Burkhard Zietz

Isomerization and Aggregation of the Solar Cell Dye D149

D149, a metal-free indoline dye, is one of the most promising sensitizers for dye-sensitized solar cells (DSSCs) and has shown very high solar energy conversion efficiencies of 9%. Effective electron injection from the excited state is a prerequisite for high efficiencies and is lowered by competing deactivation pathways. Previous investigations have shown surprisingly short-lived excited states for this dye, with maximum lifetime components of 100–720 ps in different solvents and less than 120 ps for surface-adsorbed D149. Using steady-state and time-resolved fluorescence, we have investigated the photochemical properties of D149 in nonpolar and polar solvents, polymer matrices, and adsorbed on ZrO2, partially including a coadsorbent. In solution, excitation to the S2 state yields a product that is identified as a photoisomer. The reaction is reversible, and the involved double-bond is identified by NMR spectroscopy. Our results further show that lifetimes of 100–330 ps in the solvents used are increased to more than 2 ns for D149 in polymer matrices and on ZrO2. This is in part attributed to blocked internal motion due to steric constraint. Conversely, concentration-dependent aggregation leads to a dramatic reduction in lifetimes that can affect solar cell performance. Our results explain the unexpectedly short lifetimes observed previously. We also show that photochemical properties such as lifetimes determined in solution are different from the ones determined on semiconductor surfaces used in solar cells. The obtained mechanistic understanding should help develop design strategies for further improvement of solar cell dyes.

Photoisomerization of the cyanoacrylic acid acceptor group – a potential problem for organic dyes in solar cells

Organic solar cell dyes containing the most common anchoring group, cyanoacrylic acid, are shown to be photolabile and undergo photoisomerization. This may have significant consequences for dye-sensitized solar cells, as isomerisation competes with electron injection and leads to modifications of the dye and surface arrangement.

Chemical engineering of methylammonium lead iodide/bromide perovskites: tuning of opto-electronic properties and photovoltaic performance

Hybrid (organic-inorganic) lead trihalide perovskites have attracted much attention in recent years due to their exceptionally promising potential for application in solar cells. Here a controlled ...

Control over Excited State Intramolecular Proton Transfer and Photoinduced Tautomerization : Influence of the Hydrogen-Bond Geometry

The influence of H-bond geometry on the dynamics of excited state intramolecular proton transfer (ESIPT) and photoinduced tautomerization in a series of phenol-quinoline compounds is investigated. Control over the proton donor-acceptor distance (dDA ) and dihedral angle between the proton donor-acceptor subunits is achieved by introducing methylene backbone straps of increasing lengths to link the phenol and quinoline. We demonstrate that a long dDA correlates with a higher barrier for ESIPT, while a large dihedral angle opens highly efficient deactivation channels after ESIPT, preventing the formation of the fully relaxed tautomer photoproduct.

Optical properties of nanocrystalline WO3 and WO3-x thin films prepared by DC magnetron sputtering

The optical properties of tungsten trioxide thin films prepared by DC magnetron sputtering, with different oxygen vacancy (Vo) concentration, have been studied by spectrophotometry and photoluminescence (PL) emission spectroscopy. Absorption and PL spectra show that the films exhibit similar band gap energies, Eg ≈ 2.9 eV. The absorption spectra of the films show two pronounced absorption bands in the near-infrared region. One peak (P1) is located at approximately 0.7 eV, independent of Vo concentration. A second peak (P2) shifts from 0.96 eV to 1.16 eV with decreasing Vo concentration. Peak P1 is assigned to polaron absorption due to transitions between tungsten sites (W5+ → W6+), or an optical transition from a neutral vacancy state to the conduction band, Vo0 → W6+. The origin of peak P2 is more uncertain but may involve +1 and +2 charged vacancy sites. The PL spectra show several emission bands in the range 2.07 to 3.10 eV in the more sub-stoichiometric and 2.40 to 3.02 eV in the less sub-stoichiometr...

Contribution from a hole-conducting dye to the photocurrent in solid-state dye-sensitized solar cells.

The hole transporting medium in solid-state dye-sensitized solar cells can be utilized to harvest sunlight. Herein we demonstrate that a triphenylamine-based dye, used as hole-transporting medium, contributes to the photocurrent in a squaraine-sensitized solid-state dye-sensitized solar cell. Steady-state photoluminescence measurements have been used to distinguish between electron transfer and energy transfer processes leading to energy conversion upon light absorption in the hole-transporting dye.

Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene.

The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Bairds rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Bairds rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

Cyclopropyl Group: An Excited-State Aromaticity Indicator?

The cyclopropyl (cPr) group, which is a well-known probe for detecting radical character at atoms to which it is connected, is tested as an indicator for aromaticity in the first ππ* triplet and singlet excited states (T1 and S1 ). Bairds rule says that the π-electron counts for aromaticity and antiaromaticity in the T1 and S1 states are opposite to Hückels rule in the ground state (S0 ). Our hypothesis is that the cPr group, as a result of Bairds rule, will remain closed when attached to an excited-state aromatic ring, enabling it to be used as an indicator to distinguish excited-state aromatic rings from excited-state antiaromatic and nonaromatic rings. Quantum chemical calculations and photoreactivity experiments support our hypothesis; calculated aromaticity indices reveal that openings of cPr substituents on [4n]annulenes ruin the excited-state aromaticity in energetically unfavorable processes. Yet, polycyclic compounds influenced by excited-state aromaticity (e.g., biphenylene), as well as 4nπ-electron heterocycles with two or more heteroatoms represent limitations.

Transient isomers in the photodissociation of bromoiodomethane

The photochemistry of halomethanes is fascinating for the complex cascade reactions toward either the parent or newly synthesized molecules. Here, we address the structural rearrangement of photodissociated CH2IBr in methanol and cyclohexane, probed by time-resolved X-ray scattering in liquid solution. Upon selective laser cleavage of the C-I bond, we follow the reaction cascade of the two geminate geometrical isomers, CH2I-Br and CH2Br-I. Both meta-stable isomers decay on different time scales, mediated by solvent interaction, toward the original parent molecule. We observe the internal rearrangement of CH2Br-I to CH2I-Br in cyclohexane by extending the time window up to 3 μs. We track the photoproduct kinetics of CH2Br-I in methanol solution where only one isomer is observed. The effect of the polarity of solvent on the geminate recombination pathways is discussed.

Hole transporting dye as light harvesting antenna in dye-sensitized TiO2 hybrid solar cells

Abstract. We herein demonstrate the viability of utilizing the hole transporting medium of solid-state dye-sensitized solar cells for light harvesting. When using a hole transporting dye (HTD) in addition to an interface dye (ID) bound to the surface of the mesoporous metal oxide scaffold, both are shown to contribute to the photocurrent. Efficient energy transfer (ET) from the HTD to the ID was accomplished by spectrally matching two triphenylamine dyes. The photoluminescence of the HTD was found to be quenched in the presence of the ID. In nanosecond transient absorption measurements, rapid formation of the oxidized HTD was observed after photoexcitation of the ID, demonstrating fast regeneration of the oxidized ID by the HTD. In solar cell devices comprising both the ID and HTD, the spectral response of the external quantum efficiency shows that both dyes contribute to the photocurrent, resulting in a doubling of the photocurrent. In comparison with devices comprising only TiO2 and the HTD, devices with the additional ID exhibited an increased photovoltage due to more efficient charge-carrier separation and energy transfer. Combining and matching HTDs with IDs for optimal ID regeneration but also providing ET is thus a viable means to optimize hybrid solar cells based on mesoporous TiO2.