Pressure-Induced Changes in the Phase Distribution and Carrier Dynamics of Quasi-Two-Dimensional Ruddlesden-Popper Perovskites.

Quasi-two-dimensional (quasi-2D) perovskites hold significant potential for diverse design strategies due to their tunable structures, exceptional optical properties, and environmental stability. Due to the complexity of the structure and carrier dynamics, characterization methods such as photoluminescence and absorption spectroscopy can observe but cannot precisely distinguish or identify the phase distribution within quasi-2D perovskite films or correlate phases with carrier dynamics. In this study, we used pressure to modulate the intralayer and interlayer structures of (PEA)2Csn-1PbnBr3n+1 quasi-2D perovskite films, investigating charge carrier dynamics. Steady-state spectroscopy revealed phase transitions at 1.62, 3, and 8 GPa, with free excitons transforming into self-trapped excitons after 8 GPa. Transient absorption spectroscopy elucidated the structural evolution, energy transfer, and pressure-induced transition mechanisms. The results demonstrate that combining pressure and spectroscopy enables the precise identification of phase distribution and pressure response ranges and reveals photophysical mechanisms, providing new insights for optimizing optoelectronic materials.

Modulating Carrier Dynamics in PdSe2: The Role of Pressure in Electronic and Phononic Interactions.

PdSe2 is a puckered transition metal dichalcogenide that has been reported to undergo a two-dimensional to three-dimensional structural transition under pressure. Here, we investigated the electronic and phononic evolution of PdSe2 under high pressure using pump-probe spectroscopy. We observed the electronic intraband and interband transitions occurring in the d orbitals of Pd, revealing the disappearance of the Jahn-Teller effect under high pressure. Furthermore, we found that the decay rates of interband recombination and intraband relaxation lifetimes change at 3 and 7 GPa, respectively. First-principles calculations suggest that the bandgap closure slows the decay rate of interband recombination after 3 GPa, while the saturation of phonon-phonon scattering is the main reason for the relatively constant intraband relaxation lifetime. Our work provides a novel perspective for understanding the evolution of the electron and modulation of the carrier dynamics by phonons under pressure.

Time-Resolved Dynamics of Metal Halide Perovskite under High Pressure: Recent Progress and Challenges.

Metal halide perovskites have garnered significant attention in the scientific community for their promising applications in optoelectronic devices. The application of pressure engineering, a viable technique, has played a crucial role in substantially improving the optoelectronic characteristics of perovskites. Despite notable progress in understanding ground-state structural changes under high pressure, a comprehensive exploration of excited-state dynamics influencing luminescence remains incomplete. This Perspective delves into recent advances in time-resolved dynamics studies of photoexcited metal halide perovskites under high pressure. With a focus on the intricate interplay between structural alterations and electronic properties, we investigate electron-phonon interactions, carrier transport mechanisms, and the influential roles of self-trapped excitons (STEs) and coherent phonons in luminescence. However, significant challenges persist, notably the need for more advanced measurement techniques and a deeper understanding of the phenomena induced by high pressure in perovskites.

Evidence of Surface-Mediated Carrier-Phonon Scattering in MXene.

In a two-dimensional (2D) metallic nanostructure, when a sample's thickness is shorter than a carrier mean free path, the ultrathin thickness may influence carrier and energy transport, owing to surface scattering. However, to date, for metallic 2D transition-metal carbides (MXenes), experiments and calculations related to surface scattering have not been performed. The contribution of ultrathin structures to carrier surface scattering in MXene is yet to be explored. Herein, to reveal this effect, we design various models, including metal/MXene, dielectric/MXene, and bulk structure, and analyze their carrier dynamics via ultrafast spectroscopy. The results related to carrier dynamics indicate that the influence of the dielectric/MXene interface and the temperature is negligible. In contrast, the carrier dynamic lifetimes are prolonged owing to weakened surface scattering in metal/MXene, which is supported by ab initio calculations. These results suggest that the carrier-phonon scattering is dominated by surface scattering. These findings can help guide effective energy transport and enhance energy conversion and catalysis.

Manipulating Lone-Pair-Driven Luminescence in 0D Tin Halides by Pressure-Tuned Stereochemical Activity from Static to Dynamic.

The excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low-dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero-dimensional Sn-based halides with static stereoactive 5 s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited-state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5 s2 lone pair active switching and self-trapped exciton (STE) redistribution by suppressing excited-state structural deformation of the isolated SnBr4 2- units. Our results demonstrate that the static expression of the 5 s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky-blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.

