Reduced Graphene Oxide–Silver Nanoparticle Composite as an Active SERS Material

Selectivity and enhanced sensitivity for SERS measurements are highly desirable for environmental and analytical applications. Interaction of a target molecule with SERS substrate plays a pivotal role in determining the magnitude of enhancement and spectral profile of the SERS signal. A reduced graphene oxide–Ag nanoparticle (RGO-Ag NP) composite has been designed to boost SERRS sensitivity of a porphyrin derivative. Complexation between 5,10,15,20-tetrakis­(1-methyl-4-pyridinio)­porphyrin tetra­(<i>p</i>-toluenesulfonate) (TMPyP) porphyrin and the RGO-Ag NP composite is evidenced by a red-shifted porphyrin absorption band. Results indicate complexation is influential in improved surface-enhanced resonance Raman (SERRS) signal for TMPyP and thus offers an advantage for target molecule detection at low concentration levels. The combined effects of RGO and Ag NPs in the enhancement of SERS signal of TMPyP are discussed

Transient Absorption Spectroscopy of Excitons in an Individual Suspended Metallic Carbon Nanotube

We present femtosecond transient absorption measurements of individual metallic single-wall carbon nanotubes (SWNTs) to elucidate environmental effects on their spectroscopy and dynamics. Isolated suspended SWNTs were located using atomic force microscopy, and Raman spectroscopy was employed to determine the chiral index of select nanotubes. Transient absorption spectra of the SWNTs were obtained by recording transient absorption images at different probe wavelengths. This unique experimental approach removes sample heterogeneity in ultrafast measurements of these complex materials and provides a direct means to unravel the role of the substrate. The results show a ∼40 meV red shift of the lowest exciton transition, which is attributed to dielectric screening effects by the substrate. Energy relaxation in individual metallic nanotubes was observed with decay constants of a few hundred fs and about 10 ps. We attributed the fast and slow decay components to carrier scattering by optical and acoustic phonons, respectively

Ultrafast Spatial Imaging of Charge Dynamics in Heterogeneous Polymer Blends

Proof-of-concept transient absorption microscopy (TAM) with simultaneously high spatial and temporal resolution was demonstrated to image charge generation and recombination in model systems of poly­(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) blends upon extended thermal annealing. Significant spatial heterogeneity in charge generation and recombination dynamics was revealed on the length scale of hundreds of nanometers near the micrometer-sized PCBM crystallites, suggesting that information obtained in ensemble measurements by integrating over microscopically inhomogeneous areas could be misleading. In contrast to previous studies, high sensitivity of our instrumentation allows us to employ low excitation intensities to minimize higher-order recombination processes. TAM provides a unique noncontact tool to probe local functionality in microscopically heterogeneous energy harvesting systems

Exciton Structure and Dynamics in Solution Aggregates of a Low-Bandgap Copolymer

In this work, we elucidate exciton structure, dynamics, and charge generation in the solution phase aggregates of a low-bandgap donor–acceptor polymer, poly­(4,8-bis-alkyloxybenzo­[1,2-<i>b</i>:4,5-<i>b</i>′]­dithiophene-2,6-diyl-<i>alt</i>-(alkylthieno­[3,4-<i>b</i>]­thiophene-2carboxylate)-2,6-diyl (PBDTTT). The polymer aggregates in the solution phase serve as precursors for thin film morphologies. We have identified intrachain and interchain exciton transitions and resolved their relaxation pathways by comparing excitons in solution aggregates to those in isolated polymer chains. Hot intrachain excitons have led to the generation of stabilized interchain charge-separated states in solution aggregates, which could serve as the intermediate state to the hot exciton charge separation in bulk heterojunctions (BHJs). These results have important implications for controlling morphology dependent exciton dynamics in solution processed BHJs

Direct Imaging of Exciton Transport in Tubular Porphyrin Aggregates by Ultrafast Microscopy

Long-range exciton transport is a key challenge in achieving efficient solar energy harvesting in both organic solar cells and photosynthetic systems. Self-assembled molecular aggregates provide the potential for attaining long-range exciton transport through strong intermolecular coupling. However, there currently lacks an experimental tool to directly characterize exciton transport in space and in time to elucidate mechanisms. Here we report a direct visualization of exciton diffusion in tubular molecular aggregates by transient absorption microscopy with ∼200 fs time resolution and ∼50 nm spatial precision. These direct measurements provide exciton diffusion constants of 3–6 cm² s^–1 for the tubular molecular aggregates, which are 3–5 times higher than a theoretical lower bound obtained by assuming incoherent hopping. These results suggest that coherent effects play a role, despite the fact that exciton states near the band bottom crucial for transport are only weakly delocalized (over <10 molecules). The methods presented here establish a direct approach for unraveling the mechanisms and main parameters underlying exciton transport in large molecular assemblies

Correlating Nanoscopic Energy Transfer and Far-Field Emission to Unravel Lasing Dynamics in Plasmonic Nanocavity Arrays

