444 research outputs found
Effect of Intra-molecular Disorder and Inter-molecular Electronic Interactions on the Electronic Structure of Poly-p-Phenylene Vinylene (PPV)
We investigate the role of intra-molecular conformational disorder and
inter-molecular electronic interactions on the electronic structure of disorder
clusters of poly-p-phenylene vinylene (PPV) oligomers. Classical molecular
dynamics is used to determine probable molecular geometries, and
first-principle density functional theory (DFT) calculations are used to
determine electronic structure. Intra-molecular and inter-molecular effects are
disentangled by contrasting results for densely packed oligomer clusters with
those for ensembles of isolated oligomers with the same intra-molecular
geometries. We find that electron trap states are induced primarily by
intra-molecular configuration disorder, while the hole trap states are
generated primarily from inter-molecular electronic interactions.Comment: 4 pages, 4 figures. Compile with pdflate
To bend or not to bend â are heteroatom interactions within conjugated molecules effective in dictating conformation and planarity?
We consider the roles of heteroatoms (mainly nitrogen, the halogens and the chalcogens) in dictating the conformation of linear conjugated molecules and polymers through non-covalent intramolecular interactions. Whilst hydrogen bonding is a competitive and sometimes more influential interaction, we provide unambiguous evidence that heteroatoms are able to determine the conformation of such materials with reasonable predictability
Strong Suppression of Thermal Conductivity in the Presence of Long Terminal Alkyl Chains in Low-Disorder Molecular Semiconductors
While the charge transport properties of organic semiconductors have been extensively studied over the recent years, the field of organics-based thermoelectrics is still limited by a lack of experimental data on thermal transport and of understanding of the associated structureâproperty relationships. To fill this gap, a comprehensive experimental and theoretical investigation of the lattice thermal conductivity in polycrystalline thin films of dinaphtho[2,3-b:2âČ,3âČ-f]thieno[3,2-b]thiophene (Cn-DNTT-Cn with n = 0, 8) semiconductors is reported. Strikingly, thermal conductivity appears to be much more isotropic than charge transport, which is confined to the 2D molecular layers. A direct comparison between experimental measurements (3ÏâVölklein method) and theoretical estimations (approach-to-equilibrium molecular dynamics (AEMD) method) indicates that the in-plane thermal conductivity is strongly reduced in the presence of the long terminal alkyl chains. This evolution can be rationalized by the strong localization of the intermolecular vibrational modes in C8-DNTT-C8 in comparison to unsubstituted DNTT cores, as evidenced by a vibrational mode analysis. Combined with the enhanced charge transport properties of alkylated DNTT systems, this opens the possibility to decouple electron and phonon transport in these materials, which provides great potential for enhancing the thermoelectric figure of merit ZT
On the Munn-Silbey approach to polaron transport with off-diagonal coupling
Improved results using a method similar to the Munn-Silbey approach have been
obtained on the temperature dependence of transport properties of an extended
Holstein model incorporating simultaneous diagonal and off-diagonal
exciton-phonon coupling. The Hamiltonian is partially diagonalized by a
canonical transformation, and optimal transformation coefficients are
determined in a self-consistent manner. Calculated transport properties exhibit
substantial corrections on those obtained previously by Munn and Silbey for a
wide range of temperatures thanks to a numerically exact evaluation and an
added momentum-dependence of the transformation matrix. Results on the
diffusion coefficient in the moderate and weak coupling regime show distinct
band-like and hopping-like transport features as a function of temperature.Comment: 12 pages, 6 figures, accpeted in Journal of Physical Chemistry B:
Shaul Mukamel Festschrift (2011
Energetic fluctuations in amorphous semiconducting polymers: Impact on charge-carrier mobility
We present a computational approach to model hole transport in an amorphous semiconducting fluorene-triphenylamine copolymer (TFB), which is based on the combination of molecular dynamics to predict the morphology of the oligomeric system and Kinetic Monte Carlo (KMC), parameterized with quantum chemistry calculations, to simulate hole transport. Carrying out a systematic comparison with available experimental results, we discuss the role that different transport parameters play in the KMC simulation and in particular the dynamic nature of positional and energetic disorder on the temperature and electric field dependence of charge mobility. It emerges that a semi-quantitative agreement with experiments is found only when the dynamic nature of the disorder is taken into account. This study establishes a clear link between microscopic quantities and macroscopic hole mobility for TFB and provides substantial evidence of the importance of incorporating fluctuations, at the molecular level, to obtain results that are in good agreement with temperature and electric field-dependent experimental mobilities. Our work makes a step forward towards the application of nanoscale theoretical schemes as a tool for predictive material screening
Sample-Averaged Biexciton Quantum Yield Measured by Solution-Phase Photon Correlation
