Fernando A. Castro

Origin of the Kink in Current-Density Versus Voltage Curves and Efficiency Enhancement of Polymer-C

Current-voltage (J-V ) curves of photovoltaic devices can reveal important microscopic phenomena when parameterization is properly related to physical processes. Here, we identify a pronounced effect of thermal annealing on the organic-cathode metal interface and show that this interface is related to the origin of the kink often observed in J-V curves close to the open circuit. We propose that isolated metal nanoclusters that form upon cathode evaporation lead to defect states close to the interface and change the electric field distribution in the device. We express this scenario with a modified equivalent circuit and consistently fit J- V curves as a function of the annealing process. The developed model is general in the sense that any physical process that leads to the change in electric potential as described in this paper will possibly lead to a kink in the J- V curves. Knowing the origin of the kink allowed us to largely increase the device efficiency of the archetypal material combination Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV) -C. We fabricated solar cells with an efficiency of 1.85% under 100 mW/cm AM1.5 illumination by using a deliberately designed interpenetrating bilayer film morphology, aluminium as cathode and thermal annealing. This is so far the highest reported efficiency for this particular combination of materials.

_{\bf 60}

Significant progress is being made in the photovoltaic energy conversion using soluble small organic molecules. We report the fabrication of layered heterojunction solar cells with 3% power conversion efficiency consisting of a solution-processed cyanine dye, C60 and doped polyaniline anode layers that match the cyanine energy level and facilitate hole extraction.

Heterojunction Solar Cells

In this work we propose a phenomenological microscopic approach to deal with pseudoinductive charge-relaxation processes (named also as negative capacitance phenomena) in organic molecules (tris-8-hydroxyquinoline-aluminum) and polymeric [poly(2-metoxy-5-(2′-etil-hexiloxy)-1,4-phenylene vinylene)] light-emitting diodes (OLEDs and PLEDs, respectively). The approach is based mainly on the fact that the recombination rate is higher than the slower carrier transit time to reach the recombination zone. The approach is supported by the fact that in both PLEDs and OLEDs, the strong pseudoinductive relaxation process was mainly observed when electron-hole recombination takes place, suggesting this is a recombination dependent phenomenon. Besides, the negative branch, in the real part of the complex capacitance representation as a function of the frequency, was not observed in PLED homopolar devices.

Improved performance of cyanine solar cells with polyaniline anodes

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of approximately 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of approximately 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Crossover from capacitive to pseudoinductive charge-relaxation in organic/polymeric light-emitting diodes

The effect of gamma radiation on poly{[2,5-bis(3-(N,N-diethylamino)-1-oxapropyl)-1,4-phenylene]-alt-1,4phenylene} (PPP); poly{[2,5-bis(3-(N,N-diethylammonium bromide)-1-oxapropyl)-1,4-phenylene]-alt-1,4-phenylene} (PPP-Br); and the polymerized dye poly-1-ethyl-2-[3-(1-ethyl-1,3-dihydro-3,3-dimethyl-2H-indol-2-ylidene)-1-propenyl]3,3-dimethyl-3H-indolium perchlorate (Poly-CyC) has been investigated. The stability and response of poly [2-methoxy5-(2ethyl-hexyloxy)-p-phenylenevinylene] (MEH-PPV) in mixed solutions have also been explored. To this end, samples with concentrations ranging from 0.005 to 0.500 mg/mL were irradiated with a 60 Co gamma-ray source at room temperature, using doses up to 1 kGy, and the response was analyzed by UV-Vis spectroscopy. The obtained results reinforce the previously proposed mechanism and suggest that the effect depends on specific structural characteristics of the main chain of the polymers. Moreover, the polymerized dyes display interesting dosimetric properties. Additionally, it has been noted that, contrary to what happens in other solvents, MEH-PPV is degraded in bromoform solution. Protective effects have also been observed for bromoform+toluene mixtures (1:1 vol/vol) and solutions containing molecular dyes.