Excited-state interactions between nanoscale cavities and photoactive molecules are critical in plasmonic nanolasing, although the underlying details are less-resolved. This paper reports direct visualization of the energy-transfer dynamics between two-dimensional arrays of plasmonic gold bowtie nanocavities and dye molecules. Transient absorption microscopy measurements of single bowties within the array surrounded by gain molecules showed fast excited-state quenching (2.6 ± 1 ps) characteristic of individual nanocavities. Upon optical pumping at powers above threshold, lasing action emerged depending on the spacing of the array. By correlating ultrafast microscopy and far-field light emission characteristics, we found that bowtie nanoparticles acted as isolated cavities when the diffractive modes of the array did not couple to the plasmonic gap mode. These results demonstrate how ultrafast microscopy can provide insight into energy relaxation pathways and, specifically, how nanocavities in arrays can show single-unit nanolaser properties

Tunneling-Driven Marcus-Inverted Triplet Energy Transfer in a Two-Dimensional Perovskite

Quantum tunneling, a phenomenon that allows particles to pass through potential barriers, can play a critical role in energy transfer processes. Here, we demonstrate that the proper design of organic–inorganic interfaces in two-dimensional (2D) hybrid perovskites allows for efficient triplet energy transfer (TET), where quantum tunneling of the excitons is the key driving force. By employing temperature-dependent and time-resolved photoluminescence and pump–probe spectroscopy techniques, we establish that triplet excitons can transfer from the inorganic lead-iodide sublattices to the pyrene ligands with rapid and weakly temperature-dependent characteristic times of approximately 50 ps. The energy transfer rates obtained based on the Marcus theory and first-principles calculations show good agreement with the experiments, indicating that the efficient tunneling of triplet excitons within the Marcus-inverted regime is facilitated by high-frequency molecular vibrations. These findings offer valuable insights into how one can effectively manipulate the energy landscape in 2D hybrid perovskites for energy transfer and the creation of diverse excitonic states

Ultrafast Imaging of Carrier Transport across Grain Boundaries in Hybrid Perovskite Thin Films

For optoelectronic devices based on polycrystalline semiconducting thin films, carrier transport across grain boundaries is an important process in defining efficiency. Here we employ transient absorption microscopy (TAM) to directly measure carrier transport within and across the boundaries in hybrid organic–inorganic perovskite thin films for solar cell applications with 50 nm spatial precision and 300 fs temporal resolution. By selectively imaging sub-bandgap states, our results show that lateral carrier transport is slowed down by these states at the grain boundaries. However, the long carrier lifetimes allow for efficient transport across the grain boundaries. The carrier diffusion constant is reduced by about a factor of 2 for micron-sized grain samples by the grain boundaries. For grain sizes on the order of ∼200 nm, carrier transport over multiple grains has been observed within a time window of 5 ns. These observations explain both the shortened photoluminescence lifetimes at the boundaries as well as the seemingly benign nature of the grain boundaries in carrier generation

Charge Carrier Trapping and Acoustic Phonon Modes in Single CdTe Nanowires

Semiconductor nanostructures produced by wet chemical synthesis are extremely heterogeneous, which makes single particle techniques a useful way to interrogate their properties. In this paper the ultrafast dynamics of single CdTe nanowires are studied by transient absorption microscopy. The wires have lengths of several micrometers and lateral dimensions on the order of 30 nm. The transient absorption traces show very fast decays, which are assigned to charge carrier trapping into surface defects. The time constants vary for different wires due to differences in the energetics and/or density of surface trap sites. Measurements performed at the band edge compared to the near-IR give slightly different time constants, implying that the dynamics for electron and hole trapping are different. The rate of charge carrier trapping was observed to slow down at high carrier densities, which was attributed to trap-state filling. Modulations due to the fundamental and first overtone of the acoustic breathing mode were also observed in the transient absorption traces. The quality factors for these modes were similar to those measured for metal nanostructures, and indicate a complex interaction with the environment

Relationship between Interchain Interaction, Exciton Delocalization, and Charge Separation in Low-Bandgap Copolymer Blends

We present a systematic study of the roles of crystallinity, interchain interaction, and exciton delocalization on ultrafast charge separation pathways in donor–acceptor copoloymer blends. We characterize the energy levels, excited state structures, and dynamics of the interchain species by combined ultrafast spectroscopy and computational quantum chemistry approaches. The alkyl side chain of a highly efficient donor–acceptor copolymer for solar cell applications, PBDTTT (poly­(4,8-bis-alkyloxybenzo­[1,2-b:4,5-b′]­dithiophene-2,6-diyl-<i>alt</i>-(alkylthieno­[3,4-<i>b</i>]­thiophene-2-carboxylate)-2,6-diyl), is varied to tune the molecular packing and interchain interaction of the polymers in order to elucidate the charge separation pathways originating from intrachain and interchain species. Polymers with linear side chains result in more crystalline polymer domain that lead to preferential formation of interchain excitons delocalizing over more than one polymer backbone in the solid state. Our results demonstrate that the higher polymer crystallinity leads to slower charge separation due to coarser phase segregation and formation of the interchain excited states that are energetically unfavorable for charge separation. Such energetics of the interchain excitons in low-bandgap copolymers calls for optimized solar cell morphologies that are fundamentally different from those based on homopolymers such as P3HT (poly-3-hexylthiophene). A long-range crystalline polymer domain is detrimental rather than beneficial to solar cell performance for a low-bandgap copolymer which is in direct contrast to the observed behavior in P3HT based devices