Interplay between photoinduced charge and energy transfer in manganese doped perovskite quantum dots.

A comprehensive study on the photo-excited relaxation dynamics in semiconducting perovskite quantum dots (PQDs) is pivotal in realizing their extensive potential for optoelectronics applications. Among different competing photoinduced relaxation kinetics, energy transfer and charge transfer (CT) in PQDs need special attention, as they often influence the device efficacy, particularly with the donor-acceptor hybrid architecture. In this work, we explore a detailed investigation into photoinduced CT dynamics in mixed halide undoped CsPb(Br/Cl)3 and Mn2+ doped CsPb(Br/Cl)3 PQDs with a quinone molecule, p-benzoquinone (BQ). The energy level alignment of undoped PQDs with BQ allows an efficient CT, whereas Mn2+ doping reduces the CT efficiency, experiencing a competition between energy transfer from host to dopant and CT to BQ. The conductive atomic force microscopy measurements unveil a direct correlation with the spectroscopic studies by showing a significant improvement in the conductance of undoped PQDs in the presence of BQ, while an inappreciable change is observed for doped PQDs. A much-reduced transition voltage and barrier height in the presence of BQ further validate faster CT for undoped PQD than the doped one. Furthermore, Mn2+ doping in PQDs is observed to enhance their stability, showing better air and thermal stability compared to their undoped counterparts. These results reveal that doping strategy can regulate the CT dynamics in these PQDs and increase their stability, which will be beneficial for the development of desired optoelectronic devices with long-term stability.

Modulation of carrier conduction in CsPbBr3 perovskite quantum dots with band-aligned electron and hole acceptors.

The lead halide perovskites have emerged as promising materials with intriguing photo-physical properties and have immense potential for photovoltaic applications. A comprehensive study on the kinetics of charge carrier (electron/hole) generation and transfer across the interface is key to realizing their future scope for efficient device engineering. Herein, we investigate the interfacial charge transfer (CT) dynamics in cesium lead halide (CsPbBr3) perovskite quantum dots (PQDs) with energetically favorable electron acceptors, anthraquinone (AQ) and p-benzoquinone (BQ), and hole acceptors such as pyrene and 4-(dimethylamino)pyridine (DMAP). With various steady-state and time-resolved spectroscopic and microscopic measurements, a faster electron transfer rate is estimated for CsPbBr3 PQDs with BQ compared to that of AQ, while a superior hole transfer for DMAP is divulged compared to pyrene. In concurrence with the spectroscopic measurements, conducting atomic force microscopic studies across the electrode-PQD-electrode junction reveals an increment in the conductance of the PQD in the presence of both the electron and hole acceptors. The variation of the density of states calculation in the presence of the hole acceptors offers strong support and validation for faster CT efficiency. The above findings suggest that a careful selection of simple yet efficient molecular arrangements can facilitate rapid carrier transfer, which can be designed as auxiliary layers for smooth CT and help in the engineering of cost-effective photovoltaic devices.

Unraveling the Relevance of Electron and Hole Transfer in Lead Halide Perovskite Nanocrystals on Current Conduction.

Optimization of perovskite-based optoelectronic performance demands prudent engineering in the device architecture with facile transport of generated charge carriers. Herein, we explore the charge transfer (CT) kinetics in perovskite nanocrystals (PNCs), CsPbBr3, with two redox-active quinones, menadione (MD) and anthraquinone (AQ), and its alteration in halide exchanged CsPbCl3. With a series of spectroscopic and microscopic measurements, we infer that both electron and hole transfer (ET-HT) prevail in CsPbCl3 with quinones, resulting in a faster CT, while ET predominates for CsPbBr3. Furthermore, current-sensing atomic force microscopy measurements demonstrate that the conductance across a metal-PNC-metal nanojunction is improved in the presence of quinones. The contributions of ET and HT to current conduction across PNCs are well supported and validated by theoretical calculations of the density of states. These outcomes convey a new perspective on the relevance of ET and HT in the optimal current conduction and optoelectronic device engineering of perovskites.

Deciphering the Relevance of Quantum Confinement in the Optoelectronics of CsPbBr3 Perovskite Nanostructures.

