Thomas Loewenstein

Symmetrically and unsymmetrically substituted carboxy phthalocyanines as sensitizers for nanoporous ZnO films

The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.

Photoelectrochemical characterization of electrodeposited ZnO thin films sensitized by octacarboxymetallophthalocyanine derivatives

Hybrid thin films of crystalline zinc oxide (ZnO) modified by different octacarboxymetallophthalocyanines (MOCPc) were prepared by the readsorption method. Homogeneously blue or green thin films were formed. The photoelectrochemical characteristics of the electrodes were studied by time-resolved photocurrent measurements. Zinc(II) 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine (ZnOCPc) showed considerably large quantum efficiency in sensitization of ZnO, one of the highest quantum efficiencies obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films.

Textile‐Compatible Substrate Electrodes with Electrodeposited ZnO—A New Pathway to Textile‐Based Photovoltaics

A strategy is presented to realize textile-based photovoltaic cells motivated by developments of textile-based electronics and their demand of grid-independent energy supply. Beyond this, a development of textile-based photovoltaics also represents an attractive pathway towards very flexible and rugged solar cells. The need for compatibility of an appropriate photovoltaic technology with the physical limitations of textiles is stressed. Electrodeposition from aqueous solutions is presented as a successful strategy to realize semiconductor structures on textiles and detailed control and influence of the deposition conditions is discussed. The role of microelectrode effects, options of forced convection, deposition under pulsed potential, alternative deposition baths and different substrate metals are emphasized. An active electrode material is presented which reaches a conversion efficiency close to the 1% limit under AM 1.5 illumination conditions and thereby opens the door for a further optimization towards devices of technical interest.

Electrochemically self-assembled mesoporous dye-modified zinc oxide thin films

A multistep procedure, comprising the cathodic electrodeposition of zinc oxide/Eosin Y hybrid films, the extraction of Eosin Y serving as a structure directing agent and the adsorption of another dye, e.g., the Ru-complex N3, is a highly flexible and efficient method for the preparation of hybrid inorganic/organic films for dye sensitized solar cells. Their high photoelectrochemical efficiency is due to the large surface area and good accessibility of the N3 molecules located on the inner surface of the porous films.

Nanoparticulate Dye-Semiconductor Hybrid Materials Formed by Electrochemical Self-Assembly as Electrodes in Photoelectrochemical Cells

Abstract Dye-sensitized zinc oxide thin films were prepared, characterized and optimized for applications as photoelectrochemically active electrodes. Conditions were established under which crystalline thin films of ZnO with a porous texture were formed by electrochemically induced crystallization controlled by structure-directing agents (SDA). Dye molecules were adsorbed either directly as SDA during this preparation step or, preferably, following desorption of a SDA. The external quantum efficiency (IPCE) could thereby be increased significantly. Particular emphasis was laid on dye molecules that absorb in the red part of the visible spectrum. Model experiments under ultrahigh vacuum (UHV) conditions with dye molecules adsorbed on defined crystal planes of single crystals aimed at a deeper understanding of the coupling of the chromophore electronic π-system within molecular aggregates and to the semiconductor surface. Detailed photoelectrochemical kinetic measurements were used to characterize and optimize the electrochemically prepared dye-sensitized ZnO films. Parallel electrical characterization in vacuum served to distinguish between contributions of charge transport within the ZnO semiconductor matrix and the ions of the electrolyte in the pore system of the electrode.

Modification of ZnO Layers by Molecular Adsorbates During Electrochemical Deposition

ZnO and ZnO/EosinY hybrid materials were electrodeposited from aqueous zinc salt solutions on (0001) GaN and on (0001) ZnO. Crystalline ZnO was deposited as proven by X-ray diffraction (XRD). The intensity pattern for ZnO/EosinY showed a preferential orientation with the c- plane of ZnO parallel to GaN (0001) or ZnO (0001). XRD rocking curves with FWHM=0.25° indicated a high level of in-plane orientation of the deposited ZnO crystalline domains. The peak position of (0002) ZnO was shifted by 2Θ=1.3°. This difference and the corresponding simultaneous shift of (0004) ZnO were explained by a lattice expansion by 3.6 % in the c- direction. This clearly indicated the strong influence of the Eosin Y molecules adsorbed during the electrodeposition of ZnO. Scanning electron microscopy (SEM) revealed the formation of domains with different crystal sizes pointing at a varying density of nucleation sites on the substrate.