Girish Lakhwani

Bimolecular Recombination in Organic Photovoltaics

The recombination of electrons and holes is a major loss mechanism in photovoltaic devices that controls their performance. We review scientific literature on bimolecular recombination (BR) in bulk heterojunction organic photovoltaic devices to bring forward existing ideas on the origin and nature of BR and highlight both experimental and theoretical work done to quantify its extent. For these systems, Langevin theory fails to explain BR, and recombination dynamics turns out to be dependent on mobility, temperature, electric field, charge carrier concentration, and trapped charges. Relationships among the photocurrent, open-circuit voltage, fill factor, and morphology are discussed. Finally, we highlight the recent emergence of a molecular-level picture of recombination, taking into account the spin and delocalization of charges. Together with the macroscopic picture of recombination, these new insights allow for a comprehensive understanding of BR and provide design principles for future materials and devices.

Voltage-dependent photocurrent transients of PTB7:PC70BM solar cells: Experiment and numerical simulation

Transient photocurrent measurements on efficient polymer/fullerene solar cells based on a blend of the donor polymer PTB7 with the fullerene acceptor PC70BM are reported. In particular, we examine the light intensity dependence and voltage dependence of the turn-on and turn-off photocurrent dynamics of devices in response to a 200 μs square light pulse. At short circuit, subtle changes in the turn-on and turn-off dynamics are observed consistent with charge-density-dependent transport phenomena. As the working voltage is moved from short circuit to open circuit, we observe the appearance of an initial transient photocurrent peak a few microseconds after turn-on before the device settles to steady state. Furthermore, we observe only a weak dependence of the charge extraction dynamics on the working voltage, with the amount of charge extracted monotonically decreasing as the working voltage is moved from short circuit to open circuit. This collection of features is interpreted with the aid of numerical simulations in terms of charge trapping, with increased trap-assisted recombination closer to open circuit. The operation of devices fabricated with and without the solvent additive di-iodooctane is also compared. Charge trapping features are reduced for optimized devices fabricated with the solvent additive compared to devices fabricated without. The use of the solvent additive di-iodooctane in this system is therefore important in minimizing trap-assisted recombination.

Electronic Energy Transfer in Highly Aligned MEH-PPV Single Chains

This paper describes the simultaneous measurement of excitation and emission anisotropy to visualize energy transfer in single chains of the prototypical conjugated polymer MEH-PPV, for samples with >70% of the single chains organized into extended, rod-like conformations. The uniformity and high degree of order of the single molecules in these experiments has allowed direct comparison of our experimental data to energy-transfer simulations in model polymer chains. Increases in average anisotropy from 0.62 to 0.74 from excitation to emission and average changes of <15° to the in-plane dipole principal orientation axis confirmed that energy was transferred to a relatively small number of sites in these highly ordered chains. This organization persisted even at large molecular weights (M(n) = 850 kDa). Electronic energy transfer in highly anisotropic model chains was simulated using an incoherent Förster-type mechanism to generate modulation depth histograms in good agreement with the observed data, as well as ensemble emission energies consistent with previously reported results. In these ordered model chains, excitons migrated an average of 6 nm before emission. This distance, far larger than the radius for single-step FRET, implies that energy transfer in MEH-PPV is a multistep funneling process.

Polymer Photovoltaic Cells Sensitive to the Circular Polarization of Light

Chiral conjugated polymer is used to construct a photovoltaic cell whose response depends on the circular polarization of the incoming light. The selectivity for left and right polarized light as a function of the thickness of the polymer layer is accounted for by modeling of the optical properties of all layers inside the device.

Interface limited charge extraction and recombination in organic photovoltaics

We report that the transit-time of photogenerated holes within an OPV device is significantly controlled by the interface between the photoactive layer and the electrode. We used time-resolved optical absorption spectroscopy to track the evolution and transport of photogenerated holes in situ within efficient PTB7:PC70BM (thieno [3,4-b] thiophene/benzodithiophene:[6,6]-phenyl C71-butyric acid methyl ester) devices. Our results demonstrate that the time required for 50% hole extraction is reduced from 2.3 μs for the standard devices to 0.9 μs either by introducing a thin layer of conjugated polyelectrolyte (CPE) layer at the electron-extracting cathode or simply by exposing the device to a polar solvent such as methanol which is used for spin coating the CPEs. We consider that the CPE modifies the interface between the photoactive layer and the cathode whereas the exposure of the device to associated polar solvent modifies the buried PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate) hole extracting layer.

