Fortunato Piersimoni

Investigation of defects by admittance spectroscopy measurements in poly (3-hexylthiophene):(6,6)-phenyl C61-butyric acid methyl ester organic solar cells degraded under air exposure

Electrical transport properties of poly (3-hexylthiophene) (P3HT) (6,6)-phenyl C61-butyric acid methyl ester (PCBM) solar cells, with and without encapsulation, have been investigated and analyzed using admittance spectroscopy and capacitance voltage measurements at different temperatures. The admittance spectroscopy clearly reveals two defect states with activation energies of 53 and 100 meV, and a concentration ten times higher in the unencapsulated sample. These defects seem to have a strong effect on the charge transport and the solar cell performance when they are present with a high concentration, since they lead to a decrease of the mobility and also the short-circuit current and the efficiency. The origin of these defects has been assigned to reaction of the blend with O2 which is also known to induce p-type doping in pure P3HT. In an attempt to understand the effect of these defects on the organic solar cell performance, modeling and simulation were carried out using the effective medium layer mo...

Toward bulk heterojunction polymer solar cells with thermally stable active layer morphology

Abstract. When state-of-the-art bulk heterojunction organic solar cells with ideal morphology are exposed to prolonged storage or operation at elevated temperatures, a thermally induced disruption of the active layer blend can occur, in the form of a separation of donor and acceptor domains, leading to diminished photovoltaic performance. Toward the long-term use of organic solar cells in real-life conditions, an important challenge is, therefore, the development of devices with a thermally stable active layer morphology. Several routes are being explored, ranging from the use of high glass transition temperature, cross-linkable and/or side-chain functionalized donor and acceptor materials, to light-induced dimerization of the fullerene acceptor. A better fundamental understanding of the nature and underlying mechanisms of the phase separation and stabilization effects has been obtained through a variety of analytical, thermal analysis, and electro-optical techniques. Accelerated aging systems have been used to study the degradation kinetics of bulk heterojunction solar cells in situ at various temperatures to obtain aging models predicting solar cell lifetime. The following contribution gives an overview of the current insights regarding the intrinsic thermally induced aging effects and the proposed solutions, illustrated by examples of our own research groups.

Zinc oxide modified with benzylphosphonic acids as transparent electrodes in regular and inverted organic solar cell structures

An approach is presented to modify the work function of solution-processed sol-gel derived zinc oxide (ZnO) over an exceptionally wide range of more than 2.3 eV. This approach relies on the formation of dense and homogeneous self-assembled monolayers based on phosphonic acids with different dipole moments. This allows us to apply ZnO as charge selective bottom electrodes in either regular or inverted solar cell structures, using poly(3-hexylthiophene):phenyl-C71-butyric acid methyl ester as the active layer. These devices compete with or even surpass the performance of the reference on indium tin oxide/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Our findings highlight the potential of properly modified ZnO as electron or hole extracting electrodes in hybrid optoelectronic devices.

Absorption Tails of Donor:C60 Blends Provide Insight into Thermally Activated Charge-Transfer Processes and Polaron Relaxation

In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D-A complexes occur at photon energies below the optical gaps of both the donors and the C60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes.

Charge Transfer Absorption and Emission at ZnO/Organic Interfaces

We investigate hybrid charge transfer states (HCTS) at the planar interface between α-NPD and ZnO by spectrally resolved electroluminescence (EL) and external quantum efficiency (EQE) measurements. Radiative decay of HCTSs is proven by distinct emission peaks in the EL spectra of such bilayer devices in the NIR at energies well below the bulk α-NPD or ZnO emission. The EQE spectra display low energy contributions clearly red-shifted with respect to the α-NPD photocurrent and partially overlapping with the EL emission. Tuning of the energy gap between the ZnO conduction band and α-NPD HOMO level (Eint) was achieved by modifying the ZnO surface with self-assembled monolayers based on phosphonic acids. We find a linear dependence of the peak position of the NIR EL on Eint, which unambiguously attributes the origin of this emission to radiative recombination between an electron on the ZnO and a hole on α-NPD. In accordance with this interpretation, we find a strictly linear relation between the open-circuit voltage and the energy of the charge state for such hybrid organic-inorganic interfaces.

Poly(3-alkylthiophene) Nanofibers for Photovoltaic Energy Conversion

The use of nanostructured non-conventional semiconductors such as conjugated polymers and metal oxides (e.g. TiO2), opens promising perspectives towards a new generation of solar cells based on the concept of donor:acceptor bulk heterojunctions. In this concept donor material and acceptor material form interpenetrating networks allowing light absorption, charge transfer and charge transport throughout the entire bulk of the thin film. Since nanomorphology is of crucial importance for this type of solar cells, in this contribution the use of nanofibers in bulk heterojunction solar cells is explored in order to obtain highways for charge transport. We investigate in particular the use of P3AT (poly(3-alkylthiophene)) nanofibers and show that the polymer fraction aggregated into fibers can be easily controlled by temperature. We find an optimal efficiency at intermediate fiber fraction and show that it can be linked to the morphology of the active layer.