···D, that show competing effects on the NO bond length. The dynamic differences of the NO stretch in these two solvents were further revealed by transient pump-probe IR and two-dimensional IR results: faster vibrational relaxation and faster spectral diffusion (SD) were observed in D2O, confirming stronger solvent-solute interaction and also faster solvent structural dynamics in D2O than in DMSO. Further, a significant non-decaying residual in the SD dynamics was observed in D2O but not in DMSO, suggesting the formation of a stable solvation shell in water due to strong multi-site ligand-solvent hydrogen-bonding interactions, which is in agreement with the observed blue-shifted NO stretching frequency. This work demonstrates that small solvent molecules such as water can form a relatively rigid solvation shell for certain transition metal complexes due to cooperative ligand-solvent interactions and show slower dynamics.

Micellar and bicontinuous microemulsion structures show different solute-solvent interactions: a case study using ultrafast nonlinear infrared spectroscopy.

Microemulsions are transparent, thermodynamically stable liquid mixtures of oil, water and surfactant. They typically exist in the form of micellar and bicontinuous structures, which appear to be equilibrium systems but are actually complex in structure and are difficult to characterize at the molecular level. In this work, potassium ferrocyanide [K4Fe(CN)6] and tungsten hexacarbonyl [W(CO)6] were chosen as two probe molecules for water and organic phases respectively to simultaneously explore the structures and dynamics of commonly prepared reverse micellar and bicontinuous microemulsion structures using aerosol OT (AOT) as the surfactant and isooctane as the oil phase. Even though these two structures have quite different solvent environments due to the varying geometry and boundary conditions, the steady-state infrared spectra of the C[triple bond, length as m-dash]N- stretching mode in the water phase are quite similar, and so are those of the C[triple bond, length as m-dash]O stretching mode in the oil phase. However, vibrational and anisotropic relaxation dynamics obtained from infrared pump-probe spectroscopy and spectral diffusion dynamics extracted from two-dimensional infrared spectroscopy of the two infrared chromophores in the two probe molecules are found to be quite sensitive to whether the probe molecules are in pure solvent or in a restricted microemulsion environment. The results in the water phase and oil phase are discussed separately. Our work demonstrated that ultrafast nonlinear infrared spectroscopy can be used to differentiate the structural details at the molecular level for different microemulsion systems.