Conformational effect on energy transfer in single polythiophene chains.

Herein we describe the use of regioregular (rr-) and regiorandom (rra-) P3HT as models to study energy transfer in ordered and disordered single conjugated polymer chains. Single molecule fluorescence spectra and excitation/emission polarization measurements were compared with a Förster resonance energy transfer (FRET) model simulation. An increase in the mean single chain polarization anisotropy from excitation to emission was observed for both rr- and rra-P3HT. The peak emission wavelengths of rr-P3HT were at substantially lower energies than those of rra-P3HT. A simulation based on FRET in single polymer chain conformations successfully reproduced the experimental observations. These studies showed that ordered conformations facilitated efficient energy transfer to a small number of low-energy sites compared to disordered conformations. As a result, the histograms of spectral peak wavelengths for ordered conformations were centered at much lower energies than those obtained for disordered conformations. Collectively, these experimental and simulated results provide the basis for quantitatively describing energy transfer in an important class of conjugated polymers commonly used in a variety of organic electronics applications.

Probing the switching mechanism in ZnO nanoparticle memristors

We investigate the resistance switching mechanism in memristors based on colloidal ZnO nanoparticles using electroabsorption (EA) spectroscopy. In this EA experiment, we incorporate a small amount of low-bandgap polymer, poly(9,9-dioctylfluorene-co-benzothiadiazole), as a probe molecule in ZnO-nanoparticle memristors. By characterizing this polymer, we can study the change of built-in potential (VBI) in the device during the resistance switching process without disturbing the resistance state by the EA probe light. Our results show that VBI increases when the device is switched to the high resistance state, suggesting a shift of effective workfunction of the electrode. Thus, we attribute the resistance switching to the field-dependent migration of oxygen vacancies associated with the adsorption and desorption of oxygen molecules at the Al/ZnO interface. This process results in the modulation of the interfacial injection barrier, which governs the resistance state of the device.

Intensive Chiroptical Properties of Chiral Polyfluorenes Associated with Fibril Formation

Thin films of chiral poly{9,9-bis[(3S)-3,7-dimethyloctyl]-2,7-fluorene} (1) were studied using circular dichroism (CD) spectroscopy. Films spin coated from chloroform solution, show CD with a degree of polarization g(abs) (= +4 x 10(-4) at 400 nm) that is independent of film thickness (50-290 nm). This implies that g(abs) is an intensive property of the material and related to the chiral organization of the molecules on a length scale less than 50 nm. Atomic force microscopy (AFM) on the films reveals fibrils. Addition of nonsolvent methanol to a solution of 1 in chloroform leads to fibril formation in solution and results in CD similar in band shape to that of the pristine spin coated films from chloroform solution and a g(abs) comparable in magnitude. Thus the chiral molecular arrangement leading to circular dichroism is part of the internal structure of these fibrils.

Near-field circular polarization probed by chiral polyfluorene

We demonstrate that a high degree of circular polarization can be delivered to the near field (NF) of an aperture at the apex of hollow-pyramid probes for scanning optical microscopy. This result is achieved by analyzing the dichroic properties of an annealed thin polymer film containing a chiral polyfluorene derivative, placed in close proximity to the optical probe. We also prove that the degree of circular polarization in the probe NF does not depend in a significant way on the shape of the aperture, at variance with the far-field behavior. These results demonstrate the feasibility of nano-optics applications exploiting circularly polarized NFs.

Anisotropic dielectric tensor for chiral polyfluorene at optical frequencies

The anisotropic dielectric tensor of chiral poly[9,9-bis((3S)-3,7-dimethyloctyl)-2,7-fluorene] is determined via variable angle spectroscopic ellipsometry and circular dichroism spectroscopy. The uniaxial anisotropy indicates a high in-plane alignment of polymer chains in the thin film. Chirality of the polymer results in small but nonzero off-diagonal matrix elements in the dielectric tensor, indicating a helical interchain organization in the vertical direction. This method for determining the dielectric tensor appears to be self-consistent when checked against various theoretical models for the optical activity in the reflection of light. The dielectric constants for the chiral polyfluorene are compared to those for an achiral polyfluorene.