Hans-Joachim Egelhaaf

Influence of the bridging atom on the performance of a low-bandgap bulk heterojunction solar cell.

Bulk heterojunction solar cells have attracted considerable attention over the past several years due to their potential for low-cost photovoltaic technology. The possibility of manufacturing modules via a standard printing/coating method in a roll-to-roll process in combination with the use of low-cost materials will lead to a watt-peak price of less than 1 US

Towards highly luminescent phenylene vinylene films

within the next few years. [1] Despite the low-cost potential, the power conversion efficiency of bulk heterojunction devices is low compared to inorganic solar cells. Efficiencies in the range of 5‐6% have been certified at NREL and AIST usually on devices with small active areas. [2] The current understanding of bulk heterojunction solar cells suggests that the maximum efficiency is in the range of 10‐12%. [3] Several reasons for the power conversion efficiency limitation have been identified. [1] Some of the prerequisites for achieving highest efficiencies are donor and acceptor materials with optimized energy levels [highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)], efficient charge transport in the donor‐acceptor blend, efficient charge generation and limited recombination losses. Power conversion efficiency is strongly dependent on charge transport and charge generation, which are dominated by the phase behavior of the donor and acceptor molecules. The resulting, and often unfavorable, nanomorphology of this two-component blend limits the power conversion efficiency of bulk heterojunction solar cells. Precise control of the nanomorphology is very difficult and has been achieved only for a few systems. [4‐6] The relation between the chemical structure of donor and acceptor materials and the nanomorphology that they form when they are blended is currently not well understood, and as will be shown in this paper, minor changes in the chemical structure can cause major changes in the performance of the materials in organic solar cells. In this work we demonstrate the effect of replacing a carbon atom with a silicon atom on the main chain of the conjugated polymer. The approach has been used previously, and promising materials for field-effect transistors and organic solar cells have been demonstrated. [7‐9] We find that making this simple substitution in poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4b 0 ]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) yields a polysilole, e.g., poly[(4,4 0 -bis(2-ethylhexyl)dithieno[3,2b:2 0 ,3 0 -d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5 0 -diyl] (Si-PCPDTBT), with a higher crystallinity, improved charge transport properties, reduced bimolecular recombination, and a reduced formation of charge transfer complexes when blended with a fullerene derivative. This silole-based polymer is found to form a highly functional nanomorphology when blended with [6,6]-phenyl C71-butyric acid methyl ester (C70-PCBM), and solar cells prepared using this blend gave efficiencies of 5.2%, certified by the National Renewable Energy Laboratory. [1] The presented polymer is the first low-bandgap semiconducting polymer to have a certified efficiency of over 5%. The chemical structure of the subject polymer is shown in Figure 1. The material was synthesized following the procedure described previously. [10] The synthesis and properties of the carbon-bridged polymer have been described before. [11,12] Figure 2a shows the absorbance and photoluminescence (PL) spectra of a thin solid film of the pristine Si-bridged polymer and

Structural correlations in the generation of polaron pairs in low-bandgap polymers for photovoltaics

Abstract Fluorescence and electronic absorption spectra, fluorescence decay curves and fluorescence quantum yields of a series of oligo (p-phenylene vinylenes) are investigated in solution, nanoaggregates and vapour-deposited or cast ultrathin films. The film constituting molecules are varied in chain length and modified by electron donating and withdrawing substituents and bulky alkyl spacers. PPP-MO calculations serve to rationalize the resulting spectral changes. In dilute solutions, fluorescence yields of the short oligomers with alkyl or oxyalkyl substituents approach the region of unity. The yields decrease with chain length, reaching a long-chain limit of ΦF=0.4–0.7. Introduction of electron withdrawing -CN or -SO2CF3 groups can reduce the yields to almost zero, due to facilitated excited-state torsions around the vinylene double bonds. In films, the situation changes drastically. Fluorescence yields of the parent compounds become very low because of molecular excition coupling which reduces the radiative rates and increases the nonradiative rates of charge separation or internal conversion. Introduction of bulky or polar substituents reduces excitonic coupling, but keeps the molecular environment rigid enough to suppress nonradiative torsional deactivation, so that finally the substituted oligophenylene vinylenes produce highly luminescent films with a present maximum of ΦF≈0.6 for 1,4-bis(α-cyanostyryl)-2,5-di-n-hexylbenzene (HTCo).

High-performance ternary organic solar cells with thick active layer exceeding 11% efficiency

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (η=8%). π-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.