Highly Efficient Photosensitizers with Molecular Vibrational Torsion for Cancer Photodynamic Therapy.

The development of highly effective photosensitizers (PSs) for photodynamic therapy remains a great challenge at present. Most PSs rely on the heavy-atom effect or the spin-orbit charge-transfer intersystem crossing (SOCT-ISC) effect to promote ISC, which brings about additional cytotoxicity, and the latter is susceptible to the interference of solvent environment. Herein, an immanent universal property named photoinduced molecular vibrational torsion (PVT)-enhanced spin-orbit coupling (PVT-SOC) in PSs has been first revealed. PVT is verified to be a widespread intrinsic property of quinoid cyanine (QCy) dyes that occurs on an extremely short time scale (10-10 s) and can be captured by transient spectra. The PVT property can provide reinforced SOC as the occurrence of ISC predicted by the El Sayed rules (1ππ*-3nπ*), which ensures efficient photosensitization ability for QCy dyes. Hence, QTCy7-Ac exhibited the highest singlet oxygen yield (13-fold higher than that of TCy7) and lossless fluorescence quantum yield (ΦF) under near-infrared (NIR) irradiation. The preeminent photochemical properties accompanied by high biosecurity enable it to effectively perform photoablation in solid tumors. The revelation of this property supplies a new route for constructing high-performance PSs for achieving enhanced cancer phototherapy.

Exploring the Potential Applications of Lanthanide-Based Double Perovskite in Remote Pressure and Temperature Sensing.

Remote optical sensing with nondestructive, fast, and accurate detection capabilities is a powerful noncontact method widely used in natural, industrial, and biological fields. In this work, Cs2NaErCl6 double perovskite was synthesized via a hydrothermal method. The pressure-dependent photoluminescence (PL) lifetime of Er3+ in the range of 0-20 GPa was investigated, demonstrating its potential for pressure monitoring. The high-pressure relative sensitivity (SR) is ∼18.45% GPa-1. Temperature measurements were conducted using the fluorescence intensity ratio (FIR) of the thermal couple energy level (TCEL) and the nonthermal couple energy level (NTCEL) of Er3+ across a temperature range of 100-660 K, with a maximum SR of 5.36% K-1. By combining MXene with Cs2NaErCl6 and recording the FIR of Cs2NaErCl6 under 1550 nm excitation, the photothermal conversion temperature of MXene can be accurately determined. These findings highlight the potential of Cs2NaErCl6 for remote pressure and temperature sensing, particularly in the biomedical field.

Carbon Dots with Blue-to-Near-Infrared Lasing for Colorful Speckle-Free Laser Imaging and Dynamical Holographic Display.

As a new solution-processable laser material, carbon dots (CDs) offer advantages of non-toxicity, low-cost, and high-stability, which are conducive to the sustainable development of miniaturized lasers. Full-color CDs (FC-CDs) with bright-blue, green, yellow, red, deep-red, and near-infrared (NIR) fluorescence are prepared. Their photoluminescence emission ranges from 431 to 714 nm. The FC-CDs show narrow full widths at half maximum in the range of 44-76 nm, with concurrent high radiative transition rates (KR ) of 0.54-1.74 × 108  s-1 ; their performance is comparable to that of organic laser dyes, indicating their good gain potential for lasers. Laser pumping of the FC-CDs gives laser outputs at 467.3, 533.5, 577.4, 616.3, 653.5, and 705.1 nm, spanning from blue to NIR region, and covering 140% of the NTSC color gamut. The FC-CDs show high Q-factors (2000-5500), appreciable gain coefficients (9-21.5 cm-1 ), and better stability (≈100%@4-7 h) than commercial laser dyes. These excellent properties make them suitable for high-quality, colorful, speckle-free laser imaging and dynamic holographic display. The findings will be helpful in promoting the practical applications and development of solution-processable CD-based lasers.

Tailoring the high-brightness "warm" white light emission of two-dimensional perovskite crystals via a pressure-inhibited nonradiative transition.

