12 research outputs found
Measuring Intermolecular Excited State Geometry for Favorable Singlet Fission in Tetracene
Singlet fission (SF) is the process of converting an
excited singlet
to a pair of excited triplets. Harvesting two charges from a single
photon has the potential to increase photovoltaic device efficiencies.
Acenes, such as tetracene and pentacene, are model molecules for studying
SF. Despite SF being an endoergic process for tetracene and exoergic
for pentacene, both acenes exhibit near unity SF quantum efficiencies,
raising questions about how tetracene can overcome the energy barrier.
Here, we use recently developed instrumentation to measure inelastic
neutron scattering (INS) while optically exciting the model molecules
using two different excitation energies. The spectroscopic results
reveal intermolecular structural relaxation due to the presence of
a triplet excited state. The structural dynamics of the combined excited
state molecule and surrounding tetracene molecules are further studied
using time-dependent density functional theory (TD-DFT), which shows
that the singlet and triplet levels shift due to the excited state
geometry, reducing the uphill energy barrier for SF to within kT
J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers
Nanofibers (NFs) of poly-3-hexylthiophene (P3HT) assembled
in toluene
exhibit single-chain J-aggregate character. Absorption, fluorescence
emission, and Raman spectroscopy of dilute NF dispersions demonstrate
that P3HT chains possess long-range intrachain order (planarity) that
suppresses interchain exciton coupling. We demonstrate that a delicate
interplay exists
between intrachain order and interchain coupling as revealed through
the emission 0ā0/0ā1 vibronic intensity ratios. Lowering
temperature and application
of pressure induces minor perturbations in the NF packing, which destroys
J-aggregate character and partially restores predominant interchain
interactions (i.e., H-aggregate behavior). The fact that ĻāĻ
stacked P3HT chains can exhibit both H- and J-aggregate behavior
opens up new possibilities for controlling electronic coupling through
noncovalent
stacking interactions
J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers
Nanofibers (NFs) of poly-3-hexylthiophene (P3HT) assembled
in toluene
exhibit single-chain J-aggregate character. Absorption, fluorescence
emission, and Raman spectroscopy of dilute NF dispersions demonstrate
that P3HT chains possess long-range intrachain order (planarity) that
suppresses interchain exciton coupling. We demonstrate that a delicate
interplay exists
between intrachain order and interchain coupling as revealed through
the emission 0ā0/0ā1 vibronic intensity ratios. Lowering
temperature and application
of pressure induces minor perturbations in the NF packing, which destroys
J-aggregate character and partially restores predominant interchain
interactions (i.e., H-aggregate behavior). The fact that ĻāĻ
stacked P3HT chains can exhibit both H- and J-aggregate behavior
opens up new possibilities for controlling electronic coupling through
noncovalent
stacking interactions
Excited-State Self-Trapping and Ground-State Relaxation Dynamics in Poly(3-hexylthiophene) Resolved with Broadband PumpāDumpāProbe Spectroscopy
Broadband femtosecond transient absorption spectroscopy is used to explore the mechanisms underlying excited-state and ground-state exciton relaxation in poly(3-hexylthiophene) (P3HT) solution. We focus on the picosecond spectral shifts in the ground and excited states of P3HT, using pumpāprobe (PP) and pumpādumpāprobe (PDP) techniques to investigate exciton relaxation mechanisms. Excited-state PP signals resolved a dynamic stimulated emission Stokes shift and ground-state reorganization; PDP signals resolved a blue-shifting nonequilibrium ground-state bleach. Initial structural reorganization is shown to be faster in the excited state. Ground-state reorganization is shown to be dependent on dump time, with later times resulting in relatively more population undergoing slow (ā¼20 ps) reorganization. These observations are discussed in the context of structural relaxation involving small-scale (<1 ps) and large-scale (>1 ps) planarization of thiophene groups following photoexcitation. Excited-state and ground-state dynamics are contrasted in terms of electronic structure defining the torsional potential energy surfaces. It is shown that the primary excitonic relaxation mechanism is excited-state self-trapping via torsional relaxation rather than exciton energy transfer
Measurement of Small Molecular Dopant F4TCNQ and C<sub>60</sub>F<sub>36</sub> Diffusion in Organic Bilayer Architectures
The diffusion of molecules through
and between organic layers is a serious stability concern in organic
electronic devices. In this work, the temperature-dependent diffusion
of molecular dopants through small molecule hole transport layers
is observed. Specifically we investigate bilayer stacks of small molecules
used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C<sub>60</sub>F<sub>36</sub>) used in hole injection layers for organic
light emitting diodes and hole collection electrodes for organic photovoltaics.
