Stimulating Phonon Bottleneck Effect in Organic Semiconductors by Charge-Transfer-Mediated J-Aggregation.

Hot carriers rapidly lose kinetic energies on a subpicosecond time scale, posing significant limitations on semiconductors' photon-conversion efficiencies. To slow the hot carrier cooling, the phonon bottleneck effect is constructed prevalently in quantum-confined structures with discrete energy levels. However, the maximum energy separation (ΔEES) between the energy levels is in a range of several hundred meV, leading to unsatisfactory cooling time. To address this, we design a novel organic semiconductor capable of forming intermolecular charge transfer (CT) in J-aggregates, where the lowest singlet excited state (S1) splits into two states due to the significant interplay between the Coulomb interaction and intermolecular CT coupling. The ΔEES between the two states can be adjusted up to 1.02 eV, and an extremely slow carrier cooling process of ∼72.3 ps was observed by femtosecond transient absorption spectroscopy. Moreover, the phonon bottleneck effect was identified in organic materials for the first time, and CT-mediated J-aggregation with short-range interactions was found to be the key to achieving large ΔEES. The significantly prolonged carrier cooling time, compared to <100 fs in the isolated molecule (10-6 M), highlights the potential of organic molecules with diversified aggregation structures in achieving long-lived hot carriers. These findings provide valuable insights into the intrinsic photophysics of electron-phonon scattering in organic semiconductors.

Obtaining Ligand-Free Aqueous Au-Nanoparticles Using Reversible CsPbBr3 ↔ Au@CsPbBr3 Nanocrystal Transformation.

Water-hexane interfacial preparation of photostable Au@CsPbBr3 (Au@CPB) hybrid nanocrystals (NCs) from pure CsPbBr3 (CPB) NCs is reported, with the coexistence of exciton and localized surface plasmon resonance with equal dominance. This enables strong exciton-plasmon coupling in these plasmonic perovskite NCs where not only the photoluminescence is quenched intrinsically due to ultrafast charge separation, but also the light absorption property increases significantly, covering the entire visible region. Using a controlled interfacial strategy, a reversible chemical transformation between CPB and Au@CPB NCs is shown, with the simultaneous eruption of larger-size ligand-free aqueous Au nanoparticles (NPs). An adsorption-desorption mechanism is proposed for the reversible transformation, while the overgrowth reaction of the Au NPs passes through the Au aggregation intermediate. This study further shows that the plasmonic Au@CPB hybrid NCs as well as ligand-free Au NPs exhibit clear surface enhanced Raman scattering (SERS) effect of a commercially available probe molecule. Overall, the beautiful interfacial chemistry delivers two independent plasmonic materials, i.e., Au@CPB NCs and ligand-free aqueous Au NPs, which may find important implications in photocatalytic and biomedical applications.

Ultrafast electron shuttling suppresses the energy transfer process in Mn-doped CsPbCl3 nanocrystals.

Taking advantage of the slow exciton-to-dopant energy transfer process, we dissociated the exciton in Mn-doped perovskite via ultrafast electron shuttling to a surface adsorbed 4-nitro phenol molecule. The observed ultrafast electron transfer process is competitive to the ultrafast exciton scattering process (∼140 fs) to the continuum states via optical phonons, but three-orders faster than the exciton-to-Mn energy transfer timescale.

Water-Triggered Chemical Transformation of Perovskite Nanocrystals.

Recently emerged lead-halide perovskite nanocrystals (PNCs) are promising optoelectronic material due to their easy solution processability, wide range of color tunability, as well as very high photoluminescence quantum yield. Despite their significant success in lab-scale optoelectronic applications, the long-term stability becomes the main issue, hindering them towards commercialization. The highly ionic nature of such lead-halide structure makes them extremely unstable in water and air. But a very few groups have taken the advantage of such nature of the crystal structure for water-triggered chemical transformation towards shape, composition, and morphology controlled stable and bright PNCs, which are otherwise difficult to obtain by typical direct approach. Furthermore, using polymer as an encapsulating layer for the PNCs, water-soluble stable PNCs have been prepared. In this review, the recent progress on the water-hexane interface chemistry towards chemical transformation to produce several PNCs is described. Such method not only ensure to yield several shape-controlled perovskites nanocrystals, but also formation of perovskites in aqueous phase that show promising application towards bio-imaging.

Breaking AgInTe2 Quantum Dot Chain to Fabricate AgInTe2-ZnS Janus Nanocrystals.