Effect of fluorination on the electronic structure and optical excitations of π-conjugated molecules

We present a novel ternary organic solar cell with an uncommonly thick active layer (∼300 nm), featuring thickness invariant charge carrier recombination and delivering 11% power conversion efficiency (PCE). A ternary blend was used to demonstrate photovoltaic modules of high technological relevance both on glass and flexible substrates, yielding 8.2% and 6.8% PCE, respectively.

Morphological and electrical control of fullerene dimerization determines organic photovoltaic stability

Fluorination of pi-conjugated organic molecules is a strategy to obtain possible n-type conducting and air-stable materials due to the lowering of the frontier molecular orbitals (MOs) by the high electronegativity of fluorine. Nevertheless, the resulting optical gaps may be widened or narrowed, depending on the molecular backbone and/or the number and position of the fluorine atoms. The authors have performed time-dependent density functional theory calculations to address the subtle influence of fluorine substitution on the absolute MO energies and the subsequent impact on the optical transitions in homologous conjugated oligomers based on thiophene and acene units.

Solar Trees: First Large‐Scale Demonstration of Fully Solution Coated, Semitransparent, Flexible Organic Photovoltaic Modules

Fullerene dimerization has been linked to short circuit current (Jsc) losses in organic solar cells comprised of certain polymer–fullerene systems. We investigate several polymer–fullerene systems, which present Jsc loss to varying degrees, in order to determine under which conditions dimerization occurs. By reintroducing dimers into fresh devices, we confirm that the photo-induced dimers are indeed the origin of the Jsc loss. We find that both film morphology and electrical bias affect the photodimerization process and thus the associated loss of Jsc. In plain fullerene films, a higher degree of crystallinity can inhibit the dimerization reaction, as observed by high performance liquid chromatography (HPLC) measurements. In blend films, the amount of dimerization depends on the degree of mixing between polymer and fullerene. For highly mixed systems with very amorphous polymers, no dimerization is observed. In solar cells with pure polymer and fullerene domains, we tune the fullerene morphology from amorphous to crystalline by thermal annealing. Similar to neat fullerene films, we observe improved light stability for devices with crystalline fullerene domains. Changing the operating conditions of the investigated solar cells from Voc to Jsc also significantly reduces the amount of dimerization-related Jsc loss; HPLC analysis of the active layer shows that more dimers are formed if the cell is held at Voc instead of Jsc. The effect of bias on dimerization, as well as a clear correlation between PL quenching and reduced dimerization upon addition of small amounts of an amorphous polymer into PC60BM films, suggests a reaction mechanism via excitons.

INVESTIGATING THE SELECTIVITY OF TRIACONTYL INTERPHASES

The technology behind a large area array of flexible solar cells with a unique design and semitransparent blue appearance is presented. These modules are implemented in a solar tree installation at the German pavilion in the EXPO2015 in Milan/IT. The modules show power conversion efficiencies of 4.5% and are produced exclusively using standard printing techniques for large‐scale production.

Spatially resolved single bead analysis: homogeneity, diffusion, and adsorption in cross-linked polystyrene.

What causes the shape selectivity of C30 phases? This question can be answered by combining NMR and fluorescence spectroscopies with HPLC separations at various temperatures. The selectivities depend on the ratio of trans to gauche conformations of the alkyl chains, whose dynamic behavior was characterized with a two-dimensional solid-state NMR spectrum (shown on the right).

The effect of oxygen induced degradation on charge carrier dynamics in P3HT:PCBM and Si-PCPDTBT:PCBM thin films and solar cells

Spatially resolved single bead analysis in the micrometer range was employed as a tool for evaluating homogeneity, diffusion, and adsorption in solid-phase supported reactions. Fluorescence microscopy (confocal and non-confocal) as well as IR microscopy were used to detect both the distribution of products and the formation of product gradients in representative reactions. For the first time, the optical slices of whole beads obtained by confocal fluorescence microscopy were compared with the fluorescence images of microtome-sliced beads. The experiments revealed that only physical slices of polystyrene beads deliver realistic representations of the distribution of fluorophores, and confirmed-in contrast to a recent report-the homogeneity of functional site distribution in polystyrene beads. Moreover, the pattern of product formation obtained from an acylation reaction as well as from an alkylation reaction were employed as probes to study the impact of bead size, diffusion, and adsorption on the reaction progress. A simulation of the diffusion process was conducted and compared with the experimental results. Diffusional control was found neither in the case of the alkylation nor in the case of the acylation reaction under investigation. As a consequence, the reaction progress was not a function of the bead sizes as proposed in the literature. Interestingly, in the case of rhodamine acylation with substoichiometric amounts an adsorption-controlled reaction was found. This result highlights the significance of adsorptive effects in solid-phase supported chemistry.