Unraveling Defect-Mediated Enhancement of Transient Photoconductivity and Slower Carrier's Mobility Decay in Cu-Doped Cs2AgBiBr6 Nanocrystals Using Ultrafast Pump-Probe Spectroscopy.

Lead-free double perovskite nanocrystals (A2B'(III)B″(I)X6 NCs) address the instability and toxicity concerns of lead-based counterparts, but their device performance is limited by subpar absorption and unexplored carrier dynamics. Impurity ion doping offers a route to tune electrical conductivity and charge carrier transport. Herein, we synthesized Cu-doped Cs2AgBiBr6 (CABB) nanocrystals using a hot-injection approach and investigated the charge carrier's dynamics through ultrafast pump-probe spectroscopy. Copper introduction into the CABB lattice enhanced absorption in the near-infrared region and introduced sub-band gap defect states in CABB NCs. The transient absorption study revealed a faster bleach decay with increased copper doping, as a result of charge transfer from the conduction band to copper defect states. Also, an optical pump terahertz probe study displays higher photoconductivity and mobility in Cu-doped CABB NCs. Slower mobility decay in Cu-doped systems was attributed to the charge carrier's entrapment at the defect state. These findings suggest that copper-doped CABB is a superior contender for optoelectronic applications over conventional CABB.

Unraveling the cation dependent carrier cooling and transient mobility in lead-free A3Sb2I9 perovskites.

Lead halide perovskites (LHPs) have gained prominence for their exceptional photophysical properties, holding promise for applications in high-end optoelectronic devices. However, the presence of lead is one of the major obstacles to the commercialization of LHPs in the field of photovoltaics. To address this, researchers have explored environment friendly lead-free perovskite solar cells by investigating non-toxic perovskite materials. This study explores the enhancement of photophysical properties through chemical engineering, specifically cation exchange, focusing on the crucial photophysical process of hot carrier cooling. Employing femtosecond transient absorption spectroscopy and optical pump terahertz probe spectroscopy, we have probed the carrier relaxation dynamics in A3Sb2I9 with cesium and rubidium cations. This study unravels that the carrier relaxation is found to be slower in Rb3Sb2I9; along with this, the transient mobility decay is found to be retarded. Overall, this study suggests that an antimony-based Rb3Sb2I9 perovskite could be a substantial lead-free perovskite in photovoltaics. These findings provide valuable insights into cation engineering strategies, aiming to improve the overall performance of lead-free-based photovoltaic devices.

Plasmon-Induced Ultrafast Hot Hole Transfer in Nonstoichiometric CuxInyS/CdS Heteronanocrystals.

Plasmonic semiconductors are promising candidates for developing energy conversion devices due to their tunable band gap, cost-effectiveness, and nontoxicity. Such materials exhibit remarkable capabilities for harvesting infrared photons, which constitute half of the solar energy spectrum. Herein, we have synthesized near-infrared (NIR) active CuxInyS nanocrystals and CuxInyS/CdS heterostructure nanocrystals (HNCs) to investigate plasmon-induced charge transfer dynamics on an ultrafast time scale. Employing femtosecond transient absorption spectroscopy, we demonstrate that upon exciting the HNCs with sub-band gap NIR photons (λ = 840 nm), the hot holes are generated in the valence band of plasmonic CuxInyS and transferred to the adjacent semiconductor. The decreased signal intensity and accelerated hole phonon relaxation dynamics for HNCs reveal efficient transfer of plasmon-induced hot carriers from CuxInyS to CdS under both 840 and 350 nm laser excitations, providing a pathway for enhanced carrier utilization. These findings shed light on the potential of ternary chalcogenides in plasmonic applications, highlighting efficient hot carrier extraction to adjacent semiconductors.

Novel Au/Cu2NiSnS4 Nano-Heterostructure: Synthesis, Structure, Heterojunction Band Offset and Alignment, and Interfacial Charge Transfer Dynamics.