Efficient warm white light emission is an ideal characteristic of single-component materials for light-emitting applications. Although two-dimensional hybrid perovskites are promising candidates for light-emitting diodes, as they possess broadband self-trapped emission and outstanding stability, they rarely achieve a high photoluminescence quantum yield of warm white light emissions. Here, an unusual pressure-induced warm white emission enhancement phenomenon from 2.1 GPa to 9.9 GPa was observed in two-dimensional perovskite (2meptH2)PbCl4, accompanied by a large increase in the relative quantum yield of photoluminescence. The octahedral distortions, accompanied with the evolution of organic cations, triggered the structural collapse, which caused the sudden emission enhancement at 2.1 GPa. Afterwards, the further intra-octahedral collapse promotes the formation of self-trapped excitons and the substantial suppression of nonradiative transitions are responsible for the continuous pressure-induced photoluminescence enhancement. This study not only clearly illustrates the relationship between crystal structure and photoluminescence, but also provides an experimental basis for the synthesis of high-quality warm white light-emitting 2D metal halide perovskite materials.

Multiphoton excited singlet/triplet mixed self-trapped exciton emission.

Multiphoton excited luminescence is of paramount importance in the field of optical detection and biological photonics. Self-trapped exciton (STE) emission with self-absorption-free advantages provide a choice for multiphoton excited luminescence. Herein, multiphoton excited singlet/triplet mixed STE emission with a large full width at half-maximum (617 meV) and Stokes shift (1.29 eV) has been demonstrated in single-crystalline ZnO nanocrystals. Temperature dependent steady state, transient state and time-resolved electron spin resonance spectra demonstrate a mixture of singlet (63%) and triplet (37%) mixed STE emission, which contributes to a high photoluminescence quantum yield (60.5%). First-principles calculations suggest 48.34 meV energy per exciton stored by phonons in the distorted lattice of excited states, and 58 meV singlet-triplet splitting energy for the nanocrystals being consistent with the experimental measurements. The model clarifies long and controversial debates on ZnO emission in visible region, and the multiphoton excited singlet/triplet mixed STE emission is also observed.

Carbon Quantum Dots with Near-Unity Quantum Yield Bandgap Emission for Electroluminescent Light-Emitting Diodes.

Carbon quantum dots (CQDs) feature bright and tunable photoluminescence, solution processability, and low toxicity, showing great potential in optoelectronics. However, the large-scale synthesis of CQDs with near-unity photoluminescence quantum yield (PLQY) has not been achieved so far. In this study, we perform radical-assisted synthesis of hexagon-shaped CQDs (H-CQDs) delivering near-unity PLQY (96 %). Experimental and theoretical analyses revealed that the large vertically oriented transition dipole moment of H-CQDs originating from high symmetry results in nearly 100 % PLQY. The H-CQDs also exhibited a high electron mobility of up to 0.07 cm2  V-1 s-1 . These properties enable the H-CQD-based light-emitting diodes with a high external quantum efficiency of 4.6 % and a record maximum brightness of over 11 000 cd m-2 . This study represents a significant advance that CQDs-based electroluminescent device can be utilized for potential display and lighting applications.

Centralized Excited States and Fast Radiation Transitions Reduce Laser Threshold in Carbon Dots.

As a new type of solution-processed nano-laser material, carbon dots (CDs) have shown considerable potential in optical communication, laser displays, micro/nano processing, and biomedicine. Reducing the laser threshold of the gain material is of considerable significance for further development of CDs' applications in the field of micro/nano lasers. A series of blue-emissive CDs (B-CDs) are synthesized by changing the molar ratios of the precursors (citric acid (CA): L-Cysteine (L-Cys)). B-CDs have a structure of carbon nanoparticles with their surface being modified with 5-oxo-3,5-dihydro-2Hthiazolo [3,2-a]pyridine-7-carboxylic acid (TPCA). The laser can only be generated when the molar ratio of the precursors is between 1:1 and 2:1. With an increase in this ratio, the laser threshold decreases from 341.6 to 165.5 mJ cm-2 . The decrease in the laser threshold is attributed to the increase in the radiation transition rate and centralized sp3 -related excited state levels, which are favorable for light amplification and population inversion. These results will be instructional for the reasonably design of CDs-based laser materials and prompt their potential use in practical photonics.

Revealing the Mechanism of Pressure-Induced Emission in Layered Silver-Bismuth Double Perovskites.

Pressure-induced emission (PIE) associated with self-trapping excitons (STEs) in low-dimensional halide perovskites has attracted great attention for better materials-by-design. Here, using 2D layered double perovskite (C6 H5 CH2 CH2 NH3 + )4 AgBiBr8 as a model system, we advance a fundamental physicochemical mechanism of the PIE from the perspective of carrier dynamics and excited-state behaviors of local lattice distortion. We observed a pressure-driven STE transformation from dark to bright states, corresponding a strong broadband Stokes-shifted emission. Further theoretical analysis demonstrated that the suppressed lattice distortion and enhanced electronic dimensionality in the excited-state play an important role in the formation of stabilized bright STEs, which could manipulate the self-trapping energy and lattice deformation energy to form an energy barrier between the potential energy curves of ground- and excited-state, and enhance the electron-hole orbital overlap, respectively.

