Molecular photovoltaics that mimic photosynthesis

Learning from the concepts used by green plants, we have developed a photovoltaic cell based on molecular light absorbers and mesoporous electrodes. The sensitized nanocrystalline injection solar cell employs organic dyes or transition-metal complexes for spectral sensitization of oxide semiconductors, such as TiO2, ZnO, SnO2, and Nb2O5. Mesoporous films of these materials are contacted with redox electrolytes, amorphous organic hole conductors, or conducting polymers, as well as inorganic semiconductors. Light harvesting occurs efficiently over the whole visible and near-IR range due to the very large internal surface area of the films. Judicious molecular engineering allows the photoinduced charge separation to occur quantitatively within femtoseconds. The certified overall power conversion efficiency of the new solar cell for standard air mass 1.5 solar radiation stands presently between 10 and 11. The lecture will highlight recent progress in the development of solar cells for practical use. Advancement in the understanding of the factors that govern photovoltaic performance, as well as improvement of cell components to increase further its conversion efficiency will be discusse

Beyond Vibrationally Mediated Electron Transfer: Coherent Phenomena Induced by Ultrafast Charge Separation

Wave packet propagation succeeding electron transfer (ET) from alizarin dye molecules into the nanocrystalline TiO2 semiconductor has been studied by ultrafast transient absorption spectroscopy. Due to the ultrafast time scale of the ET reaction of about 6 fs the system shows substantial differences to molecular ET systems. We show that the ET process is not mediated by molecular vibrations and therefore classical ET theories lose their applicability. Here the ET reaction itself prepares a vibrational wave packet and not the electromagnetic excitation by the laser pulse. Furthermore, the generation of phonons during polaron formation in the TiO2 lattice is observed in real time for this system. The presented investigations enable an unambiguous assignment of the involved photoinduced mechanisms and can contribute to a corresponding extension of molecular ET theories to ultrafast ET systems like alizarin/TiO2.Comment: This work was supported by the German Research Foundation (DFG) (Hu 1006/6-1, WA 1850/6-1) and European Union projects FDML-Raman (FP7 ERC StG, contract no. 259158) and ENCOMOLE-2i (Horizon 2020, ERC CoG no. 646669

Ultrafast photoinduced electron transfer in coumarin 343 sensitized TiO2-colloidal solution

Photoinduced electron transfer from organic dye molecules to semiconductor nanoparticles is the first and most important reaction step for the mechanism in the so called “wet solar cells” [1]. The time scale between the photoexcitation of the dye and the electron injection into the conduction band of the semiconductor colloid varies from a few tens of femtoseconds to nanoseconds, depending on the specific electron transfer parameters of the system, e.g., electronic coupling or free energy values of donor and acceptor molecules [2–10]. We show that visible pump/ white light probe is a very efficient tool to investigate the electron injection reaction allowing to observe simultaneously the relaxation of the excited dye, the injection process of the electron, the cooling of the injected electron and the charge recombination reaction

Photovoltaic performance of injection solar cells and other applications of nanocrystalline oxide layers

The direct conversion of sunlight to electricity via photoelectrochemical solar cells is an attractive option that has been pursued for nearly two decades in several laboratories. In this paper, we review the principles and performance features of very efficient solar cells that are being developed in our laboratories. These are based on the concept of dye-sensitization of wide bandgap semiconductors used in the form of mesoporous nanocrystalline membrane-type films. The key feature is charge injection from the excited state of an anchored dye to the conduction band of an oxide semiconductor such as TiO2. In the use of the semiconductor in the form of high surface area, highly porous film offers several unique advantages: monomeric distribution of a large quantity of the dye in a compact (few micron thick) film, efficient charge collection and drastic inhibition of charge recombination (‘capture of charge carriers by oxidized dye'). Near quantitative efficiency for charge collection for monochromatic light excitation gives rise to sunlight conversion efficiency in the range of 8-10% This has led to fruitful collaboration with several industrial partners. Possible applications and commercialization of these solar cells and also other practical applications of nanosized films are briefly outline

Fast computation of the Kohn-Sham susceptibility of large systems

For hybrid systems, such as molecules grafted onto solid surfaces, the calculation of linear response in time dependent density functional theory is slowed down by the need to calculate, in N^4 operations, the susceptibility of N non interacting Kohn-Sham reference electrons. We show how this susceptibility can be calculated N times faster within finite precision. By itself or in combination with previous methods, this should facilitate the calculation of TDDFT response and optical spectra of hybrid systems.Comment: submitted 25/1/200

Excitation-Wavelength Dependence of Photoinduced Charge Injection at the Semiconductor-Dye Interface: Evidence for Electron Transfer from Vibrationally Hot Excited States

Heterodyad systems composed of a redox photosensitizer adsorbed on the surface of a wide band gap semiconductor were designed in a way that the ν'=0 energy level of the electronically excited state of the dye lies below the bottom of the conduction band of the solid. Under these conditions, the quantum yield of the charge injection from the sensitizer into the conduction band of the solid was found to depend upon the excitation photon energy. This observation provides an evidence that interfacial charge transfer is occurring prior to nuclear relaxation of the sensitizer's excited state. It allows the use of a simplified kinetic model and offers an easy experimental path to the determination of the electronic coupling that controls the rate of the ultrafast injection process