Considering the importance of physics and chemistry at material interfaces, we have explored the coupling of multinary chalcogenide semiconductor Cu2NiSnS4 nanoparticles (CNTS NPs) for the first time with the noble metal (Au) to form Au-CNTS nano-heterostructures (NHSs). The Au-CNTS NHSs is synthesized by a simple facile hot injection method. Synergistic experimental and theoretical approaches are employed to characterize the structural, optical, and electrical properties of the Au-CNTS NHSs. The absorption spectra demonstrate enhanced and broadened optical absorption in the ultraviolet-visible-near-infrared (UV-Vis-NIR) region, which is corroborated by cyclic voltammetry (CV) readings. CV measurements show type II staggered band alignment, with a conduction band offset (CBO) of 0.21 and 0.23 eV at the Au-CNTS/CdS and CNTS/CdS interface, respectively. Complementary first-principles density functional theory (DFT) calculations predict the formation of a stable Au-CNTS NHSs, with the Au nanoparticle transferring its electrons to the CNTS. Moreover, our interface analysis using ultrafast transient absorption experiments demonstrate that the Au-CNTS NHSs facilitates efficient transport and separation of photoexcited charge carriers when compared to pristine CNTS. The transient measurements further reveal a plasmonic electronic transfer from the Au nanoparticle to CNTS. Our advanced analysis and findings will prompt investigations into new functional materials and their photo/electrocatalysis and optoelectronic device applications in the future.

Delineating the core and surface state heterogeneity of carbon dots during electron transfer.

Exploring the heterogeneity of carbon dots (C-Dots) is challenging because of the existence of complex structural diversity, and it is a demanding task for the development and designing of efficient C-Dots for various applications. Herein, we studied the role of the core state and surface state of C-Dots in heterogeneity via the successful investigation of the electron transfer (ET) process between different (blue, green, and red) emitting C-Dots and an electron acceptor methyl viologen (MV2+) using steady-state and time-resolved fluorescence and ultrafast transient absorption (TA) spectroscopic techniques. Selective excitation in the steady-state and time-resolved mode shows that the ET ability of the core state is higher than that of the surface state. Moreover, the kinetics of MV+˙ generation was probed using TA spectroscopy after the excitation of the core and surface state, where we observed that the surface state becomes less efficient due to the presence of an oxygen-containing functional group in the surface state, which acts as an electron scavenger. Moreover, the heterogeneity of the core and surface state was explored through the detection of the MV+˙ generation yield after the irradiation of UV and visible light (exciting the core and surface state). The result indicates that the graphitic nitrogen content in the core state and the oxygen-containing functional group in the surface state play an important role in the heterogeneity in the structure and the ET process. Our findings on the fundamental understanding of the heterogeneity of different emissive C-Dots will provide a new way of designing and developing a metal-free light-harvesting system.

Ultrafast Electron and Hole Transfer and Efficient Charge Separation in a Sb2Se3/CdS Thin Film p-n Heterojunction.

Harvesting solar energy for different applications requires the continuous development of new semiconducting materials to exploit a broad part of the solar spectrum. In this direction, antimony selenide (Sb2Se3) has attracted a tremendous amount of attention over the past few years as a light-harvesting material for photovoltaic device applications owing to its phase stability, high absorption coefficient, earth abundance, and low toxicity. Here, we have fabricated a high-quality heterojunction of a p-type Sb2Se3 film and an n-type CdS film using the thermal evaporation technique. The photocurrent of the heterosystem was significantly higher than that of the pristine materials. This optoelectronic response was investigated using femtosecond transient absorption (TA) spectroscopy. TA study reveals the existence of an instantaneous electron transfer from Sb2Se3 to CdS, accompanied by a substantial charge separation at the heterojunction. Our study deals with the investigation of a well-designed p-n device, paving the way for the fabrication of highly efficient photovoltaic devices.

Thermo-Chemical Cues-Mediated Strategy to Control Peptide Self-Assembly and Charge Transfer Complexation.

