An adaptable strategy to introduce different anchors to [Ru(N⁁N)2(C⁁N)]+ dyes is described; use of a phosphonic acid anchor on NiO leads to p-type DSCs with JSC = 3.38 mA cm−2 and PEC of 0.116%.
The properties of metal oxides, such as charge-transport mechanisms or optoelectronic characteristics, can be modified by functionalization with organic molecules. This kind of organic/inorganic surface is nowadays highly regarded, in particular, for the design of hybrid devices such as dye-sensitized solar cells. However, a key parameter for optimized interfaces is not only the choice of the compounds but also the properties of adsorption. Here, we investigated the deposition of an organic dye precursor molecule on a NiO(001) single crystal surface by means of non-contact atomic force microscopy at room temperature. Depending on the coverage, single molecules, groups of adsorbates with random or recognizable shapes, or islands of closely packed molecules were identified. Single molecules and self assemblies are resolved with submolecular resolution showing that they are lying flat on the surface in a trans-conformation. Within the limits of our Kelvin probe microscopy setup a charge transfer from NiO to the molecular layer of 0.3 electrons per molecules was observed only in the areas where the molecules are closed packed.
The balance between optimal photoconversion efficiency and long-term stability in p-type DSCs with a cyclometallated ruthenium dye is presented, with mixtures of acetonitrile and propionitrile being the best solvent with an I3−/I− redox couple.
Conformational
isomers are stereoisomers that can interconvert
over low potential barriers by rotation around a single bond. However,
such bond rotation is hampered by geometrical constraints when molecules
are adsorbed on surfaces. Here, we show that the adsorption of 4,4′-bis(4-carboxyphenyl)-6,6′-dimethyl-2,2′-bipyridine
molecules on surfaces leads to the appearance of prochiral single
molecules on NiO(001) and to enantiopure supramolecular domains on
Au(111) surfaces containing the transoid-molecule conformation. Upon
additional Fe adatom deposition, molecules undergo a controlled interconversion
from a transoid-to-cisoid conformation as a result of coordination
of the Fe atoms to the 2,2′-bipyridine moieties. As confirmed
by atomic force microscopy images and X-ray photoelectron spectroscopy
measurements, the resulting molecular structures become irreversibly
achiral.
Properties of metal oxides, such as optical absorption, can be influenced through the sensitization with molecular species that absorb visible light. Molecular/solid interfaces of this kind are particularly suited for the development and design of emerging hybrid technologies such as dye-sensitized solar cells. A key optimization parameter for such devices is the choice of the compounds in order to control the direction and the intensity of charge transfer across the interface. Here, the deposition of two different molecular dyes, porphyrin and coumarin, as single-layered islands on a NiO(001) single crystal surface have been studied by means of non-contact atomic force microscopy at room temperature. Comparison of both island types reveals different adsorption and packing of each dye, as well as an opposite charge-transfer direction, which has been quantified by Kelvin probe force microscopy measurements.
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