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Electrically detected magnetic resonance (EDMR) and electron paramagnetic resonance (EPR) were used to investigate emeraldine base polyaniline films. The magnetic susceptibility presented a Curie (localized spins)—Pauli (delocalized spins) transition at 240 K, when we also observed a transition in the dependence of the g factor with temperature (T). Peak-to-peak linewidth decreases with increasing temperature, reflecting that motional narrowing limits the hyperfine and dipolar broadening in this polymer. EDMR spectra could only be observed above 250 K in accordance to EPR results. Surface and bulk transport could be separated and their analysis reflected the effect of magnetic interaction with oxygen.

Gamma-Ray Dosimetric Properties of Conjugated Polymers in Solution

Electrically Detected Magnetic Resonance (EDMR) was used to investigate the influence of dye doping molecules on spin-dependent exciton formation in Aluminum (III) 8-hydroxyquinoline (Alq3) based OLEDs with different device structures and temperature ranges. 4-(dicyanomethylene)-2-methyl-6-{2-[(4-diphenylamino-phenyl]ethyl}-4H-pyran (DCM-TPA) and 5,6,11,12-tetraphenylnaphthacene (Rubrene) were used as dopants. A strong temperature dependence have been observed for doped OLEDs, with a decrease of two orders of magnitude in EDMR signal for temperatures above ~200 K. The signal temperature dependence were fitted supposing different spin-lattice relaxation processes. The results suggest that thermally activated vibrations of dopants molecules induce spin pair dissociation, reducing the signal.

Electrically detected and conventional magnetic resonance investigation of surface and bulk states in polyaniline thin films

The details of the arrangement of mixtures of semiconducting materials in thin-films have a major influence on the performance of organic heterojunction solar cells. Here, we exploit the phenomenon of spinodal dewetting during spin coating of blends of PCBM and a cyanine dye for the design of phase separated morphologies with increased interfacial area. AFM snapshots of as-prepared films and after selective dissolution suggest that the solution separates into transient bilayers, which destabilize due to long-range intermolecular interactions. We propose that film destabilization is effectively driven by electrostatic forces that build up due to mobile ions that cross the junction and dissolve partially in PCBM. The resulting morphology type is mainly dependent on the ratio between the layer thicknesses, whereas the dominant wavelengths formed are determined by the absolute film thickness. Solar cells were fabricated from films with known structure and a power conversion efficiency of η = 0.29 % was measured for a vertically segregated film consisting of a cyanine layer covering the anode and an upper phase composed of dewetted PCBM domains. We explain the merits of this structure in contrast to a lateral separated blend morphology where the efficiency was 3 times smaller.

Exciton formation in dye doped OLEDs using electrically detected magnetic resonance

Significant progress is being made in the photovoltaic energy conversion using organic semiconducting materials. One of the focuses of attention is the nanoscale morphology of the donor-acceptor mixture, to ensure efficient charge generation and loss-free charge transport at the same time. Using small molecule and polymer blend systems, recent efforts highlight the problems to ensure an optimized relationship between molecular structure, morphology and device properties. Here, we present two examples using a host/guest mixture approach for the controlled, sequential design of bilayer organic solar cell architectures that consist of a large interface area with connecting paths to the respective electrodes at the same time. In the first example, we employed polymer demixing during spin coating to produce a rough interface: surface directed spinodal decomposition leads to a 2-dimensional spinodal pattern with submicrometer features at the polymer-polymer interface. The second system consists of a solution of a blend of small molecules, where phase separation into a bilayer during spin coating is followed by dewetting. For both cases, the guest can be removed using a selective solvent after the phase separation process, and the rough host surface can be covered with a second active, semiconducting component. We explain the potential merits of the resulting interdigitated bilayer films, and explore to which extent polymer-polymer and surface interactions can be employed to create surface features in the nanometer range.