With the use of absorbance spectroscopy, photoluminescence spectroscopy,
neutron reflectometry, and near-edge X-ray absorption fine structure
spectroscopy, we are able to obtain a comprehensive picture of the
diffusion of fluorinated small molecules through MeO-TPD layers. F4TCNQ
spontaneously diffuses into the MeO-TPD material even at room temperature,
while C<sub>60</sub>F<sub>36</sub>, a much bulkier molecule, is shown
to have a substantially higher morphological stability. This study
highlights that the differences in size/geometry and thermal properties
of small molecular dopants can have a significant impact on their
diffusion in organic device architectures
Identifying Atomic Scale Structure in Undoped/Doped Semicrystalline P3HT Using Inelastic Neutron Scattering
The
greatest advantage of organic materials is the ability to synthetically
tune desired properties. However, structural heterogeneity often obfuscates
the relationship between chemical structure and functional properties.
Inelastic neutron scattering (INS) is sensitive to both local structure
and chemical environment and provides atomic level details that cannot
be obtained through other spectroscopic or diffraction methods. INS
data are composed of a density of vibrational states with no selection
rules, which means that every structural configuration is equally
weighted in the spectrum. This allows the INS spectrum to be quantitatively
decomposed into different structural motifs. We present INS measurements
of the semiconducting polymer P3HT doped with F4TCNQ supported by
density functional theory calculations to identify two dominant families
of undoped crystalline structures and one dominant doped structural
motif, in spite of considerable heterogeneity. The differences between
the undoped and doped structures indicate that P3HT side chains flatten
upon doping
Introducing Solubility Control for Improved Organic PāType Dopants
To overcome the poor solubility of
the widely used p-type dopant
2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), we
have synthesized a series of structure-modified, organic p-type dopants
to include alkyl ester groups designed to enable solubility and miscibility
control. UVāvisāNIR and cyclic voltammetry measurements
show increased solubility of mono- and diester substituted dopants
with only modest changes to acceptor strength. Using absorption spectroscopy,
photoluminescence, and in-plane conductivity measurements, we demonstrate
that the new dopants can successfully p-type dope polyĀ(3-hexylthiophene-2,5-diyl)
(P3HT). Monoester substituted dopants are characterized by only slightly
reduced electron affinity relative to F4TCNQ, but greater doping effectiveness
due to increased miscibility with P3HT. Diester substituted dopants
undergo a dimerization reaction before assuming their doped states,
which may help anchor dopants into position post deposition, thus
decreasing the negative effect of dopant drift and diffusion. We conclude
that increased dopant solubility/miscibility increases the overall
effectiveness of doping in solution-cast polymer films and that ester
modification is a practical approach to achieving solubility/miscibility
control in TCNQ-type dopants
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Reversible Optical Control of Conjugated Polymer Solubility with Sub-micrometer Resolution
Organic electronics promise to provide flexible, large-area circuitry such as photovoltaics, displays, and light emitting diodes that can be fabricated inexpensively from solutions. A major obstacle to this vision is that most conjugated organic materials are miscible, making solution-based fabrication of multilayer or micro- to nanoscale patterned films problematic. Here we demonstrate that the solubility of prototypical conductive polymer poly(3-hexylthiophene) (P3HT) can be reversibly āswitched offā using high electron affinity molecular dopants, then later recovered with light or a suitable dedoping solution. Using this technique, we are able to stack mutually soluble materials and laterally pattern polymer films by evaporation or with light, achieving sub-micrometer, optically limited feature sizes. After forming these structures, the films can be dedoped without disrupting the patterned features; dedoped films have identical optical characteristics, charge carrier mobilities, and NMR spectra as as-cast P3HT films. This method greatly simplifies solution-based device fabrication, is easily adaptable to current manufacturing workflows, and is potentially generalizable to other classes of materials
Packing Dependent Electronic Coupling in Single Poly(3-hexylthiophene) H- and JāAggregate Nanofibers
Nanofibers (NFs) of the prototype conjugated polymer,
polyĀ(3-hexylthiophene)
(P3HT), displaying H- and J-aggregate character are studied using
temperature- and pressure-dependent photoluminescence (PL) spectroscopy.
