skip to main content

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 11:00 PM ET on Friday, December 13 until 2:00 AM ET on Saturday, December 14 due to maintenance. We apologize for the inconvenience.


Title: Charge separation boosts exciton diffusion in fused ring electron acceptors
Non-fullerene acceptors (NFAs) are highly promising materials for organic photovoltaics (OPVs). Exciton diffusion in NFAs is crucial to their photovoltaic performance, but is not yet well understood. Here we systematically examine exciton diffusion in a fused-ring electron acceptor (IDIC) based on a first-principles framework. We discover that low-energy excitons in disordered IDIC are charge-separated with electrons and holes residing on neighboring molecules, yielding long exciton lifetimes. With low energetic disorder, high exciton density of states (DOS) and long lifetimes, the disordered IDIC is predicted to exhibit large exciton diffusion lengths and high quantum efficiency. The temperature and energy dependences of exciton diffusion are explored and the manner in which various materials properties (exciton energy, DOS, energetic disorder, and phonon frequency) conspire to influence exciton diffusion is elucidated. Finally, we show that dilation could be an effective strategy to increase the exciton diffusion length in IDIC.  more » « less
Award ID(s):
1828019
PAR ID:
10226271
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry A
Volume:
8
Issue:
44
ISSN:
2050-7488
Page Range / eLocation ID:
23304 to 23312
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Characterizing the density of states (DOS) width accurately is critical in understanding the charge‐transport properties of organic semiconducting materials as broader DOS distributions lead to an inferior transport. From a morphological standpoint, the relative densities of ordered and disordered regions are known to affect charge‐transport properties in films; however, a comparison between molecular structures showing quantifiable ordered and disordered regions at an atomic level and its impact on DOS widths and charge‐transport properties has yet to be made. In this work, for the first time, the DOS distribution widths of two model conjugated polymer systems are characterized using three different techniques. A quantitative correlation between energetic disorder from band‐bending measurements and charge transport is established, providing direct experimental evidence that charge‐carrier mobility in disordered materials is compromised due to the relaxation of carriers into the tail states of the DOS. Distinction and quantification of ordered and disordered regions of thin films at an atomic level is achieved using solid‐state NMR spectroscopy. An ability to compare solid‐state film morphologies of organic semiconducting polymers to energetic disorder, and in turn charge transport, can provide useful guidelines for applications of organic conjugated polymers in pertinent devices.

     
    more » « less
  2. Transport properties of doped conjugated polymers (CPs) have been widely analyzed with the Gaussian Disorder Model (GDM) in conjunction with hopping transport between localized states. These models reveal that even in highly doped CPs, a majority of carriers are still localized because dielectric permittivity of CPs is well below that of inorganic materials, making Coulomb interactions between carriers and dopant counter-ions much more pronounced. However, previous studies within the GDM did not consider the role of screening the dielectric interactions by carriers. Here we implement carrier screening in the Debye-H¨uckel formalism in our calculations of dopant-induced energetic disorder, which modifies the Gaussian density of states (DOS). Then we solve the Pauli Master Equation using Miller-Abrahams hopping rates with states from the resulting screened DOS to obtain conductivity and Seebeck coefficient across a broad range of carrier concentrations and compare them to measurements. Our results show that screening has significant impact on the shape of the DOS and consequently on carrier transport, particularly at high doping. We prove that the slope of Seebeck coefficient vs electric conductivity, which was previously thought to be universal, is impacted by screening and decreases for systems with small dopant-carrier separation, explaining our measurements. We also show that thermoelectric power factor is underestimated by a factor of ∼ 10 at higher doping concentrations if screening is neglected. We conclude that carrier screening plays a crucial role in curtailing dopant-induced energetic disorder, particularly at high carrier concentrations. 
    more » « less
  3. Structural and functional heterogeneity is a consequence of the weak noncovalent interactions that direct the formation of organic materials from solution precursors. While covalent tethering of solution-phase assemblies provides a compelling strategy to enhance intermolecular order, the effects of this tethering strategy on the formed solid-state materials remain unestablished. This work uses pump–probe microscopy to compare excited-state dynamics in thin films fabricated from tethered perylene bisimide assemblies to those fabricated from noncovalent assemblies. On average, tethered films exhibit faster and more homogeneous excited-state lifetimes, consistent with stronger and more uniform intermolecular coupling. Optical measurements of excited-state diffusion show that the tethered film has ∼75% faster transport than the control film. Kinetic Monte Carlo modeling suggests that the reduction of site energetic disorder is sufficient to quantitatively explain the difference in diffusion coefficients. These results provide strong support that covalent tethering is a promising strategy to enhance the structural and energetic ordering in molecular materials. 
    more » « less
  4. Abstract

    Organic solar cells incorporating non‐fullerene acceptors (NFAs) have reached remarkable power conversion efficiencies of over 18%. Unlike fullerene derivatives, NFAs tend to crystallize from solutions, resulting in bulk heterojunctions that include a crystalline acceptor phase. This must be considered in any morphology‐function models. Here, it is confirmed that high‐performing solution‐processed indacenodithienothiophene‐based NFAs, i.e., ITIC and its derivatives ITIC‐M, ITIC‐2F, and ITIC‐Th, exhibit at least two crystalline forms. In addition to highly ordered polymorphs that form at high temperatures, NFAs arrange into a low‐temperature metastable phase that is readily promoted via solution processing and leads to the highest device efficiencies. Intriguingly, the low‐temperature forms seem to feature a continuous network that favors charge transport despite of a poorly order along the π–π stacking direction. As the optical absorption of the structurally more disordered low‐temperature phase can surpass that of the more ordered polymorphs while displaying comparable—or even higher—charge transport properties, it is argued that such a packing structure is an important feature for reaching highest device efficiencies, thus, providing guidelines for future materials design and crystal engineering activities.

     
    more » « less
  5. As in the case of a free particle, the initial growth of a broad (relative to lattice spacing) wavepacket placed on an ordered lattice is slow (its time derivative has zero initial slope), and the spread (root mean square displacement) becomes linear in t at a long time. On a disordered lattice, the growth is inhibited for a long time (Anderson localization). We consider site disorder with nearest-neighbor hopping on one- and two-dimensional systems and show via numerical simulations supported by the analytical study that the short time growth of the particle distribution is faster on the disordered lattice than on the ordered one. Such faster spread takes place on time and length scales that may be relevant to the exciton motion in disordered systems. 
    more » « less