Peptide amphiphiles (PAs) are known for their remarkable ability to undergo molecular self-assembly, a process that is highly responsive to the local microenvironment. Herein, we design a pyrene tethered peptide amphiphile Py-VFFAKK, 1 that exhibits pathway-driven self-assembly from metastable nanoparticles to kinetically controlled nanofibers and thermodynamically stable twisted bundles upon modulations in pH, temperature, and chemical cues. The presence of the pyrene moiety ensures donation of the electron to an electron acceptor, namely, 7,7,8,8-tetracyanoquinodimethane (TCNQ), to form a supramolecular charge transfer complex in aqueous solution that was studied in detail with microscopic and spectroscopic techniques. Excitation of the donor species in its excimer state facilitates electron donation to the acceptor moiety, paving away a long-lived charge-separated state that persists for over a nanosecond, as ascertained through transient absorption spectroscopy. Finally, the self-assembled charge transfer complex is explored toward antimicrobial properties with Escherichia coli while maintaining biocompatibility toward L929 mice fibroblast cells.

Understanding the charge transfer dynamics of the Cu2WS4-CNT-FeOOH ternary composite for photo-electrochemical studies.

Ternary transition metal chalcogenide (Cu2WS4) is a semiconductor with a band gap of 2.1 eV and could be a promising candidate for photoelectrochemical water splitting and solar energy conversion applications. Despite numerous reports on ternary transition metal chalcogenides, this semiconductor's ultrafast charge transfer dynamics remain unknown. Here, we report on charge carrier dynamics in a pristine Cu2WS4 system with the aid of ultrafast transient (TA) pump-probe spectroscopy and a hot carrier transfer process from Cu2WS4 to multi-walled carbon nanotubes (CNTs) and FeOOH has been observed. Furthermore, we have explored Cu2WS4-FeOOH having a type-II composite for photo-electrochemical (PEC) water oxidation and modified this with the addition of multi-walled carbon nanotubes to expedite the charge-transfer processes and photo-anodic performance. The photo-electrochemical studies demonstrate that the Cu2WS4-CNT, Cu2WS4-FeOOH, and Cu2WS4-CNT-FeOOH provide nearly 3-, 8- and 12-fold enhancement in photocurrent density relative to the bare Cu2WS4 photo-anode at 1.23 V vs. RHE. These photo-electrochemical studies support the results obtained from the TA investigation and further prove the higher charge separation in the ternary composite system. These studies probe the excited states and provide evidence of longer charge separation in the binary and ternary composites, responsible for their remarkable photo-electrochemical performance.

Temperature dependent charge carrier dynamics in 2D ternary Cu2MoS4 nanoflakes: An effect of electron-phonon coupling.

Two-dimensional transition metal chalcogenides (2D TMCs) like MoS2, WS2 etc., have established significant dominance in the field of nanoscience and nanotechnology, owing to their unique properties like strong light-matter interaction, high carrier mobility, large photo-responsivity etc. Despite the widespread utilization of these binary TMCs, their potential in the advancement of the optoelectronic research is limited due to the constraints in band tuning and charge carrier lifetime. To overcome these limitations, ternary transition metal chalcogenides have emerged as promising alternatives. Although, the optical properties of these materials have never been explored properly. Herein, we have investigated one such promising member of this group, Cu2MoS4 (CMS) using both steady state and time-resolved spectroscopic techniques. The material exhibits a broad range of visible light absorption, peaking at 576 nm. Photoluminescence spectroscopy confirmed the presence of both band gap emission and trap state-mediated emissions. Transient absorption spectroscopy unraveled the excited state charge carrier dynamics of CMS in sub-ps timescale, upon irradiation of visible light. We found significant influence of the trap mediated recombination, while Auger process being dominant at high charge density. We extended our study in a wide temperature range (5-300 K), which reveals the impact of electron-phonon coupling strength on the band gap and charge carrier dynamics of this material. This detailed study would draw more attention toward the unexplored optical properties of ternary 2D chalcogenides and will open new avenues for the construction of 2D material-based optical devices.

Correction: Understanding the charge transfer dynamics of the Cu2WS4-CNT-FeOOH ternary composite for photo-electrochemical studies.

