Jan C. Brauer

Extraordinarily Efficient Conduction in a Redox-Active Ionic Liquid

Iodine added to iodide-based ionic liquids leads to extraordinarily efficient charge transport, vastly exceeding that expected for such viscous systems. Using terahertz time-domain spectroscopy, in conjunction with dc conductivity, diffusivity and viscosity measurements we unravel the conductivity pathways in 1-methyl-3-propylimidazolium iodide melts. This study presents evidence of the Grotthuss mechanism as a significant contributor to the conductivity, and provides new insights into ion pairing processes as well as the formation of polyiodides. The terahertz and transport results are reunited in a model providing a quantitative description of the conduction by physical diffusion and the Grotthuss bond-exchange process. These novel results are important for the fundamental understanding of conduction in molten salts and for applications where ionic liquids are used as charge-transporting media such as in batteries and dye-sensitized solar cells.

The fate of electron-hole pairs in polymer:fullerene blends for organic photovoltaics.

There has been long-standing debate on how free charges are generated in donor:acceptor blends that are used in organic solar cells, and which are generally comprised of a complex phase morphology, where intermixed and neat phases of the donor and acceptor material co-exist. Here we resolve this question, basing our conclusions on Stark effect spectroscopy data obtained in the absence and presence of externally applied electric fields. Reconciling opposing views found in literature, we unambiguously demonstrate that the fate of photogenerated electron–hole pairs—whether they will dissociate to free charges or geminately recombine—is determined at ultrafast times, despite the fact that their actual spatial separation can be much slower. Our insights are important to further develop rational approaches towards material design and processing of organic solar cells, assisting to realize their purported promise as lead-free, third-generation energy technology that can reach efficiencies over 10%.

Conduction Through Viscoelastic Phase in a Redox-Active Ionic Liquid at Reduced Temperatures

The phase diagram of the redox active ionic liquid 1-methyl-3-propylimidazolium iodide (PMII) is examined as a function of temperature and iodine concentration. Beyond a threshold concentration of 3.9 M, the formation of higher polyiodides gives rise to a viscoelastic phase upon cooling. Despite of the very high viscosity of such polyiodide-containing PMII melts a strikingly high conductivity is maintained through Grotthuss-type bond exchange and ionic conduction.

Ultrafast charge carrier dynamics in CH3NH3PbI3: evidence for hot hole injection into spiro-OMeTAD

Hybrid organic–inorganic metal perovskites have emerged as highly promising materials for solar energy conversion. However, key questions regarding the working principles of perovskite solar cells remain to be answered in order to improve the design of such devices. In the present study, we have investigated the influence of excess excitation energy on the initial photo-products generated from FTO/meso-TiO2/CH3NH3PbI3 samples. We find that upon resonant excitation at the band edge, part of the formation of free charges passes via an excitonic state that dissociates on the sub-picosecond time scale. An exciton binding energy of <10 meV is estimated from the lifetime of the exciton. On the other hand, if excess energy is available, free charges are directly generated. We have then investigated the hole injection into spiro-OMeTAD at the CH3NH3PbI3/spiro-OMeTAD interface. By following spectroscopically the generation of the oxidized form of the molecular hole conductor spiro-OMeTAD, we confirm that the hole injection is essentially ultrafast and occurs on the sub-80 femtosecond time scale. On this time scale, the hole injection competes with carrier cooling after photo-excitation and therefore the charge injection can occur from non-thermalised states.

Photoinduced processes in lead iodide perovskite solid-state solar cells

Organic-inorganic hybrid systems based on lead halide compounds have recently encountered considerable success as light absorbers in solid-state solar cells. Herein we show how fundamental mechanistic processes in mesoporous oxide films impregnated with CH3NH3PbI3 can be investigated by time resolved techniques. In particular, charge separation reactions such as electron injection into the titanium dioxide film and hole injection into the hole transporting material spiro-OMeTAD as well as the corresponding charge recombination reactions were scrutinized. Femtosecond transient absorption spectroscopy and time-resolved terahertz spectroscopy were applied to CH3NH3PbI3 deposited either on TiO2 or Al2O3 mesoporous films and infiltrated with the hole transporting material spiro-OMeTAD.

Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Functional π-conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large-scale synthesis of protected quarter-, sexi-, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single-crystal X-ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide-substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.