Intramolecular hydrogen bond-tuned thermal-responsive carbon dots and their application to abnormal body temperature imaging.

A steric hindrance strategy was used to prepare intramolecular hydrogen bond-controlled thermosensitive fluorescent carbon dots (CDs) via the solvothermal treatment of o-phenylenediamine respectively with three dihydroxybenzene isomers. The CDs obtained from different isomers have very similar morphology, surfaces, and photophysical properties but exhibited different thermal sensitivities. Meanwhile, the orange-emitting CDs (p-CDs) obtained from o-phenylenediamine and p-hydroquinone exhibited an optimal thermal sensitivity of 1.1%/°C. Comprehensive experimental characterizations and theoretical calculations revealed that even a small difference in substituent locations in the phenyl ring of the precursors can considerably affect the formation of intramolecular hydrogen bonds and that the CDs with strong intramolecular hydrogen bonds exhibited poor thermosensitivity. The p-CDs were incorporated with reference CDs (B-CDs) that exhibited heating-quenching blue emission through electrostatic self-assembly to construct a dual-emission probe (p-CDs/B-CDs), which exhibited a thermal sensitivity of 2.0%/°C. Test strips based on the p-CDs/B-CDs were prepared to measure temperature fluctuations based on sensitive and instant fluorescence color evolution. Further, this fluorescent colorimetry was successfully applied to a test strip-integrated wearable wristband to measure the body temperature. This study establishes an inherent relationship between precursors and the resulting intramolecular hydrogen bonds for precisely tuning the thermal sensitivity of CDs. It also offers a visual quantitative strategy for the early warning of abnormal body temperatures.

Full-Color Circularly Polarized Luminescence of CsPbX3 Nanocrystals Triggered by Chiral Carbon Dots.

Chiral carbon dots (Ch-CDs) trigger the full-color circularly polarized luminescence (CPL) of CsPbX3  nanocrystals (NCs). Ch-CDs-CsPbBr3  NCs are successfully synthesized via simple ligand-assisted coprecipitation of Ch-CDs and metal halides precursors at room temperature. Ch-CDs-CsPbBr3  retains emission characteristics of the CsPbBr3  with near-unity photoluminescence quantum yield, and meanwhile has special CPL, with a maximum luminescence dissymmetric factor (glum ) of -3.1 × 10-3 , which is induced by Ch-CDs. This is the first report of chiral perovskite which is induced by other chiral nanomaterials. By anion exchange, CPL can cover almost the entire visible light band. Surprisingly, the chiral signal of Ch-CDs-CsPbBr3  NCs is in-versed under excitation state, which can be induced by the charge transfers between Ch-CDs and perovskite NCs. The combination of perovskites and Ch-CDs pave away for the design of new chiral perovskite on multifunctional applications.

Photoluminescence mechanisms of red-emissive carbon dots derived from non-conjugated molecules.

Red-emissive carbon dots (R-CDs) have been widely studied because of their potential application in tissue imaging and optoelectronic devices. At present, most R-CDs are synthesized by using aromatic precursors, but the synthesis of R-CDs from non-aromatic precursors is challenging, and the emission mechanism remains unclear. Herein, different R-CDs were rationally synthesized using citric acid (CA), a prototype non-aromatic precursor, with the assistance of ammonia. Their structural evolution and optical mechanism were investigated. The addition of NH3·H2O played a key role in the synthesis of CA-based R-CDs, which shifted the emission wavelength of CA-based CDs from 423 to 667 nm. Mass spectrometry (MS) analysis indicated that the amino groups served as N dopants and promoted the formation of localized conjugated domains through an intermolecular amide ring, thereby inducing a significant emission redshift. The red-emissive mechanism of CDs was further confirmed by control experiments using other CA-like molecules (e.g., aconitic acid, tartaric acid, aspartic acid, malic acid, and maleic acid) as precursors. MS, nuclear magnetic resonance characterization, and computational modeling revealed that the main carbon chain length of CA-like precursors tailored the cyclization mode, leading to hexatomic, pentatomic, unstable three/four-membered ring systems or cyclization failure. Among these systems, the hexatomic ring led to the largest emission redshift (244 nm, known for CA-based CDs). This work determined the origin of red emission in CA-based CDs, which would guide research on the controlled synthesis of R-CDs from other non-aromatic precursors.

