Size-Independent Energy Transfer in Biomimetic Nanoring Complexes

Supramolecular antenna-ring complexes are of great interest due to their presence in natural light-harvesting complexes. While such systems are known to provide benefits through robust and efficient energy funneling, the relationship between molecular structure, strain (governed by nuclear coordinates and motion), and energy dynamics (arising from electronic behavior) is highly complex. We present a synthetic antenna-nanoring system based on a series of conjugated porphyrin chromophores ideally suited to explore such effects. By systematically varying the size of the acceptor nanoring, we reveal the interplay between antenna-nanoring binding, local strain, and energy dynamics on the picosecond time scale. Binding of the antenna unit creates a local strain in the nanoring, and this strain was measured as a function of the size of the nanoring, by UV–vis-NIR titration, providing information on the conformational flexibility of the system. Strikingly, the energy-transfer rate is independent of nanoring size, indicating the existence of strain-localized acceptor states, spread over about six porphyrin units, arising from the noncovalent antenna-nanoring association

Breaking the Symmetry in Molecular Nanorings

Because of their unique electronic properties, cyclic molecular structures ranging from benzene to natural light-harvesting complexes have received much attention. Rigid π-conjugated templated porphyrin nanorings serve as excellent model systems here because they possess well-defined structures that can readily be controlled and because they support highly delocalized excitations. In this study, we have deliberately modified a series of six-porphyrin nanorings to examine the impact of lowering the rotational symmetry on their photophysical properties. We reveal that as symmetry distortions increase in severity along the series of structures, spectral changes and an enhancement of radiative emission strength occur, which derive from a transfer of oscillator strength into the lowest (<i>k</i> = 0) state. We find that concomitantly, the degeneracy of the dipole-allowed first excited (<i>k </i>= ±1) state is lifted, leading to an ultrafast polarization switching effect in the emission from strongly symmetry-broken nanorings

Morphology-Dependent Energy Transfer Dynamics in Fluorene-Based Amphiphile Nanoparticles

Nanoparticles are interesting systems to study because of their large range of potential uses in biological imaging and sensing. We investigated molecular nanoparticles formed by fast injection of a small volume of molecularly dissolved fluorene-derivative amphiphilic molecules into a polar solvent, which resulted in solid spherical particles of ∼80 nm diameter with high stability. Energy transfer studies were carried out on two-component nanoparticles that contained mixtures of donor and acceptor amphiphiles of various fractions. We conducted time-resolved photoluminescence measurements on the two-component nanoparticles in order to determine whether the fundamental donor–acceptor interaction parameter (the Förster radius) depends on the acceptor concentration. The Förster radius was found to be large for very low incorporated acceptor fractions (<0.1%), but it declined with increasing concentration. These changes were concomitant with shifts in the acceptor emission and absorption circular dichroism spectra that indicated an increasing clustering of acceptors into domains as their fraction was raised. In addition, for acceptor fractions below 2% the extracted Förster radii were found to be significantly larger than predicted from donor–acceptor spectral overlap calculations, in accordance with efficient excitation diffusion within the donor matrix, aiding the overall transfer to acceptors. We conclude that energy transfer in two-component nanoparticles shows a complex interplay between phase segregation of the constituent donor and acceptor molecules and excitation diffusion within their domains

Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i>

The organic–inorganic hybrid perovskites methylammonium lead iodide (CH₃NH₃PbI₃) and the partially chlorine-substituted mixed halide CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i> emit strong and broad photoluminescence (PL) around their band gap energy of ∼1.6 eV. However, the nature of the radiative decay channels behind the observed emission and, in particular, the spectral broadening mechanisms are still unclear. Here we investigate these processes for high-quality vapor-deposited films of CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i> using time- and excitation-energy dependent photoluminescence spectroscopy. We show that the PL spectrum is homogenously broadened with a line width of 103 meV most likely as a consequence of phonon coupling effects. Further analysis reveals that defects or trap states play a minor role in radiative decay channels. In terms of possible lasing applications, the emission spectrum of the perovskite is sufficiently broad to have potential for amplification of light pulses below 100 fs pulse duration

Photocurrent Spectroscopy of Perovskite Solar Cells Over a Wide Temperature Range from 15 to 350 K

Solar cells based on metal halide perovskite thin films show great promise for energy generation in a range of environments from terrestrial installations to space applications. Here we assess the device characteristics of the prototypical perovskite solar cells based on methylammonium lead triiodide (CH₃NH₃PbI₃) over a broad temperature range from 15 to 350 K (−258 to 77 °C). For these devices, we observe a peak in the short-circuit current density and open-circuit voltage at 200 K (−73 °C) with decent operation maintained up to 350 K. We identify the clear signature of crystalline PbI₂ contributing directly to the low-temperature photocurrent spectra, showing that PbI₂ plays an active role (beyond passivation) in CH₃NH₃PbI₃ solar cells. Finally we observe a blue-shift in the photocurrent spectrum with respect to the absorption spectrum at low temperature (15 K), allowing us to extract a lower limit on the exciton binding energy of 9.1 meV for CH₃NH₃PbI₃