Unusually Long-Lived Photocharges in Helical Organic Semiconductor Nanostructures

Photocharge generation and formation of long-lived charge carriers are relevant in photosynthesis, photocatalysis, photovoltaics, and organic electronics. A better understanding of the factors that determine these processes in synthetic polymer semiconductors is crucial, but difficult due to their morphological inhomogeneity. Here, we report the formation of exceptionally long-lived photocharges in one-dimensional organic semiconductor nanostructures. These nanostructures consist of chiral oligopeptide-substituted thienothiophene-based chromophores and exhibit a well-defined helical arrangement of these chromophores at their core. The chromophores give rise to spectroscopic H-aggregates and show strong intermolecular excitonic coupling. We demonstrate that all of these parameters are the prerequisites required for the nanostructures to show the efficient formation of polaron-like photocharges upon irradiation with a low-power white light source. The observed charge carriers in the helical nanowires show an unusually long lifetime on the order of several hours and are formed at high concentrations of up to 3 mol % in the absence of any dedicated electron acceptor. They are observed in solution as well as in film and furthermore give rise to a light-induced increase of the macroscopic charge transport. By contrast, no such photocharge generation is observed either in non-aggregating reference systems of the same chromophores or in aggregated but non-helical systems that do not form one-dimensional nanostructures. Our results thus demonstrate a clear correlation between nanoscopic confinement and the generation of long-lived photocharges.

Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems

Electron transfer and subsequent charge separation across donor-acceptor heterojunctions remain the most important areas of study in the field of third-generation photovoltaics. In this context, it is particularly important to unravel the dynamics of individual ultrafast processes (such as photoinduced electron transfer, carrier trapping and association, and energy transfer and relaxation), which prevail in materials and at their interfaces. In the frame of the National Center of Competence in Research “Molecular Ultrafast Science and Technology,” a research instrument of the Swiss National Science Foundation, several groups active in the field of ultrafast science in Switzerland have applied a number of complementary experimental techniques and computational simulation tools to scrutinize these critical photophysical phenomena. Structural, electronic, and transport properties of the materials and the detailed mechanisms of photoinduced charge separation in dye-sensitized solar cells, conjugated polymer- and small molecule-based organic photovoltaics, and high-efficiency lead halide perovskite solar energy converters have been scrutinized. Results yielded more than thirty research articles, an overview of which is provided here.

Charge separation in an acceptor–donor–acceptor triad material with a lamellar structure

Linking covalently both electron donor and acceptor components is an efficient way to gain thermodynamic control over the formation of well-ordered heterojunction materials suitable for organic photovoltaics. In this context, we attached flexible polymer segments to the termini of a (perylene bisimide)–quaterthiophene–(perylene bisimide) triad. The microphase segregation of the resulting coil-rod-coil architecture served to reliably promote the formation of lamellar phases. The lamellae were oriented vertically relative to the substrate, and they could be laterally aligned by mechanical rubbing, as determined by small and wide angle X-ray scattering, transmission electron microscopy, electron diffraction and AFM. Transient absorption spectroscopy revealed that light absorption was followed by charge separation and that charge recombination was slower in thin films than for solution-phase samples, especially when longer side chains were used. Thus, this study is a first step towards reliable lamellar phase segregation in donor–acceptor materials on the route towards improved materials for organic photovoltaics.

Charge generation in organic solar cell materials studied by terahertz spectroscopy

We have investigated the photophysics in neat films of conjugated polymer PBDTTPD and its blend with PCBM using terahertz time-domain spectroscopy. This material has very high efficiency when used in organic solar cells. We were able to identify a THz signature for bound excitons in neat PBDTTPD films, pointing to important delocalization in those excitons. Then, we investigated the nature and local mobility (orders of magnitude higher than bulk mobility) of charges in the PBDTTPPD:PCBM blend as a function of excitation wavelength, fluence and pump-probe time delay. At low pump fluence (no bimolecular recombination phenomena), we were able to observe prompt and delayed charge generation components, the latter originating from excitons created in neat polymer domains which, thanks to delocalization, could reach the PCBM interface and dissociate to charges on a time scale of 1 ps. The nature of the photogenerated charges did not change between 0.5 ps and 800 ps after photo-excitation, which indicated that the excitons split directly into relatively free charges on an ultrafast time scale.