John B. Asbury

Barrierless Free Carrier Formation in an Organic Photovoltaic Material Measured with Ultrafast Vibrational Spectroscopy

The dynamics of free carrier formation following photoinduced electron transfer from the conjugated polymer, CN-MEH-PPV, to the electron-accepting functionalized fullerene, PCBM, are directly measured using ultrafast vibrational spectroscopy. The vibrational frequency of the carbonyl (C horizontal lineO) stretch of PCBM is sensitive to the location of the molecules relative to the interfaces formed between PCBM clusters and CN-MEH-PPV. The correlation between the carbonyl frequency and the proximity to the interfaces provides the ability to directly measure the escape of electrons from their Coulombically bound radical pairs. The data indicate that the rate of free carrier formation is temperature independent from 200 to 350 K suggesting that excess vibrational energy resulting from the electron transfer reaction enables electrons to escape their Coulombic potentials on ultrafast time scales.

Spectral diffusion in a fluctuating charge model of water.

We apply the combined electronic structure/molecular dynamics approach of Corcelli, Lawrence, and Skinner [J. Chem. Phys. 120, 8107 (2004)] to the fluctuating charge (SPC-FQ) model of liquid water developed by Rick, Stuart, and Berne [J. Chem. Phys. 101, 6141 (1994)]. For HOD in H(2)O the time scale for the long-time decay of the OD stretch frequency time-correlation function, which corresponds to the time scale for hydrogen-bond rearrangement in the liquid, is about 1.5 ps. This result is significantly longer than the 0.9 ps decay previously calculated for the nonpolarizable SPC/E water model. Our results for the SPC-FQ model are in better agreement with recent vibrational echo experiments.

Hydrogen bond breaking probed with multidimensional stimulated vibrational echo correlation spectroscopy

H bond population dynamics are extricated with exceptional detail using ultrafast (<50 fs) IR multidimensional stimulated vibrational echo correlation spectroscopy with full phase information and frequency resolved IR pump-probe expts. performed on the hydroxyl stretch of MeOH-OD oligomers in CCl4. H bond breaking makes it possible to acquire data for times much greater than the hydroxyl stretch vibrational lifetime. The correlation spectra and detailed calcns. demonstrate that vibrational relaxation leads to H bond breaking for oligomers that have hydroxyl stretch frequencies on the low energy (red) side of the hydroxyl stretch spectrum, the spectral region that is assocd. with the strongest H bonds. Frequency resolved pump-probe data support the conclusions drawn from the correlation spectra. Using a global fit to the pump-probe spectra, in conjunction with assignments made possible through the correlation spectra, the residual ground state and photoproduct of H bond breaking were prepd. near their thermal equil. distribution. The spectrum of the H bond breaking photoproduct and the residual ground state approach the steady-state temp. difference spectrum on the tens of picoseconds time scale, indicating the system thermalizes on this time scale. [on SciFinder(R)]

Ultrafast heterodyne detected infrared multidimensional vibrational stimulated echo studies of hydrogen bond dynamics

Multidimensional vibrational stimulated echo correlation spectra with full phase information are presented for the broad hydroxyl stretch band of methanol-OD oligomers in CCl4 using ultrashort ( 1 ps) shows that there is frequency correlation between the initially excited hydroxyl stretch and the frequency shifted hydroxyl stretch formed by hydrogen bond breaking.

Observation of Two Triplet-Pair Intermediates in Singlet Exciton Fission

Singlet fission is an excitation multiplication process in molecular systems that can circumvent energy losses and significantly boost solar cell efficiencies; however, the nature of a critical intermediate that enables singlet fission and details of its evolution into multiple product excitations remain obscure. We resolve the initial sequence of events comprising the fission of a singlet exciton in solids of pentacene derivatives using femtosecond transient absorption spectroscopy. We propose a three-step model of singlet fission that includes two triplet-pair intermediates and show how transient spectroscopy can distinguish initially interacting triplet pairs from those that are spatially separated and noninteracting. We find that the interconversion of these two triplet-pair intermediates is limited by the rate of triplet transfer. These results clearly highlight the classical kinetic model of singlet fission and expose subtle details that promise to aid in resolving problems associated with triplet extraction.

Approaching Bulk Carrier Dynamics in Organo-Halide Perovskite Nanocrystalline Films by Surface Passivation

The electronic properties of organo-halide perovskite absorbers described in the literature have been closely associated with their morphologies and processing conditions. However, the underlying origins of this dependence remain unclear. A combination of inorganic synthesis, surface chemistry, and time-resolved photoluminescence spectroscopy was used to show that charge recombination centers in organo-halide perovskites are almost exclusively localized on the surfaces of the crystals rather than in the bulk. Passivation of these surface defects causes average charge carrier lifetimes in nanocrystalline thin films to approach the bulk limit reported for single-crystal organo-halide perovskites. These findings indicate that the charge carrier lifetimes of perovskites are correlated with their thin-film processing conditions and morphologies through the influence these have on the surface chemistry of the nanocrystals. Therefore, surface passivation may provide a means to decouple the electronic properties of organo-halide perovskites from their thin-film processing conditions and corresponding morphologies.

