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

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

Influence of different Ni coatings on the long-term behavior of ultrasonic welded EN AW 1370 cable/EN CW 004A arrestor dissimilar joints

The increasing demand for energy-efficient vehicles requires suitable methods for cost and weight reduction. This can be achieved by the replacement of copper by aluminum, in particular for the on-board power systems. However, the complete substitution is restricted by the mechanical and physical material properties of aluminum as well as challenges in the aluminum copper interface. The challenges concern the corrosion vulnerability and the occurrence of brittle intermetallic compounds (IMC) which can negatively influence the mechanical properties and the electrical conductivity. Therefore, current investigations focus on the one hand on the realization of dissimilar aluminum copper joints by suitable joining technologies, like ultrasonic welding, and on the other hand on the assurance of a sufficient prevention against harmful corrosion effects. In cases where the joint cannot be protected against corrosion by sealing, nickel coatings can be used to protect the joint. In the present study, the influence of electroless, electroplated, and sulfamate nickel coatings was investigated regarding the long-term stability. The joints were performed as industry-related arrester connections, consisting of EN AW 1370 cables and EN CW 004A terminals. The samples were exposed to corrosive as well as electrical, thermal, and mechanical stress tests according to current standards and regulations

Hetero-Supramolecular Modification of Nanocrystalline TiO₂-Film Electrodes: Photoassisted Electrocatalysis at B₁₂-on-TiO₂

Nanocrystalline TiO2-film electrodes exhibit a unique set of intrinsic properties (transparency for visible light, electric conductivity in the doped state, semiconductor properties, large surface area, surface affinity towards organic anchoring groups). These can be combined with those of TiO2-surface-anchored molecular subunits such as light emitters or absorbers, redoxactive–possibly electrochromic–compounds, and electroactive molecular hosts or catalysts. The number of macroscopic devices resulting from such a hetero-supramolecular architecture includes photovoltaic cells, erasable photochromic devices, electrochromic displays and filters, and electrocatalytically active surfaces. The principals behind these applications are reviewed with special emphasis on a new type of photo assisted electrocatalysis using vitamin B12-modified TiO2

Molecular Photovoltaic Devices Mimic Photosynthesis

Photoinduced charge-transfer processes involving molecules adsorbed at interfaces are a fascinating topic which is presently attracting wide attention. Our investigations have focused on the identification of the factors that control the dynamics of such processes. The goal is to design molecular electronic devices that achieve efficient light-induced charge separation. Applications of similar systems in photochromic and electrochromic devices appear also feasible