Perovskites (PVKs) have emerged as an exciting class of semiconducting materials owing to their magnificent photophysical properties and been used in solar cells, light-emitting diodes, photodetectors, etc. The growth of multidimensional nanostructures has revealed many exciting alterations in their optoelectronic properties compared to those of their bulk counterparts. In this work, we have spotlighted the influence of quantum confinement in CsPbBr3 PVKs like the quantum dot (PQD), nanoplatelet (PNPL), and nanorod (PNR) on their charge transfer (CT) dynamics with 1,4-naphthoquinone (NPQ). The energy band alignment facilitates the transfer of both electrons and holes in the PNPL to NPQ, enhancing its CT rate, while only electron transfer in the PQD and PNR diminishes CT. The tunneling current across a metal-nanostructure-metal junction for the PNPL is observed to be higher than others. The higher exciton binding energy in the PNPL results in efficient charge transport by enhancing the mobility of the excited-state carrier and its lifetime compared to those of the PNR and PQD.

Förster Resonance Energy Transfer Assisted Enhancement in Optoelectronic Properties of Metal Halide Perovskite Nanocrystals.

Regulated excited state energy and charge transfer play a pivotal role in nanoscale semiconductor device performance for efficient energy harvesting and optoelectronic applications. Herein, we report the influence of Förster resonance energy transfer (FRET) on the excited-state dynamics and charge transport properties of metal halide perovskite nanocrystals (PNCs), CsPbBr3, and its anion-exchanged counterpart CsPbCl3 with CdSe/ZnS quantum dots (QDs). We report a drop in the FRET efficiency from ∼85% (CsPbBr3) to ∼5% (CsPbCl3) with QDs, inviting significant alteration in their charge transport properties. Using two-probe measurements we report substantial enhancement in the current for the blend structure of PNCs with QDs, originating from the reduced trap sites, compared to that of the pristine PNCs. The FRET-based upshot in the conduction mechanism with features of negative differential resistance and negligible hysteresis for CsPbBr3 PNCs can add new directions to high performance-based photovoltaics and optoelectronics.

Tunable Conductance of MoS2 and WS2 Quantum Dots by Electron Transfer with Redox-Active Quinone.

Due to their uniqueness in tunable photophysics, transition metal dichalcogenide (TMD) based quantum dots (QDs) have emerged as the next-generation quantum materials for technology-based semiconductor applications. This demands frontline research on the rational synthesis of the TMD QDs with controlled shape, size, nature of charge migration at the interface, and their easy integration in optoelectronic devices. In this article, with a controlled solution-processed synthesis of MoS2 and WS2 QDs, we demonstrate the disparity in their structural, optical, and electrical characteristics in bulk and confinement. With a series of steady-state and time-resolved spectroscopic measurements in different media, we explore the uncommon photophysics of MoS2 and WS2 QDs such as excitation-dependent photoluminescence and assess their excited state charge transfer kinetics with a redox-active biomolecule, menadione (MQ). In comparison to the homogeneous aqueous medium, photoinduced charge transfer between the QDs and MQ becomes more plausible in encapsulated cetyltrimethylammonium bromide (CTAB) micelles. Current sensing atomic force microscopy (CS-AFM) measurements at a single molecular level reveal that the facilitated charge transfer of QDs with MQ strongly correlates with an enhancement in their charge transport behavior. An increase in charge transport further depends on the density of states of the QDs directing a change in Schottky emission to Fowler-Nordheim (FN) type of tunneling across the metal-QD-metal junction. The selective response of the TMD QDs while in proximity to external molecules can be used to design advanced optoelectronic devices and applications involving rectifiers and tunnel diodes for future quantum technology.

Metal nanoparticle alters adenine induced charge transfer kinetics of vitamin K3 in magnetic field.

In this article, we highlight the alterations in the photoinduced electron transfer (ET) and hydrogen atom transfer (HAT) pathways between an anti-tumor drug vitamin-K3 (MQ) and a nucleobase adenine (ADN) in the presence of gold (Au) and iron (Fe) nanoparticles (NPs). Inside the confined micellar media, with laser flash photolysis corroborated with an external magnetic field (MF), we have detected the transient geminate radicals of MQ and ADN, photo-generated through ET and HAT. We observe that the presence of AuNP on the MQ-ADN complex (AuMQ-ADN) assists HAT by limiting the ET channel, on the other hand, FeNP on the MQ-ADN complex (FeMQ-ADN) mostly favors a facile PET. We hypothesize that through selective interactions of the ADN molecules with AuNP and MQ molecules with FeNP, a preferential HAT and PET process is eased. The enhanced HAT and PET have been confirmed by the escape yields of radical intermediates by time-resolved transient absorption spectroscopy in the presence of MF.