Garry Rumbles

Organic solar cells with carbon nanotubes replacing In2O3:Sn as the transparent electrode

We report two viable organic excitonic solar cell structures where the conventional In2O3:Sn (ITO) hole-collecting electrode was replaced by a thin single-walled carbon nanotube layer. The first structure includes poly(3,4-ethylenedioxythiophene) (PEDOT) and gave a nonoptimized device efficiency of 1.5%. The second did not use PEDOT as a hole selective contact and had an efficiency of 0.47%. The strong rectifying behavior of the device shows that nanotubes are selective for holes and are not efficient recombination sites. The reported excitonic solar cell, produced without ITO and PEDOT, is an important step towards a fully printable solar cell.

Optimal negative electrodes for poly(3-hexylthiophene): [6,6]-phenyl C61-butyric acid methyl ester bulk heterojunction photovoltaic devices

The role of the work function and interfacial chemistry on organic device performance was investigated by using a series of contact materials. The active layer was a standard blend of poly(3-hexylthiophene) and [6-6]-phenyl C61-butyric acid methyl ester. Over 100 devices were fabricated and measured to obtain good statistics. Ba∕Al and Ca∕Al electrodes performed best, with similar open-circuit voltages and power conversion efficiencies. Device stability studies showed devices with these two electrodes remained similar after six weeks with degradation of 11%–16% in net conversion efficiency observed. The incorporation of silver into the electrodes led to considerably more degradation than other electrode types.

Controlled assembly of hydrogenase-CdTe nanocrystal hybrids for solar hydrogen production

We present a study of the self-assembly, charge-transfer kinetics, and catalytic properties of hybrid complexes of CdTe nanocrystals (nc-CdTe) and Clostridium acetobutylicum [FeFe]-hydrogenase I (H(2)ase). Molecular assembly of nc-CdTe and H(2)ase was mediated by electrostatic interactions and resulted in stable, enzymatically active complexes. The assembly kinetics was monitored by nc-CdTe photoluminescence (PL) spectroscopy and exhibited first-order Langmuir adsorption behavior. PL was also used to monitor the transfer of photogenerated electrons from nc-CdTe to H(2)ase. The extent to which the intramolecular electron transfer (ET) contributed to the relaxation of photoexcited nc-CdTe relative to the intrinsic radiative and nonradiative (heat dissipation and surface trapping) recombination pathways was shown by steady-state PL spectroscopy to be a function of the nc-CdTe/H(2)ase molar ratio. When the H(2)ase concentration was lower than the nc-CdTe concentration during assembly, the resulting contribution of ET to PL bleaching was enhanced, which resulted in maximal rates of H(2) photoproduction. Photoproduction of H(2) was also a function of the nc-CdTe PL quantum efficiency (PLQE), with higher-PLQE nanocrystals producing higher levels of H(2), suggesting that photogenerated electrons are transferred to H(2)ase directly from core nanocrystal states rather than from surface-trap states. The duration of H(2) photoproduction was limited by the stability of nc-CdTe under the reactions conditions. A first approach to optimization with ascorbic acid present as a sacrificial donor resulted in photon-to-H(2) efficiencies of 9% under monochromatic light and 1.8% under AM 1.5 white light. In summary, nc-CdTe and H(2)ase spontaneously assemble into complexes that upon illumination transfer photogenerated electrons from core nc-CdTe states to H(2)ase, with low H(2)ase coverages promoting optimal orientations for intramolecular ET and solar H(2) production.

PHTHALOCYANINE FLUORESCENCE AT HIGH CONCENTRATION: DIMERS OR REABSORPTION EFFECT?

Abstract— For tetrasulfonated aluminum phthalocyanine (AlPcS4), dimer formation is characterized in the absorption spectrum by a broadening of the Q‐band and the appearance of a new band at the red edge of the spectrum. The high concentrations required to produce dimers, however, often leads to anomalous observations in fluorescence spectroscopy. In the present study, we have examined the photophysical characteristics of two dye systems; AlPcS4 in a 66% ethanol/water mixture and disulfonated aluminum phthalocyanine in methanol. Using absorption spectroscopy, the formation of dimers is shown to be prevalent only in the case of AlPcS4. The fluorescence emission spectra in both cases, however, exhibit similar spectral changes with increasing dye concentration. The measured fluorescence decay profiles for both dyes also show similar trends: They are monoexponential, invariant with emission wavelength and have decay times that increase with dye concentration. These distortions are sometimes incorrectly attributed to dimer fluorescence. We find no evidence for the existence of dimer fluorescence and demonstrate that these data can be readily explained, by taking into consideration the effects of reabsorption of fluorescence.