Colloidal multinary chalcogenides (MnCs) have emerged as excellent optoelectronic materials, where S- and Se-based MnCs show considerable progress; however, the Te counterpart suffers from detrimental surface oxidation. Moreover, Te-based I-III-VI MnCs (e.g., AgInTe2) tend to form a one-dimensional (1-D) anisotropic structure via the self-assembly of surface-oxidized Te, thus restricting the isolation of AgInTe2 quantum dots (QDs). We report successful control of the self-assembly of Te-based MnCs to arrest the growth of AgInTe2 QDs by using a synergistic capping agent (dodecanethiol and oleic acid). The reaction proceeds with several intermediates, including hexagonal microrods (MR), tetragonal QDs in a chain arrangement, and tetragonal MRs. Importantly, we note that the incorporation of ZnS QDs triggers the breaking of the chain arrangement of the AgInTe2 QDs and the emergence of evenly distributed AgInTe2-ZnS Janus nanocrystals with significantly reduced long-term Te-oxidative properties. Arresting the AgInTe2 QD chain and the subsequent Janus nanocrystal formation could have promising opportunities for 1-D charge hopping and efficient charge transport for optoelectronic applications, respectively.

Interfacial band offset engineering with barium-doping towards enhanced performance of all inorganic CsPbI2Br perovskite solar cells.

This study investigates the incorporation of Ba2+ at a low concentration into CsPbI2Br, resulting in the formation of mixed CsPb1-xBaxI2Br perovskite films. Photovoltaic devices utilizing these Ba-doped CsPbI2Br (Ba-CsPbI2Br) perovskite films achieved a higher stabilized power conversion efficiency of 14.07% compared to 11.60% for pure CsPbI2Br films. First-principles density functional theory calculations indicate that the improved device performance can be attributed to the efficient transport of conduction electrons across the interface between Ba-CsPbI2Br and the TiO2 electron transporting layer (ETL). The Ba-CsPbI2Br/TiO2 interface exhibits a type-II staggered band alignment with a smaller conduction band offset (CBO) of 0.25 eV, in contrast to the CsPbI2Br/TiO2 interface with a CBO of 0.48 eV. The reduced CBO at the Ba-CsPbI2Br/TiO2 interface diminishes the barrier for conduction electrons to transfer from the Ba-CsPbI2Br layer to the TiO2 layer, facilitating efficient charge transport.

Confined Excitons in Spherical-Like Halide Perovskite Quantum Dots.

Quantum dots (QDs) offer unique physical properties and novel application possibilities like single-photon emitters for quantum technologies. While strongly confined III-V and II-VI QDs have been studied extensively, their complex valence band structure often limits clear observations of individual transitions. In recently emerged lead-halide perovskites, band degeneracies are absent around the bandgap reducing the complexity of optical spectra. We show that for spherical-like CsPbBr3 QDs with diameters >6 nm, excitons confine with respect to their center-of-mass motion leading to well-pronounced resonances in their absorption spectra. Optical pumping of the lowest-confined exciton with femtosecond laser pulses not only bleaches all excitons but also reveals a series of distinct induced absorption resonances which we attribute to exciton-to-biexciton transitions and are red-shifted by the biexciton binding energy (∼40 meV). The temporal dynamics of the bleached excitons further support our exciton confinement model. Our study provides the first insight into confined excitons in CsPbBr3 QDs and gives a detailed understanding of their linear and nonlinear optical spectra.

Simultaneous Hydrogen Generation and Exciplex Stimulated Emission in Photobasic Carbon Dots.

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps-to-ns timescales, is much faster than proton delivery (∼µs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady-state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four-level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.

Ultrafast proton transfer of the aqueous phenol radical cation.

Proton transfer (PT) reactions are fundamental to numerous chemical and biological processes. While sub-picosecond PT involving electronically excited states has been extensively studied, little is known about ultrafast PT triggered by photoionization. Here, we employ femtosecond optical pump-probe spectroscopy and quantum dynamics calculations to investigate the ultrafast proton transfer dynamics of the aqueous phenol radical cation (PhOH˙+). Analysis of the vibrational wave packet dynamics reveals unusually short dephasing times of 0.18 ± 0.02 ps and 0.16 ± 0.02 ps for the PhOH˙+ O-H wag and bend frequencies, respectively, suggestive of ultrafast PT occurring on the ∼0.1 ps timescale. The reduced potential energy surface obtained from ab initio calculations shows that PT is barrierless when it is coupled to the intermolecular hindered translation between PhOH˙+ and the proton-acceptor water molecule. Quantum dynamics calculations yield a lifetime of 193 fs for PhOH˙+, in good agreement with the experimental results and consistent with the PT reaction being mediated by the intermolecular O⋯O stretch. These results suggest that photoionization can be harnessed to produce photoacids that undergo ultrafast PT. In addition, they also show that PT can serve as an ultrafast deactivation channel for limiting the oxidative damage potential of radical cations.

