6 research outputs found
Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer
We investigate the delocalization of holes in the semicrystalline conjugated
polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) by
directly measuring the hyperfine coupling between photogenerated polarons and
bound nuclear spins using electron nuclear double resonance spectroscopy. An
extrapolation of the corresponding oligomer spectra reveals that charges tend
to delocalize over 4.0â4.8 nm with delocalization strongly dependent on
molecular order and crystallinity of the PBTTT polymer thin films. Density
functional theory calculations of hyperfine couplings confirm that long-range
corrected functionals appropriately describe the change in coupling strength
with increasing oligomer size and agree well with the experimentally measured
polymer limit. Our discussion presents general guidelines illustrating the
various pitfalls and opportunities when deducing polaron localization lengths
from hyperfine coupling spectra of conjugated polymers
Rubrene single crystal solar cells and the effect of crystallinity on interfacial recombination
Single crystal studies provide a better understanding of the basic properties of organic photovoltaic devices. Therefore, in this work, rubrene single crystals with a thickness of 250 nm to 1000 nm were used to produce an inverted bilayer organic solar cell. Subsequently, polycrystalline rubrene (orthorhombic, triclinic) and amorphous bilayer solar cells of the same thickness as single crystals were studied to make comparisons across platforms. To investigate how single crystal, polycrystalline (triclinic-orthorhombic) and amorphous forms alter the charge carrier recombination mechanism at the rubrene/PCBM interface, light intensity measurements were carried out. The light intensity dependency of the J(SC), V-OC and FF parameters in organic solar cells with different forms of rubrene was determined. Monomolecular (Shockley Read Hall) recombination is observed in devices employing amorphous and polycrystalline rubrene in addition to bimolecular recombination, whereas the single crystal device is weakly affected by trap assisted SRH recombination due to reduced trap states at the donor acceptor interface. To date, the proposed work is the only systematic study examining transport and interface recombination mechanisms in organic solar cells produced by different structure forms of rubrene.D. A. K. acknowledges the Turkey research fellowship (TUBITAK 2214/A-1059B141501315). K. K. thanks the Turkey Scholarship Council (2214/A-1059B141501316). B. G acknowledges the 1003 -Primary Subjects R;D Funding Program (218M940) and A. L. B. acknowledges the Office of Naval Research (N0001416-1-2612 and N000147-14-1-0053).Office of Naval Research [N0001416-1-2612, N000147-14-1-0053]; Turkey research fellowship [TUBITAK 2214/A-1059B141501315]; Turkey Scholarship Council [2214/A-1059B141501316]; 1003 -Primary Subjects R;D Funding Program [218M940
Breaking the Bimolecular Crystal: The Effect of Side-Chain Length on Oligothiophene/Fullerene Intercalation
Polymer/fullerene
bimolecular crystal formation has been investigated
using a variety of conjugated polymers and fullerenes to understand
the design rules that influence donorâacceptor interaction.
Modifications of the polymer by varying the substitution side-chain
position, density, and branching have demonstrated the importance
of the âpocketâ dimensions (free volume between side
chains where the fullerene resides) for controlling intercalation.
Yet the effect of pocket height has not been systematically explored
because of the solubility limitations in polymers. In this report,
we present an experimental investigation into the effect of the pocket
height by synthesizing polyÂ[2,5-bisÂ(3-<i>alkyl</i>thiophen-2-yl)ÂthienoÂ[3,2-<i>b</i>]Âthiophene] dimers with varied side chain lengths and track
the morphological changes of the dimer/fullerene blends using grazing-incidence
X-ray scattering, thermal measurements, and photoluminescence quenching.
We identify two regimes: (1) oligomers with side chains greater than
or equal to heptyl (C7) form bimolecular crystals and (2) oligomers
with less than or equal to hexyl (C6) form amorphous blends. This
work provides the first observation of an order-to-disorder transition
mediated by side-chain length in donor-fullerene intercalated blends
Poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2â<i>b</i>]thiophene] Oligomer Single-Crystal Nanowires from Supercritical Solution and Their Anisotropic Exciton Dynamics
Supercritical fluids,
exhibiting a combination of liquid-like solvation
power and gas-like diffusivity, are a relatively unexplored medium
for processing and crystallization of oligomer and polymeric semiconductors
whose optoelectronic properties critically depend on the microstructure.
Here we report oligomer crystallization from the polymer organic semiconductor,
polyÂ[2,5-bisÂ(3-dodecylthiophen-2-yl)ÂthienoÂ[3,2-<i>b</i>]Âthiophene]
(PBTTT) in supercritical hexane, yielding needle-like single crystals
up to several microns in length. We characterize the crystalsâ
photophysical properties by time- and polarization-resolved photoluminescence
(TPRPL) spectroscopy. These techniques reveal two-dimensional interchromophore
coupling facilitated by the high degree of Ï-stacking order
within the crystal. Furthermore, the crystals obtained from supercritical
fluid were found to be similar photophysically as the crystallites
found in solution-cast thin films and distinct from solution-grown
crystals that exhibited spectroscopic signatures indicative of different
packing geometries