Anomalous Dynamics of Defect-Assisted Phonon Recycling in Few-Layer Mo0.5W0.5S2.

Alloying has emerged as a new strategy to tune the function of 2D transition metal dichalcogenides (TMDCs). However, the lack of research on the electrical and structural properties of these alloys limits their practical applications. Here, femtosecond transient absorption spectroscopy with pump pulse tunability is performed to elucidate the ultrafast carrier dynamics in the few-layer Mo0.5W0.5S2 prepared by the liquid phase exfoliation method. An anomalous rebleaching of the ground state is observed at high pump fluence by 3.1 eV excitation. We ascribe this rebleaching of the ground state to the mechanism that the carriers trapped in the defect are thermally excited back to the untrapped exciton state due to the phonon recycling, which hinders the dissipation of nonradiative energy, through comparative experiments and global analysis. Our findings demonstrate a novel energy transfer channel assisted by defect in few-layer TMDCs which is critical for their advanced applications.

Physical Insights on the Thermoelectric Performance of Cs2SnBr6 with Ultralow Lattice Thermal Conductivity.

This study has investigated the microscopic mechanisms of ultralow lattice thermal conductivity by the first-principles density functional theory. By solving the phonon Boltzmann equation iteratively, we find that the thermal conductivity of the lattice is abnormally low and that glass like heat transfer behavior occurs. Therefore, in addition to the contribution about the particle-like propagation to heat transport, the off-diagonal elements of the heat-flux operator through wave-like interbranch tunneling of phonon modes are also considered. The results provided new insights into the minimum thermal conductivity (κL) for Cs2SnBr6 (0.17 W m-1 K-1 at 450 K). It was also found that polar optical phonon scattering severely affects carrier lifetime. In addition, an impressive thermoelectric figure of merit of 0.55 at 450 K for Cs2SnBr6 was obtained in the case of doping p-type carriers. The study helps us understand the ultralow κL in complex crystals with strong anharmonicity and find that Cs2SnBr6 is a new and promising thermoelectric material.

Electron-phonon coupling-assisted universal red luminescence of o-phenylenediamine-based carbon dots.

Due to the complex core-shell structure and variety of surface functional groups, the photoluminescence (PL) mechanism of carbon dots (CDs) remain unclear. o-Phenylenediamine (oPD), as one of the most common precursors for preparing red emissive CDs, has been extensively studied. Interestingly, most of the red emission CDs based on oPD have similar PL emission characteristics. Herein, we prepared six different oPD-based CDs and found that they had almost the same PL emission and absorption spectra after purification. Structural and spectral characterization indicated that they had similar carbon core structures but different surface polymer shells. Furthermore, single-molecule PL spectroscopy confirmed that the multi-modal emission of those CDs originated from the transitions of different vibrational energy levels of the same PL center in the carbon core. In addition, the phenomenon of "spectral splitting" of single-particle CDs was observed at low temperature, which confirmed these oPD-based CDs were unique materials with properties of both organic molecules and quantum dots. Finally, theoretical calculations revealed their potential polymerization mode and carbon core structure. Moreover, we proposed the PL mechanism of red-emitting CDs based on oPD precursors; that is, the carbon core regulates the PL emission, and the polymer shell regulates the PL intensity. Our work resolves the controversy on the PL mechanism of oPD-based red CDs. These findings provide a general guide for the mechanism exploration and structural analysis of other types of CDs.

Pressure-Induced Restricting Intermolecular Vibration of a Herringbone Dimer for Significantly Enhanced Multicolor Emission in Rotor-Free Truxene Crystals.

Organic solid-state luminescent materials exhibit numerous exciting photoelectric properties that are central to emergent organic light-emitting diodes, smart sensors, and data encryption. However, the luminescence of pure organic rotor-free materials has been afflicted with strong intermolecular π-π stacking interactions. Herein, an unprecedented pressure-induced emission enhancement (PIEE) is realized in a system of rigid planar pure polycyclic aromatics, i.e., truxene crystals. The emission intensity is enhanced 7-fold below 3.0 GPa with a photoluminescence quantum yield increased to 10.17% compared with the initial value of 1.78%, and the emission colors change from green (520 nm) to red (640 nm) within 11.8 GPa. Spectral characterizations and first-principles calculations reveal that the PIEE and piezochromism can mainly be attributed to the restricted intermolecular vibration and the decreased energy gap. Our findings enrich the PIEE mechanism and provide a new guideline for designing pressure-responsive luminescent materials in advancing their photoelectric applications.