Interfacial Manganese-Doping in CsPbBr3 Nanoplatelets by Employing a Molecular Shuttle.

Mn-doping in cesium lead halide perovskite nanoplatelets (NPls) is of particular importance where strong quantum confinement plays a significant role towards the exciton-dopant coupling. In this work, we report an immiscible bi-phasic strategy for post-synthetic Mn-doping of CsPbX3 (X=Br, Cl) NPls. A systematic study shows that electron-donating oleylamine acts as a shuttle ligand to transport MnX2 through the water-hexane interface and deliver it to the NPls. The halide anion also plays an essential role in maintaining an appropriate radius of Mn2+ and thus fulfilling the octahedral factor required for the formation of perovskite crystals. By varying the thickness of parent NPls, we can tune the dopant incorporation and, consequently, the exciton-to-dopant energy transfer process in doped NPls. Time-resolved optical measurements offer a detailed insight into the exciton-to-dopant energy transfer process. This new approach for post-synthetic cation doping paves a way towards exploring the cation exchange process in several other halide perovskites at the polar-nonpolar interface.

Observation of intra- and intermolecular vibrational coherences of the aqueous tryptophan radical induced by photodetachment.

The study of the photodetachment of amino acids in aqueous solution is pertinent to the understanding of elementary processes that follow the interaction of ionizing radiation with biological matter. In the case of tryptophan, the tryptophan radical that is produced by electron ejection also plays an important role in numerous redox reactions in biology, although studies of its ultrafast molecular dynamics are limited. Here, we employ femtosecond optical pump-probe spectroscopy to elucidate the ultrafast structural rearrangement dynamics that accompany the photodetachment of the aqueous tryptophan anion by intense, ∼5-fs laser pulses. The observed vibrational wave packet dynamics, in conjunction with density functional theory calculations, identify the vibrational modes of the tryptophan radical, which participate in structural rearrangement upon photodetachment. Aside from intramolecular vibrational modes, our results also point to the involvement of intermolecular modes that drive solvent reorganization about the N-H moiety of the indole sidechain. Our study offers new insight into the ultrafast molecular dynamics of ionized biomolecules and suggests that the present experimental approach can be extended to investigate the photoionization- or photodetachment-induced structural dynamics of larger biomolecules.

Manganese-Doping-Induced Quantum Confinement within Host Perovskite Nanocrystals through Ruddlesden-Popper Defects.

The concept of doping Mn2+ ions into II-VI semiconductor nanocrystals (NCs) was recently extended to perovskite NCs. To date, most studies on Mn2+ doped NCs focus on enhancing the emission related to the Mn2+ dopant via an energy transfer mechanism. Herein, we found that the doping of Mn2+ ions into CsPbCl3 NCs not only results in a Mn2+ -related orange emission, but also strongly influences the excitonic properties of the host NCs. We observe for the first time that Mn2+ doping leads to the formation of Ruddlesden-Popper (R.P.) defects and thus induces quantum confinement within the host NCs. We find that a slight doping with Mn2+ ions improves the size distribution of the NCs, which results in a prominent excitonic peak. However, with increasing the Mn2+ concentration, the number of R.P. planes increases leading to smaller single-crystal domains. The thus enhanced confinement and crystal inhomogeneity cause a gradual blue shift and broadening of the excitonic transition, respectively.

An Insight into the Interface through Excited-State Carrier Dynamics for Promising Enhancement of Power Conversion Efficiency in a Mn-Doped CdZnSSe Gradient Alloy.