Performance of Bulk Heterojunction Photovoltaic Devices Prepared by Airbrush Spray Deposition

We have used airbrush spray deposition to fabricate organic photovoltaic devices with an active layer composed of a blend of poly(3-hexylthiophene) and [6,6]-phenyl-C61 butyric acid methyl ester. Working devices were prepared in ambient conditions from a variety of common organic solvents; active layers prepared from chlorobenzene exhibit improved homogeneity, resulting in narrower distributions of the relevant device parameters. Further studies on devices prepared from chlorobenzene showed that annealing at 120°C for 10min resulted in optimum performance, and that an active layer thickness of 150nm resulted in a maximum efficiency of 2.35% under AM1.5 illumination at 1sun.

Bulk heterojunction organic photovoltaic devices based on phenyl-cored thiophene dendrimers

Bulk heterojunction organic photovoltaic devices have been fabricated by blending phenyl-cored thiophene dendrimers with a fullerene derivative. A power conversion efficiency of 1.3% under simulated AM1.5 illumination is obtained for a four-arm dendrimer, despite its large optical band gap of 2.1eV. The devices exhibit an increase in short-circuit current and power conversion efficiency as the length of the arm is increased. The fill factors of the devices studied are characteristically low, which is attributed to overly uniform mixing of the blend.

The efficiency and time-dependence of luminescence from poly (p-phenylene vinylene) and derivatives

Abstract We report measurements of the quantum efficiency and time decay of photoluminescence in the conjugated polymers poly ( p -phenylenevinylene) (PPV) and poly (2-methoxy, 5- (2′ethyl-hexyloxy)- p -phenylenevinylene ) (MEH-PPV). MEH-PPV is soluble and we measure values for the quantum yield for luminescence of order 35% for dilute solutions in toluene and chloroform. By comparison of luminescence decay rates in solution and in solid films we estimate luminescence efficiencies in solid films, which can be as high as 50% in partially conjugated PPV. Decay time distribution analysis of the luminescence reveals a broad distribution of decay rates, and this is consistent with the distribution of conjugation lengths known to be present in these materials Exciton migration in better conjugated material results in narrower distributions of emitting chromophores.

Prolonging Charge Separation in P3HT−SWNT Composites Using Highly Enriched Semiconducting Nanotubes

Single-walled carbon nanotubes (SWNTs) have potential as electron acceptors in organic photovoltaics (OPVs), but the currently low-power conversion efficiencies of devices remain largely unexplained. We demonstrate effective redispersion of isolated, highly enriched semiconducting and metallic SWNTs into poly(3-hexylthiophene) (P3HT). We use these enriched blends to provide the first experimental evidence of the negative impact of metallic nanotubes. Time-resolved microwave conductivity reveals that the long-lived carrier population can be significantly increased by incorporating highly enriched semiconducting SWNTs into semiconducting polymer composites.

Chromism and luminescence in regioregular poly(3-dodecylthiophene)

Abstract We report photoluminescence studies of poly(3-dodecylthiophene) (P3DT) in solution. In a good solvent the polymer exhibits luminescence with a high quantum efficiency and a decay time of 500 ps. In a poor solvent the emission is red shifted with a 20-fold reduction in quantum efficiency and a decay profile that is non-monoexponential, but has an average lifetime that is very similar to the good solvent environment. The data indicate a large increase in the natural radiative lifetime from approximately 1 ns in a good solvent to 20 ns in a poor solvent, which implies an emitting state that is different in the two situations. In the poor solvent the spectrum is almost identical to that of the thin film, suggesting that the polymer aggregates in the solution and the emitting species is the same in both environments. The data are consistent with the formation of an excited state that is not localized on a single chain but is delocalized over more than one chain.

Picosecond Time-Resolved Photoluminescence of PPV Derivatives

We report some time-resolved luminescence measurements on the conjugated polymer, MEH-PPV, that show a marked dependence on the intensity of the excitation light. At low laser powers the excited state lifetime is longer than has been reported previously and is consistent with emission from an interchain excitation that has low oscillator strength and hence a long natural radiative lifetime. We rationalise these data with a simple scheme that summarises the excited state kinetics in this and other conjugated, electroluminescent polymers.