Correction for 'Understanding the charge transfer dynamics of the Cu2WS4-CNT-FeOOH ternary composite for photo-electrochemical studies' by Preeti Dagar et al., Phys. Chem. Chem. Phys., 2023, https://doi.org/10.1039/D3CP03498D.

Ultrafast Hole Migration at the p-n Heterojunction of One-Dimensional SnS Nanorods and Zero-Dimensional CdS Quantum Dots.

The p-n heterojunctions fabricated from one-dimensional (1D) p-type tin sulfide nanorods (SnS NRs) decorated with n-type zero-dimensional (0D) cadmium sulfide quantum dots (CdS QDs) have gained significant research attention in energy storage devices. Herein, we have successfully synthesized a 1D/0D SnS@CdS heterostructure (HS) using a hot injection method. Structural and morphological studies clearly suggest that CdS QDs are uniformly anchored on the surface of SnS NRs, resulting in intimate contact between two components. The photoluminescence (PL) study revealed the transfer of photoexcited holes from CdS QDs to SnS NRs, which was further confirmed by transient absorption (TA) studies. TA measurements demonstrate the hole transfer from the valence band of CdS QDs to SnS NRs and delocalization of electrons between the conduction band of SnS NRs and CdS QDs in SnS@CdS HS, resulting in efficient charge separation across the p-n heterojunction. These findings will open up a new paradigm for improving the efficiency of optoelectronic devices.

Ultrafast glimpses of the excitation energy-dependent exciton dynamics and charge carrier mobility in Cs2SnI6 nanocrystals.

Advancements in photovoltaic research suggest that tin-based perovskites are potential alternatives to traditional lead-based structures. Cs2SnI6, specifically, stands out as a notable candidate, exhibiting impressive performance. However, its complete potential remains untapped primarily owing to the limited understanding of its photophysics. In light of this, this study aims to bridge this knowledge gap. To commence our study, we first executed theoretical investigations to locate the energetically diverse excitons within the Brillouin zone. Building on this knowledge, we then utilized transient absorption spectroscopy to investigate their temporal evolution. Herein, we observed the formation of high-energy excitons even when the incident photon energy was below the necessary threshold, which is quite distinctive and intriguing. Of particular interest is the generation of ultraviolet (UV) domain exciton using visible photons, which implies that Cs2SnI6 has the potential for efficient solar light harvesting. Tracking the kinetics revealed that this unique finding arises due to the intertwined formation and decay pathways undertaken by the different excitons, aided by intervalley scattering and phonon absorption processes. In addition, we found that the decay of the UV exciton was unusually slow. Transient mobility investigations were undertaken to probe the carrier transport behavior that further established hot carriers (HCs) in Cs2SnI6 to be highly mobile and susceptible to polaron formation. Overall, our findings demonstrate that Cs2SnI6 is a strong candidate for HC-based photovoltaics because it possesses all the prerequisites desired for such applications.

Efficient Charge Transfer in the Perovskite Quantum Dot-Hemin Biocomposite: Is This Effective for Optoelectronic Applications?

Inorganic perovskite quantum dots (PQDs) have great potential for optoelectronic applications as a result of their tunable optical properties, significant absorption coefficient, and high mobility. Combining PQDs with molecular adsorbates offers exciting possibilities for future applications, making it important to study interfacial electron transfer in PQD-molecular composites. Here, we present a study of PQD and hemin composites (PQD-hemin) to understand how their interfacial electron transfer dynamics are affected by adsorbate and PQD properties. Our femtosecond ultrafast transient absorption and time-resolved photoluminescence (TRPL) studies reveal that hot carrier relaxation, charge separation, and charge recombination processes are significantly impacted in the PQD-hemin composite system under different excitations, both higher and lower energy. Additionally, our alternating current (AC)- and direct current (DC)-bias-driven electrical studies show that, despite efficient charge separation in the PQD-hemin composite system, the light-induced transient photocurrent drops. The findings on the PQD-molecular composite will give useful outlooks for designing a variety of optoelectronic devices.