To explore the significance of impurity doping in power conversion efficiency, quaternary gradient CdZnSSe alloy nanocrystals (NCs) and its Mn-doped analogues were synthesized by high-temperature pyrolysis. The undoped and Mn-doped CdZnSSe alloy NCs have been characterized by employing high-resolution TEM, X-ray diffraction, energy-dispersive X-ray spectroscopy, and electron paramagnetic resonance spectroscopy measurements. A low-temperature injection of chalcogens led to a gradient interface in the alloy, comprised of a CdSe/CdS/ZnSe/ZnS nanostructure. Both steady-state and ultrafast time-resolved absorption studies suggested the formation of a charge-transfer (CT) state due to the inner quasi-type II CdSe/CdS part of the gradient CdZnSSe alloy NCs, in which electrons are delocalized throughout the conduction band (CB) of both CdSe and CdS. The CT-state bleach recovery kinetics gave an additional slow electron cooling component (8 ps) in the undoped alloy NCs, which has been assigned to electron equilibration in the delocalized CB before recombination (or trapping). Interestingly, in the presence of dopant Mn, the slow electron cooling component became even more sluggish at 10 ps due to Mn-mediated electron cooling, in which Mn acts as an electron storage center. An unprecedented increase in the photocurrent conversion efficiency (PCE) of approximately 30 % from (3.3±0.11) to (4.29±0.07) % was observed in the Mn-doped gradient alloy compared with the undoped alloy.

Tuning Hole and Electron Transfer from Photoexcited CdSe Quantum Dots to Phenol Derivatives: Effect of Electron-Donating and -Withdrawing Moieties.

Charge-transfer processes from photoexcited CdSe quantum dots (QDs) to phenol derivatives with electron- donating (4-methoxy) and -withdrawing (4-nitro) moieties have been demonstrated by using steady-state and time- resolved emission and femtosecond transient absorption spectroscopy. Steady-state and time-resolved emission studies suggest that in the presence of both 4-nitrophenol (4NP) and 4-methoxyphenol (4MP) CdSe QDs luminescence is quenched. Stern-Volmer analysis suggests both static and dynamic mechanisms are active for both the QD/phenol composites. Cyclic voltammetric analysis recommends that photoexcited CdSe QDs can donate electrons to 4NP and holes to 4MP. To reconfirm both electron- and hole-transfer mechanisms, CdSe/CdS quasi-type II and CdSe/CdTe type II core-shell nanocrystals were synthesized and photoluminescence quenching was monitored in the absence and presence of both 4NP and 4MP, for which hole and electron transfer were systematically restricted. Results suggest that indeed electron and hole transfer take place from photoexcited CdSe to 4NP and 4MP, respectively. To monitor the charge-transfer dynamics in both systems on an early timescale, femtosecond transient absorption spectroscopic techniques have been employed. Electron and hole transfer and charge-recombination dynamics are discussed and the effect of electron-donating and -withdrawing groups has been demonstrated.

Effect of Molecular Coupling on Ultrafast Electron-Transfer and Charge-Recombination Dynamics in a Wide-Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes.

Wide-band-gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge-transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower-like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340 nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge-transfer complexes with the ZnS NCs, with the appearance of a red-shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady-state and time-resolved emission studies. To unravel charge-transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM-sensitized ZnS NCs. The electron-injection dynamics is pulse-width-limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above-mentioned processes are discussed.

Restriction of molecular twisting on a gold nanoparticle surface.

To understand the photophysical properties of intramolecular charge transfer (ICT) and twisted intramolecular charge transfer (TICT) states on a gold nanoparticle (Au NP) surface, we have designed and synthesized a new coumarin molecule (C3) that exists both as ICT and TICT states in its excited state in a polar environment. On a Au NP surface, an excited C3 molecule only exists as an ICT state owing to restricted molecular rotation of a diethylamino group; as a result, no conversion from the ICT to TICT state was observed. Selection of the preferential state of a molecule with dual emitting states can be helpful for selected biological applications.

Super sensitization: grand charge (hole/electron) separation in ATC dye sensitized CdSe, CdSe/ZnS type-I, and CdSe/CdTe type-II core-shell quantum dots.

Ultrafast charge-transfer dynamics has been demonstrated in CdSe quantum dots (QD), CdSe/ZnS type-I core-shell, and CdSe/CdTe type-II core-shell nanocrystals after sensitizing the QD materials by aurin tricarboxylic acid (ATC), in which CdSe QD and ATC form a charge-transfer complex. Energy level diagrams suggest that the conduction and valence band of CdSe lies below the LUMO and the HOMO level of ATC, respectively, thus signifying that the photoexcited hole in CdSe can be transferred to ATC and that photoexcited ATC can inject electrons into CdSe QD, which has been confirmed by steady state and time-resolved luminescence studies and also by femtosecond time-resolved absorption measurements. The effect of shell materials (for both type-I and type-II) on charge-transfer processes has been demonstrated. Electron injection in all the systems were measured to be <150 fs. However, the hole transfer time varied from 900 fs to 6 ps depending on the type of materials. The hole-transfer process was found to be most efficient in CdSe QD. On the other hand, it has been found to be facilitated in CdSe/CdTe type-II and retarded in CdSe/ZnS type-I core-shell materials. Interestingly, electron injection from photoexcited ATC to both CdSe/CdTe type-II and CdSe/ZnS type-I core-shell has been found to be more efficient as compared to pure CdSe QD. Our observation suggests the potential of quantum dot core-shell super sensitizers for developing more efficient quantum dot solar cells.

