Screen printed Pb₃O₄ films and their application to photoresponsive and photoelectrochemical devices

A new and simple procedure for the deposition of lead (II, IV) oxide films by screen printing was developed. In contrast to conventional electrochemical methods, films can be also deposited on non-conductive substrates without any specific dimensional restriction, being the only requirement the thermal stability of the substrate in air up to 500 °C to allow for the calcination of the screen printing paste and sintering of the film. In this study, films were exploited for the preparation of both photoresponsive devices and photoelectrochemical cell photoanodes. In both cases, screen printing was performed on FTO (Fluorine-Tin Oxide glass) substrates. The photoresponsive devices were tested with I-V curves in dark and under simulated solar light with different irradiation levels. Responses were evaluated at different voltage biases and under light pulses of different durations. Photoelectrochemical cells were tested by current density⁻voltage (J-V) curves under air mass (AM) 1.5 G illumination, incident photon-to-current efficiency (IPCE) measurements, and electrochemical impedance spectroscopy

Influence of the conditions of sensitization on the characteristics of p-DSCs sensitized with asymmetric squaraines

The effect of the conditions of sensitization on the photoelectrochemical performance of p-type dye-sensitized solar cells (p-DSCs) with screen-printed nickel oxide (NiO) photocathodes is analyzed. The dye-sensitizers employed in the present study are asymmetric squaraines. The conditions of sensitization differ for the relative concentration of the anti-aggregating agentCDCA(chenideoxycholic acid) with respect to the concentration of the dye-sensitizer. The co-adsorption of CDCA onto NiO electrode brings about a decrease in the surface concentration of the anchored dye as well as a blueshift of the characteristic wavelengths of optical absorption of the asymmetric squaraines considered here. Beside this, the employment of CDCA as co-adsorbent reduces the overall conversion performance of the resulting squaraine-sensitized p-DSCs with consequent diminution of the short-circuit current density. This result is ascribed to the acid action of CDCA toward the amminic nitrogen of the squaraines. Quantum efficiency spectra show that CDCA acts as a quencher of the intrinsic photoelectrochemical activity of NiO. Moreover, CDCA does not interfere with the mechanism of charge injection effectuated by the photoexcited squaraines. The photoelectrochemical impedance spectra was analyzed employing a model of equivalent circuit developed for semiconducting nanostructure electrodes

Important Considerations in Plasmon-Enhanced Electrochemical Conversion at Voltage-Biased Electrodes.

In this perspective we compare plasmon-enhanced electrochemical conversion (PEEC) with photoelectrochemistry (PEC). PEEC is the oxidation or reduction of a reactant at the illuminated surface of a plasmonic metal (or other conductive material) while a potential bias is applied. PEC uses solar light to generate photoexcited electron-hole pairs to drive an electrochemical reaction at a biased or unbiased semiconductor photoelectrode. The mechanism of photoexcitation of charge carriers is different between PEEC and PEC. Here we explore how this difference affects the response of PEEC and PEC systems to changes in light, temperature, and surface morphology of the photoelectrode

Photoelectrochemical electrodes

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein

First examples of pyran based colorants as sensitizing agents of p-Type Dye-Sensitized solar cells

Three different pyran based dyes were synthesized and tested for the first time as photosensitizers of NiO based p-type dye-sensitized solar cells (p-DSSC). The molecules feature a similar molecular structure and are based on a pyran core that is functionalized with electron acceptor groups of different strength and is symmetrically coupled to phenothiazine donor branches. Optical properties of the dyes are deeply influenced by the nature of the electron-acceptor group, so that the overall absorption of the three dyes covers the most of the visible spectrum. The properties of devices based on the NiO electrodes sensitized with the investigated dyes were evaluated under simulated solar radiation: the larger short circuit current density exceeded 1mA/cm2 and power conversion efficiency as high as 0.04% could be recorded. The performances of the fabricated p-DSSC have been compared to a reference cell sensitized with P1, a high level benchmark, which afforded a photoelectrochemical activity similar to the best example of our pyran sensitized devices (1.19 mA/cm2 and 0.049%)

Limits on the use of cobalt sulfide as anode of p-type dye-sensitized solar cells

Thin films of cobalt sulfide (CoS) of thickness l < 10m have been employed as anodes of p-type dye-sensitized solar cells (p-DSCs) when P1-sensitized nickel oxide (NiO) was the photoactive cathode and /I - constituted the redox mediator. In the role of counter electrode for p-DSCs, CoS was preferred over traditional platinized fluorine-doped indium oxide (Pt-FTO) due to the lower cost of the starting materials (Co salts) and the easier procedure of deposition onto large area substrates. The latter process was carried out via direct precipitation of CoS from aqueous solutions. The photoconversion efficiency (η) of the corresponding device was 0.07%. This value is about 35% less than the efficiency that is obtained with the analogous p-DSC employing the Pt-FTO anode (η = 0.11). Unlike p-DSCs based on Pt-FTO anodes, the photoelectrochemical cells employing CoS electrodes showed that this anodic material was not able to sustain the photocurrent densities generated by P1-sensitized NiO at a given photopotential. Illumination of the p-DSCs with CoS anodes and P1-sensitized NiO cathodes actually induced the reverse bias of the photoelectrochemical cell with CoS behaving like a p-type semiconductor with no degeneracy. © 2017 IOP Publishing Ltd

Photoelectrochemical fabrication of spectroscopic diffraction gratings

Photoelectrochemical etching was demonstrated as a means of fabricating a variety of periodic structures in semiconductors. The semiconductor is used as an electrode in an electrochemical cell, and is in contact with a liquid electrolyte. When the crystal is held at a positive voltage and illuminated, etching occurs in only the illuminated regions to a depth proportional to the illumination intensity and exposure time. In Phase 1, it was determined that diffraction gratings could be produced in gallium arsenide crystals by this method, using either a scanned focused laser beam or by uniform illumination of a ruling mask defined in metal or photoresist on the crystal surface. The latter approach was determined to produce V-grooves if the mask is oriented along certain crystallographic directions. These V-grooves were produced with an exceedingly smooth crystal morphology due to the highly controllable nature of the process and the mild electrolytes involved. The results form the basis for photoelectrochemical fabrication of deep, low pitch Eschelle gratings for use in high orders in NASA spectrographic instrumentation such as the Space Telescope Imaging Spectrograph

Photoelectrochemical fabrication of spectroscopic diffraction gratings, phase 2

This program was directed toward the production of Echelle diffraction gratings by a light-driven, electrochemical etching technique (photoelectrochemical etching). Etching is carried out in single crystal materials, and the differential rate of etching of the different crystallographic planes used to define the groove profiles. Etching of V-groove profiles was first discovered by us during the first phase of this project, which was initially conceived as a general exploration of photoelectrochemical etching techniques for grating fabrication. This highly controllable V-groove etching process was considered to be of high significance for producing low pitch Echelles, and provided the basis for a more extensive Phase 2 investigation