Radiative Monomolecular Recombination Boosts Amplified Spontaneous Emission in HC(NH₂)₂SnI₃ Perovskite Films

Hybrid metal-halide perovskites have potential as cost-effective gain media for laser technology because of their superior optoelectronic properties. Although lead-halide perovskites have been most widely studied to date, tin-based perovskites have been proposed as a less toxic alternative. In this Letter, we show that amplified spontaneous emission (ASE) in formamidinium tin triiodide (FASnI₃) thin films is supported by an observed radiative monomolecular charge recombination pathway deriving from its unintentional doping. Such a radiative component will be active even at the lowest charge-carrier densities, opening a pathway for ultralow light-emission thresholds. Using time-resolved THz photoconductivity analysis, we further show that the material has an unprecedentedly high charge-carrier mobility of 22 cm² V^–1 s^–1 favoring efficient transport. In addition, FASnI₃ exhibits strong radiative bimolecular recombination and Auger rates that are over an order of magnitude lower than for lead-halide perovskites. In combination, these properties reveal that tin-halide perovskites are highly suited to light-emitting devices

Effect of Structural Phase Transition on Charge-Carrier Lifetimes and Defects in CH₃NH₃SnI₃ Perovskite

Methylammonium tin triiodide (MASnI₃) has been successfully employed in lead-free perovskite solar cells, but overall power-conversion efficiencies are still significantly lower than for lead-based perovskites. Here we present photoluminescence (PL) spectra and time-resolved PL from 8 to 295 K and find a marked improvement in carrier lifetime and a substantial reduction in PL line width below ∼110 K, indicating that the cause of the hindered performance is activated at the orthorhombic to tetragonal phase transition. Our measurements therefore suggest that targeted structural change may be capable of tailoring the relative energy level alignment of defects (e.g., tin vacancies) to reduce the background dopant density and improve charge extraction. In addition, we observe for the first time an above-gap emission feature that may arise from higher-lying interband transitions, raising the prospect of excess energy harvesting

High Electron Mobility and Insights into Temperature-Dependent Scattering Mechanisms in InAsSb Nanowires

InAsSb nanowires are promising elements for thermoelectric devices, infrared photodetectors, high-speed transistors, as well as thermophotovoltaic cells. By changing the Sb alloy fraction the mid-infrared bandgap energy and thermal conductivity may be tuned for specific device applications. Using both terahertz and Raman noncontact probes, we show that Sb alloying increases the electron mobility in the nanowires by over a factor of 3 from InAs to InAs_0.65Sb_0.35. We also extract the temperature-dependent electron mobility via both terahertz and Raman spectroscopy, and we report the highest electron mobilities for InAs_0.65Sb_0.35 nanowires to date, exceeding 16,000 cm² V^–1 s^–1 at 10 K

Impact of the Organic Cation on the Optoelectronic Properties of Formamidinium Lead Triiodide

Metal halide perovskites have proven to be excellent light-harvesting materials in photovoltaic devices whose efficiencies are rapidly improving. Here, we examine the temperature-dependent photon absorption, exciton binding energy, and band gap of FAPbI₃ (thin film) and find remarkably different behavior across the β–γ phase transition compared with MAPbI₃. While MAPbI₃ has shown abrupt changes in the band gap and exciton binding energy, values for FAPbI₃ vary smoothly over a range of 100–160 K in accordance with a more gradual transition. In addition, we find that the charge-carrier mobility in FAPbI₃ exhibits a clear <i>T</i>^–0.5 trend with temperature, in excellent agreement with theoretical predictions that assume electron–phonon interactions to be governed by the Fröhlich mechanism but in contrast to the <i>T</i>^–1.5 dependence previously observed for MAPbI₃. Finally, we directly observe intraexcitonic transitions in FAPbI₃ at low temperature, from which we determine a low exciton binding energy of only 5.3 meV at 10 K

Nanoengineering Coaxial Carbon Nanotube–Dual-Polymer Heterostructures

We describe studies of new nanostructured materials consisting of carbon nanotubes wrapped in sequential coatings of two different semiconducting polymers, namely, poly(3-hexylthiophene) (P3HT) and poly(9,9′-dioctylfluorene-<i>co</i>-benzothiadiazole) (F8BT). Using absorption spectroscopy and steady-state and ultrafast photoluminescence measurements, we demonstrate the role of the different layer structures in controlling energy levels and charge transfer in both solution and film samples. By varying the simple solution processing steps, we can control the ordering and proportions of the wrapping polymers in the solid state. The resulting novel coaxial structures open up a variety of new applications for nanotube blends and are particularly promising for implementation into organic photovoltaic devices. The carbon nanotube template can also be used to optimize both the electronic properties and morphology of polymer composites in a much more controlled fashion than achieved previously, offering a route to producing a new generation of polymer nanostructures