Tuning the Dielectric Properties of Organic Semiconductors via Salt Doping

Enhancing the dielectric permittivity of organic semiconductors may open new opportunities to control charge generation and recombination dynamics in organic solar cells. The potential to tune the dielectric permittivity of organic semiconductors by doping them with redox inactive salts was explored using a combination of organic synthesis, electrical characterization, and time-resolved infrared spectroscopy. The addition of the salt, LiTFSI (lithium bis(trifluoro-methyl-sulfonyl)imide), to a conjugated polymer specifically designed to incorporate ions into its bulk phase increased the density of holes and enhanced the static dielectric permittivity of the polymer blend by more than an order of magnitude. The frequency and phase dependence of the real dielectric function demonstrates that the increase in dielectric permittivity resulted from dipolar motion of bound ion pairs or clusters of ions. Interestingly, the increases in the hole density and dielectric permittivity were associated with enhancement of the hole mobility by 2 orders of magnitude relative to the undoped polymer. The charge recombination lifetime also increased by an order of magnitude in the blend with a fullerene electron acceptor when ions were added to the polymer. The findings indicate that ion doping enables organic semiconductors with large increases in low frequency dielectric permittivity and that these changes result in improved charge transport and suppressed charge recombination on the microsecond time scale.

Vibrational spectroscopy of electronic processes in emerging photovoltaic materials.

Molecules affect the electronic properties of many emerging materials, ranging from organic thin film transistors and light emitting diodes for flexible displays to colloidal quantum dots (CQDs) used in solution processed photovoltaics and photodetectors. For example, the interactions of conjugated molecules not only influence morphological and charge transport properties of organic photovoltaic (OPV) materials, but they also determine the primary photophysical events leading to charge generation. Ligand-nanocrystal interactions affect the density and energetic distributions of trap states, which in turn influence minority carrier transport in CQD photovoltaics. Therefore, it is critical for scientists to understand how the underlying molecular structures and morphologies determine the electronic properties of emerging materials. Recently, chemists have used vibrational spectroscopy to study electronic processes in emerging materials, and been able to directly measure the influence molecular properties have on those processes. Time-resolved vibrational spectroscopy is uniquely positioned to examine molecular species involved in electronic processes because it combines ultrafast time resolution with measurement of the vibrational spectra of molecules. For instance, molecules at the electron donor/acceptor interfaces in OPV materials have unique vibrational features because vibrational frequencies of molecules are sensitive to their local molecular environments. Through ultrafast vibrational spectroscopy, researchers can directly examine the dynamics of charge transfer (CT) state formation and dissociation to form charge separated states specifically at donor/acceptor interfaces. Vibrational modes of ligands are also sensitive to their bonding interactions with nanocrystal surfaces, which enables chemists to directly probe the molecular nature of charge trap states in colloidal quantum dot solids. Because of the ability to connect electrical properties with the underlying molecular species, scientists can use ultrafast vibrational spectroscopy to address fundamental challenges in the development of emerging electronic materials. In this Account, we focus on two applications of vibrational spectroscopy to examine electronic processes in OPV and CQD photovoltaic materials. In the first application, we examine archetypal classes of electron acceptors in OPV materials and reveal how their molecular structures influence the dynamics and energetic barriers to CT state formation and dissociation. In the second application, we discuss the surface chemistry of ligand-nanocrystal interactions and how they impact the density and energetic distribution of charge trap states in CQD photovoltaic materials. Through direct observations of the vibrational features of ligands attached to surface trap states, we can obtain valuable insights into the nature of charge traps and begin to understand pathways for their elimination. We expect that further examination of electronic processes in materials using ultrafast vibrational spectroscopy will lead to new design rules in support of continued materials development efforts.

Temperature-independent vibrational dynamics in an organic photovoltaic material.

Ultrafast orientational motion and spectral diffusion of the carbonyl stretch vibration of the functionalized fullerene, PCBM, blended with the conjugated polymer, CN-MEH-PPV, are examined with two-dimensional infrared and polarization-resolved IR pump probe spectroscopy. In previous contributions from our group, the carbonyl stretch frequency of PCBM has been used as a local vibrational reporter to measure the temperature dependence of the time scale for dissociation of charge transfer excitons in CN-MEH-PPV:PCBM polymer blends. It was found that the rate of charge separation is independent of temperature, indicating that charge separation occurs through an activationless pathway. This assignment was supported by the observation at room temperature that thermal fluctuations do not give rise to spectral diffusion of the carbonyl stretch vibration on the picosecond and longer time scale. In this contribution, we examine the temperature dependence of the carbonyl vibrational dynamics to determine whether thermal fluctuations might give rise to spectral diffusion at other temperatures. We find that the time scale for fast wobbling-in-cone orientational motion is independent of temperature on the subpicosecond time scale. Similarly, spectral diffusion is not observed on the picosecond and longer time scale at all temperatures examined confirming our earlier interpretation of the frequency shift dynamics exclusively in terms of charge separation. Interestingly, the half angle characterizing the wobbling-in-cone orientational motion does increase at higher temperature due to increased free-volume resulting from thermal expansion of the polymer blend.

Accidental vibrational degeneracy in vibrational excited states observed with ultrafast two-dimensional IR vibrational echo spectroscopy

The coupling between the OD stretch v=2 level and benzene-ring modes in 2-methoxyphenol-OD (hydroxyl H replaced by D) is observed with ultrafast two-dimensional (2D) IR vibrational echo spectroscopy. Because of this coupling, the 1-2 transition peak in the 2D spectrum is split into a doublet with peaks of approximately equal amplitudes. Several molecules and solvents were used to study this phenomenon. Near-IR (NIR) spectroscopy measurements and density-functional theory calculations (B3LYP6-31+G(d,p) level) were also applied. Experimental results and calculations show that the OD stretch 1-2 transition is coupled to a combination band related to the benzene-ring motions. A simple quantum-mechanical model indicates that the combination band has a frequency of 5172 and 5176.5 cm(-1) in CCl4 and hexane, respectively. The transition between this combination band and the ground state is too weak to detect by NIR. The transition between this band and the OD stretch first excited state is also so weak that most of the intensity of the doublet comes from the oscillator strength produced by coupling to the OD stretch. The model gives the coupling strengths as 6.5 and 7 cm(-1) in CCl4 and hexane, respectively.