Oligothiophene-Ring-Strapped Perylene Bisimides: Functionalizable Coaxial Donor-Acceptor Macrocycles.

Aesthetic designs from nature enable new knowledge to be gained and, at the same time, inspire scientific models. In this context, multicomponent macrocycles embody the advantage of precisely positioning the structural units to achieve efficient communication between them. However, the construction of a functionalizable macrocycle for ultrafast charge separation and stabilization has not been attempted. Herein, we report the synthesis, crystal structure, and transient absorption of a new functionalizable macrocycle consisting of an oligothiophene-ring-strapped perylene bisimide. Transient absorption results point to a sequential improvement in charge separation and stabilization from the macrocycle to the corresponding linear dimer and 2D polymer due to the unique design. Our macrocycle design with a supportive spatial arrangement of the donor and acceptor units will inspire the development of more complex synthetic systems with exciting electron-transfer and charge-separation features.

Temperature driven charge transfer process in quantum confined two-dimensional Mn-doped CsPbBr3 perovskite nanoplatelets.

A temperature dependent transient absorption study has been demonstrated for Mn2+ doped CsPbBr3 nanoplatelets. At 5 K, charge transfer is suppressed due to the trapping of charge carriers in defect states. By contrast, at 300 K, an efficient charge/energy transfer process is observed as the thermally active carriers become de-trapped from the defect states upon strong exciton-phonon coupling.

Efficient Hot Electron Transfer and Extended Separation of Charge Carriers at the 1P Hot State in Sb2Se3/CdSe p-n Heterojunction.

Utilization of hot carriers is very crucial in improving the efficiency of solar energy devices. In this work, we have fabricated an Sb2Se3/CdSe p-n heterojunction via a cation exchange method and investigated the possibility of hot electron transfer and relaxation pathways through ultrafast spectroscopy. The enhanced intensity of the CdSe hot excitonic (1P) bleach in the heterostructure system confirmed the hot electron transfer from Sb2Se3 to CdSe. Both the 1S and 1P signals are dynamically very slow in the heterosystem, validating this charge migration phenomenon. Interestingly, recovery of the 1P signal is much slower than that of 1S. This is very unusual as 1S is the lowest-energy state. This observation indicates the strength of hot electron transfer in this unique heterojunction, which helps in increasing the carrier lifetime in the hot state. Extended separation of charge carriers and enhanced hot carrier lifetime would be extremely helpful in extracting carriers and boost the performance of optoelectronic devices.

Ultrafast insights into full-colour light-emitting C-Dots.

Designing carbon dots (C-Dots) in a controlled way requires a profound understanding of their photophysical properties, such as the origin of their fluorescence and excitation wavelength-dependent emission properties, which has been a perennial problem in the last few decades. Herein, we synthesized three different C-Dots (blue, green, and red-emitting C-Dots) from the same starting materials via a hydrothermal method and separated them by silica column chromatography. All the purified C-Dots exhibited three different emission maxima after a certain range of different excitations, showing a high optical uniformity in their emission properties. It was also observed that the average distributions of the particle size in all the C-Dots were the same with a typical size of 4 nm and the same interplanar d spacing of ∼0.21 nm. Here, we tried to establish a well-defined conclusive answer to the puzzling optical properties of C-Dots via successfully investigating the carrier dynamics of their core and surface state with a myriad use of steady-state, time-resolved photoluminescence, and ultrafast transient absorbance spectroscopy techniques. The ultrafast charge-carrier dynamics of the core and surface state clearly indicated that the graphitic nitrogen in the core state and the oxygen-containing functional group in the surface state predominately contribute to controlling their wide range of emission properties. We believe that these findings will give the C-Dots their own designation in the fluorophore world and create a new avenue for designing and developing C-Dot-based new architectures.

Atomically thin 2D photocatalysts for boosted H2 production from the perspective of transient absorption spectroscopy.