Extensive reduction in back electron transfer in twisted intramolecular charge-transfer (TICT) coumarin-dye-sensitized TiO(2) nanoparticles/film: a femtosecond transient absorption study.

We report the synthesis, characterization, and optical and electrochemical properties of two structurally similar coumarin dyes (C1 and C2). These dyes have been deployed as sensitizers in TiO2 nanoparticles and thin films, and the effect of molecular structure on interfacial electron-transfer dynamics has been studied. Steady-state optical absorption, emission, and time-resolved emission studies on both C1 and C2, varying the polarity of the solvent and the solution pH, suggest that both photoexcited dyes exist in a locally excited (LE) state in solvents of low polarity. In highly polar solvents, however, C1 exists in an intramolecular charge-transfer (ICT) state, whereas C2 exists in both ICT and twisted intramolecular charge-transfer (TICT) states, their populations depending on the degree of polarity of the solvent and the pH of the solution. We have employed femtosecond transient absorption spectroscopy to monitor the charge-transfer dynamics in C1- and C2-sensitized TiO2 nanoparticles and thin films. Electron injection has been confirmed by direct detection of electrons in the conduction band of TiO2 nanoparticles and of radical cations of the dyes in the visible and near-IR regions of the transient absorption spectra. Electron injection in both the C1/TiO2 and C2/TiO2 systems has been found to be pulse-width limited (<100 fs); however, back-electron-transfer (BET) dynamics has been found to be slower in the C2/TiO2 system than in the C1/TiO2 system. The involvement of TICT states in C2 is solely responsible for the higher electron injection yield as well as the slower BET process compared to those in the C1/TiO2 system. Further pH-dependent experiments on C1- and C2-sensitized TiO2 thin films have corroborated the participation of the TICT state in the slower BET process in the C2/TiO2 system.

Reversible CsPbBr3 ↔ CsPb2Br5 Transformation via Reverse Micellar Aqueous Solution.

Lead halide perovskites suffer from water and moisture instability due to the highly ionic nature of the crystal structures, though a few groups took advantage of it for chemical transformation via water-assisted strategy. However, direct exposure of the perovskite to bulk water leads to uncontrolled chemical transformation. Here, we report a controlled chemical transformation of CsPbBr3 to CsPb2Br5 triggered by nanoconfined water by placing CsPbBr3 in the nonpolar phase within a reverse micelle. The chemical transformation reaction is probed by using steady-state and time-resolved optical spectroscopy. We observe absorption and photoluminescence in the UV region stemming clearly from the CsPb2Br5 phase upon interaction with the reverse micellar aqueous solution. Transmission electron microscopy and X-ray diffraction measurements further provided the structure and morphology. Our results direct the formation of CsPbBr3-CsPb2Br5 nanocomposite under dry conditions while the chemically transformed CsPb2Br5 phase exists only in moist conditions, which we explain via the CsBr-stripping mechanism.

CuInS2-Decorated Perovskite Nanoarchitecture: Halide-Driven Energy and Electron Transfer.

Perovskite nanocrystals (NCs) are an emergent and game-changing entrant in semiconductor research, yet the research on the corresponding nanoheterostructures remains in its infancy. In this work, we fabricate a type II nanoarchitecture of CsPbX3 NCs (where X = Cl, Br, or I) and CuInS2 quantum dots to investigate the energy and charge transfer (ET and CT, respectively) processes. Optical measurements of CsPbX3/CuInS2 show efficient photoluminescence (PL) quenching when X = Br or I, while the PL quenching efficiency of the X = Cl compound is 2 orders of magnitude lower. We argue the drastic PL quenching in the X = I compound is solely due to the CT process, while for the X = Br compound, a predominantly ET process is active. In contrast to the driving force (-ΔG) for the CT process, we observe the reverse order of the electron transfer process, for which we propose the electron transfer occurs in the Marcus inverted region. Our halide-dependent controlled regulation of CT and ET processes in these nanoarchitectures may find promising optoelectronic applications.