The brightness of nanoscale optical materials such as semiconductor nanocrystals is currently limited in high excitation flux applications by inefficient multiexciton fluorescence. We have devised a solution-phase photon correlation measurement that can conveniently and reliably measure the average biexciton-to-exciton quantum yield ratio of an entire sample without user selection bias. This technique can be used to investigate the multiexciton recombination dynamics of a broad scope of synthetically underdeveloped materials, including those with low exciton quantum yields and poor fluorescence stability. Here, we have applied this method to measure weak biexciton fluorescence in samples of visible-emitting InP/ZnS and InAs/ZnS core/shell nanocrystals, and to demonstrate that a rapid CdS shell growth procedure can markedly increase the biexciton fluorescence of CdSe nanocrystals.United States. Dept. of Energy. Office of Basic Energy Sciences (DE-FG02-07ER46454)United States. Dept. of Energy. Office of Basic Energy Sciences (DE-SC0001088)National Institutes of Health (U.S.) (9P41EB015871-26A1
A model for the dynamics and internal structure of planar doping fronts in organic semiconductors
The dynamics and internal structure of doping fronts in organic
semiconductors are investigated theoretically using an extended drift-diffusion
model for ions, electrons and holes. The model also involves the injection
barriers for electrons and holes in the partially doped regions in the form of
the Nernst equation, together with a strong dependence of the electron and hole
mobility on concentrations. Closed expressions for the front velocities and the
ion concentrations in the doped regions are obtained. The analytical theory is
employed to describe the acceleration of the p- and n-fronts towards each
other. The analytical results show very good agreement with the experimental
data. Furthermore, it is shown that the internal structure of the doping fronts
is determined by the diffusion and mobility processes. The asymptotic behavior
of the concentrations and the electric field is studied analytically inside the
doping fronts. The numerical solution for the front structure confirms the most
important predictions of the analytical theory: a sharp head of the front in
the undoped region, a smooth relaxation tail in the doped region, and a plateau
at the critical point of transition from doped to undoped regions.Comment: 13 pages, 11 figure
Operating organic light-emitting diodes imaged by super-resolution spectroscopy
Super-resolution stimulated emission depletion (STED) microscopy is adapted here for materials characterization that would not otherwise be possible. With the example of organic light-emitting diodes (OLEDs), spectral imaging with pixel-by-pixel wavelength discrimination allows us to resolve local-chain environment encoded in the spectral response of the semi-conducting polymer, and correlate chain packing with local electroluminescence by using externally applied current as the excitation source. We observe nanoscopic defects that would be unresolvable by traditional microscopy. They are revealed in electroluminescence maps in operating OLEDs with 50 nm spatial resolution. We find that brightest emission comes from regions with more densely packed chains. Conventional microscopy of an operating OLED would lack the resolution needed to discriminate these features, while traditional methods to resolve nanoscale features generally cannot be performed when the device is operating. This points the way towards real-time analysis of materials design principles in devices as they actually operateope
Freezing-in orientational disorder induces crossover from thermally-activated to temperature-independent transport in organic semiconductors
The crystalline structure of organic materials dictates their physical properties, but while significant research effort is geared towards understanding structure-property relationships in such materials, the details remain unclear. Many organic crystals exhibit transitions in their electrical properties as a function of temperature. One example is the 1:1 charge-transfer complex trans--stilbene-2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. Here we show that the mobility and resistivity of this material undergo a transition from being thermally activated at temperatures above 235 K to being temperature independent at low temperatures. On the basis of our experimental and theoretical results, we attribute this behaviour to the presence of a glass-like transition and the accompanied freezing-in of orientational disorder of the stilbene molecule
Exciton/Charge-transfer Electronic Couplings in Organic Semiconductors
Charge transfer (CT) states and excitons are important in energy conversion processes that occur in organic light emitting devices (OLEDS) and organic solar cells. An ab initio density functional theory (DFT) method for obtaining CTâexciton electronic couplings between CT states and excitons is presented. This method is applied to two organic heterodimers to obtain their CTâexciton coupling and adiabatic energy surfaces near their CTâexciton diabatic surface crossings. The results show that the new method provides a new window into the role of CT states in excitonâexciton transitions within organic semiconductors.United States. Dept. of Energy (DEFG02- 07ER46474)David & Lucile Packard Foundation (Fellowship
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