Single J-aggregate NF spectra show a decrease of the 0ā0/0ā1
vibronic intensity ratio from ā¼2.0 at 300 K to ā¼1.3
at 4 K. Temperature-dependent PL line shape parameters (i.e., 0ā0
energies and 0ā0/0ā1 intensity ratios) undergo an abrupt
change in the range of ā¼110īø130 K suggesting a change
in NF chain packing. Pressure-dependent PL lifetimes also show increased
contributions from an instrument-limited decay component which is
attributed to greater torsional disorder of the P3HT backbone upon
decreasing NF volume. It is proposed that the P3HT alkyl side groups
change their packing arrangement from a type I to type II configuration
causing a decrease in J-aggregate character (lower intrachain order)
in both temperature- and pressure-dependent PL spectra. Chain packing
dependent exciton and polaron relaxation and recombination dynamics
in NF aggregates are next studied using transient absorption spectroscopy
(TAS). TAS data reveal faster polaron recombination dynamics in H-type
P3HT NFs indicative of interchain delocalization whereas J-type NFs
exhibit delayed recombination suggesting that polarons (in addition
to excitons) are more delocalized along individual chains. Both time-resolved
and steady-state spectra confirm that excitons and polarons in J-type
NFs are predominantly intrachain in nature that can acquire interchain
character with small structural (chain packing) perturbations
Quantitative Dedoping of Conductive Polymers
Although doping is
a cornerstone of the inorganic semiconductor
industry, most devices using organic semiconductors (OSCs) make use
of intrinsic (undoped) materials. Recent work on OSC doping has focused
on the use of dopants to modify a materialās physical properties,
such as solubility, in addition to electronic and optical properties.
However, if these effects are to be exploited in device manufacturing,
a method for dedoping organic semiconductors is required. Here, we
outline two chemical strategies for dedoping OSC films. In the first
strategy, we use an electron donor (a tertiary amine) to act as competitive
donor. This process is based on a thermodynamic equilibrium between
ionization of the donor and OSC and results in only partial dedoping.
In the second strategy, we use an electron donor that subsequently
reacts with the p-type dopant to create a nondoping product molecule.
Primary and secondary amines undergo a rapid addition reaction with
the dopant molecule 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane
(F4TCNQ), with primary amines undergoing a further reaction eliminating
HCN. Under optimized conditions, films of semiconducting polymer polyĀ(3-hexylthiophene)
(P3HT) dedoped with 1-propylamine (PA) reach as-cast fluorescence
intensities within 5 s of exposure to the amine, eventually reaching
140% of the as-cast values. Field-effect mobilities similarly recover
after dedoping. Quantitative fluorescence recovery is possible even
in highly fluorescent polymers such as PFB, which are expected to
be much more sensitive to residual dopants. Interestingly, treatment
of undoped films with PA also yields increased fluorescence intensity
and a reduction in conductivity of at least 2 orders of magnitude.
These results indicate that the process quantitatively removes not
only F4TCNQ but also intrinsic p-type impurities present in as-cast
films. The dedoping strategies outlined in this article are generally
applicable to other p- and n-type molecular dopants in OSC films