Excited state photophysical processes play the most important role in deciding the efficiency of any photonic applications like solar light driven H2 evolution, which is considered to be the next big thing in the global search of renewable energy sources. Two-dimensional (2D) materials are getting enormous attention in the field of photocatalysis owing to their exquisite optical and catalytic properties, like high absorption coefficient, appropriate band positions, large specific surface area, high charge carrier mobility, etc. Considering the huge potential of these, many different approaches are being adapted to fabricate suitable photocatalytic systems for the efficient production of H2. Transient absorption spectroscopy (TAS) could be a great help in this regard, considering its efficacy in understanding any optical application. This perspective primarily deals with a few recent reports on 2D photocatalyst fabrication techniques using mechanistic insights from TAS. We have discussed the effect of doping, exfoliation and heterojunction fabrication on the photocatalytic activity of different 2D materials and explored the inherent photophysical phenomena influencing the optical behavior of these materials. A tentative future direction and possible challenges are also highlighted in this report. Overall, this unique perspective throws light on all the possible aspects of a 2D material, which are crucial and need to be addressed prior to fabrication of a photocatalyst and would be extremely helpful for the growth of the 2D photocatalytic field.

Probing the charge transfer mechanisms in type-II Cs2AgBiBr6-CdSe composite system: ultrafast insights.

Lead-free halide-based double perovskites (DPs) have established themselves as the emerging nontoxic alternatives for photovoltaic (PV) applications thus substituting the long-standing lead halide perovskites. Among the prospective lead-free DPs, Cs2AgBiBr6has gained immense popularity owing to the fascinating properties demonstrated by them including low carrier effective mass and microsecond lifetime for electron-hole recombination. Nevertheless, the large, indirect bandgap remains the prime hurdle that restrains commercialization of the Cs2AgBiBr6DPs based PV devices. A rational solution could be designing its heterostructure with another suitable material that could mitigate the inadequacies of Cs2AgBiBr6DPs. With this line of thought, herein we synthesized a composite of Cs2AgBiBr6DPs with CdSe NCs and then performed transient absorption (TA) spectroscopic measurements to introspect its photophysical aspects. Executing excitation energy-dependent studies clearly reveal the carrier transfer efficiency to be strongly pump-dependent. Upon exciting with 350 nm pump, in compliance with the energy band alignment and tendency of both the constituents to be photoexcited across their bandgap, there is a bidirectional transfer of hot electrons anticipated in the composite system. Nevertheless, the TA outcomes indicate the transfer of hot electrons from CdSe to Cs2AgBiBr6to be more favorable out of the bidirectional pathways. Employing further lower pump energies (480 nm) when only CdSe NCs are capable of being excited, the transfer efficiency of the electrons from CdSe to Cs2AgBiBr6is noticed to be fairly low. Besides this, when the pump wavelength is tuned to 530 nm i.e. quite close to the CdSe band edge, no electron transfer is noticeable despite the anticipation from thermodynamic feasibility. Thus, as reflected by the TA kinetics, electron transfer is discerned to be more efficient from the hot states rather than the band edges. Most advantageously, charge separation is successfully achieved in this never explored composite architecture which eases the carrier extraction and minimizes the otherwise prevalent fast recombination processes.

Chemically Engineered Avenues: Opportunities for Attaining Desired Carrier Cooling in Perovskites.

Hot carrier extraction-based devices are presently being persuaded as the most revolutionary means of surpassing the theoretical thermodynamic conversion efficiency limit (∼67 % for a model hot carrier solar cell). However, for practical realisation, there stand various hurdles that need to be surmounted, a major among all being the rapid hot carrier cooling rate. Though, the perovskite family has already demonstrated itself to exhibit slower cooling in contrast to the prototypical semiconductors. Decelerating this entire process of cooling further can prove to be a crucial stride in this regard. Quite contrarily, for the optoelectronic applications the situation is entirely conflicting where quick rate of cooling is a chief prerequisite. In the recent times, there have been various key developments that have targeted altering this cooling rate by various chemically engineered strategies. This review highlights such blueprints that can be utilized towards the advantageous alteration of the carrier cooling in accordance with the device requirements.