Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.
The topology of a conjugated molecule plays a significant role in controlling both the electronic properties and the conformational manifold that the molecule may explore. Fully π-conjugated molecular nanorings are of particular interest, as their lowest electronic transition may be strongly suppressed as a result of symmetry constraints. In contrast, the simple Kasha model predicts an enhancement in the radiative rate for corresponding linear oligomers. Here we investigate such effects in linear and cyclic conjugated molecules containing between 6 and 42 butadiyne-linked porphyrin units (corresponding to 600 C-C bonds) as pure monodisperse oligomers. We demonstrate that as the diameter of the nanorings increases beyond ∼10 nm, its electronic properties tend toward those of a similarly sized linear molecule as a result of excitation localization on a subsegment of the ring. However, significant differences persist in the nature of the emitting dipole polarization even beyond this limit, arising from variations in molecular curvature and conformation.
This work describes the unexpected alignment of a common perylene bisimide fluorescent dye (Lumogen Red305) in a host liquid crystal matrix. The negative dichroic fluorophore orients with the primary absorption/emission dipole, corresponding to the physical long axis of the perylene bisimide core, perpendicular to the director of a host liquid crystal. A second absorption dipole, which lies perpendicular to the primary dipole and corresponding to the physical short axis of the perylene core, lies parallel to the host liquid crystal. Individual illumination of the two absorbing optical transition dipole moments of the Red305 dye results in a single linearly polarized emission. When Red305 is combined with a second positive dichroic Coumarin‐type fluorophore that aligns in the conventional manner in a liquid crystal host, that is, with an absorption dipole along the physical long axis of the fluorophore and the director of the host liquid crystal, advanced light management is possible, such as electrically switchable colors and directing emission light to different edges in a luminescent solar concentrator device.
Solid-state
electroabsorption is demonstrated as a powerful tool
for probing the charge transfer (CT) character and state mixing in
the low-energy optical transitions of two structurally similar thermally
activated delayed fluorescent (TADF) materials with divergent photophysical
and device performances. The Liptay model is used to fit differentials
of the low-energy absorption bands to the measured electroabsorption
spectra, with both emitters showing CT characteristics and large changes
in dipole moments upon excitation despite the associated absorption
bands appearing to be structured. High electric fields then reveal
transfer of oscillator strength to a state close to the CT in the
better performing molecule. With supporting TDDFT-TDA and DFT/MRCI
calculations, this state showed ππ* characteristics of
a local acceptor triplet that strongly mixes with the σπ*
of the CT. The emitter with poor TADF performance showed no evidence
of such mixing.
Materials showing rapid intramolecular energy transfer and polarization switching are of interest for both their fundamental photophysics and potential for use in real-world applications. Here, we report two donor-acceptor-donor triad dyes based on perylene-bisimide subunits, with the long axis of the donors arranged either parallel or perpendicular to that of the central acceptor. We observe rapid energy transfer (<2 ps) and effective polarization control in both dye molecules in solution. A distributed-dipole Förster model predicts the excitation energy transfer rate for the linearly arranged triad but severely underestimates it for the orthogonal case. We show that the rapid energy transfer arises from a combination of through-bond coupling and through-space transfer between donor and acceptor units. As they allow energy cascading to an excited state with controllable polarization, these triad dyes show high potential for use in luminescent solar concentrator devices.
Periodic metal-dielectric structures attract substantial interest since it was previously proposed that the spontaneous emission amplification rates (the Purcell factor) in such structures can reach enormous values up to 10
5
. However, the role of absorption in real metals has not been thoroughly considered. We provide a theoretical analysis showing that absorption leads to diminishing values of Purcell factor. We also suggest that using emitting organic compounds such as CBP (4,4-Bis(N-carbazolyl)-1,1-biphenyl) can lead to a moderate increase of about an order of magnitude in the Purcell factor. Defining the experimentally measured Purcell factor as a ratio between the excited state lifetimes in bare CBP and in periodic structure, this increase in the fabricated periodic structure is demonstrated through a 4–8 times decrease in excited state radiative lifetime compared to a bare organic material in a wide emission spectrum.
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