ABSTRACT
In this study, ultrafast transient absorption spectroscopy (TAS) is utilized to examine the excited-state dynamics in methylammonium lead iodide/bromide (MAPb(I1-xBrx)3) perovskites as a function of bromide content. TAS spectral behavior reveals characteristic lifetimes for thermalization, recombination, and charge carrier injection of MAPb(I1-xBrx)3 from x = 0 to 0.3 infiltrated in mesoporous titania films. Carrier recombination and charge injection lifetimes demonstrated a discernable increase with Br content likely because high carrier populations are supported by the higher density of vacant electronic states in mixed-halide perovskites due to the increased capacity of the conduction band. However, we observe for the first time that carrier thermalization lifetimes significantly decrease with increasing Br. This suggests that the shift in crystal structure from tetragonal towards pseudocubic accelerates carrier cooling, resulting in the relief of the hot phonon bottleneck. Furthermore, the stabilized MAPb(I1-xBrx)3 samples exhibit a lower Burstein-Moss shift of 0.07-0.08 eV compared to pure MAPbI3 (0.12 eV). Our results provide evidence that Br inclusion contributes to a broadening of the parabolic conduction band and to improvement in electron-phonon coupling and phonon propagation in the lattice.
ABSTRACT
In this work, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr3) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3 perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.
ABSTRACT
In this work, we demonstrate controlled drug delivery from low-temperature-sensitive liposomes (LTSLs) mediated by photothermal heating from multibranched gold nanoantennas (MGNs) in triple-negative breast cancer (TNBC) cells in vitro. The unique geometry of MGNs enables the generation of mild hyperthermia (â¼42 °C) by converting near-infrared light to heat and effectively delivering doxorubicin (DOX) from the LTSLs in breast cancer cells. We confirmed the cellular uptake of MGNs by using both fluorescence confocal Z-stack imaging and transmission electron microscopy (TEM) imaging. We performed a cellular viability assay and live/dead cell fluorescence imaging of the combined therapeutic effects of MGNs with DOX-loaded LTSLs (DOX-LTSLs) and compared them with free DOX and DOX-loaded non-temperature-sensitive liposomes (DOX-NTSLs). Imaging of fluorescent live/dead cell indicators and MTT assay outcomes both demonstrated significant decreases in cellular viability when cells were treated with the combination therapy. Because of the high phase-transition temperature of NTSLs, no drug delivery was observed from the DOX-NTSLs. Notably, even at a low DOX concentration of 0.5 µg/mL, the combination treatment resulted in a higher (33%) cell death relative to free DOX (17% cell death). The results of our work demonstrate that the synergistic therapeutic effect of photothermal hyperthermia of MGNs with drug delivery from the LTSLs can successfully eradicate aggressive breast cancer cells with higher efficacy than free DOX by providing a controlled light-activated approach and minimizing off-target toxicity.
ABSTRACT
In this work, we investigate plasmonic enhancement in poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester organic photovoltaics (OPVs) by integrating shape- and size-controlled bimetallic gold core-silver shell nanocrystals (Au-Ag NCs) into the poly(3,4-ethylenedioxythiophene):polystyrene sulfonate hole-transport layer. We observed that the best-performing Au-Ag NC-incorporated OPVs improved the power conversion efficiency by 9% via a broadband increase in photocurrent throughout the visible spectrum. Our experimental and computational results suggest that the observed photocurrent enhancement in plasmonic OPVs originates from both enhanced absorption and improved exciton dissociation and charge collection. This is particularly achieved by placing metal NCs near the interface of the active layer and hole-transport layer. The impedance spectroscopy results suggest that Au-Ag NCs reduce recombination and also increase the internal exciton to carrier efficiency by driving the dissociation of bound charge-transfer states to free carriers.
