Teresa Lana-Villarreal

Improving the performance of colloidal quantum-dot-sensitized solar cells

Solar cells based on a mesoporous structure of TiO2 and the polysulfide redox electrolyte were prepared by direct adsorption of colloidal CdSe quantum dot light absorbers onto the oxide without any particular linker. Several factors cooperate to improve the performance of quantum-dot-sensitized solar cells: an open structure of the wide bandgap electron collector, which facilitates a higher covering of the internal surface with the sensitizer, a surface passivation of TiO2 to reduce recombination and improved counter electrode materials. As a result, solar cells of 1.83% efficiency under full 1 sun illumination intensity have been obtained. Despite a relatively large short circuit current (J(sc) = 7.13 mA cm(-2)) and open circuit voltage (V(oc) = 0.53 V), the colloidal quantum dot solar cell performance is still limited by a low fill factor of 0.50, which is believed to arise from charge transfer of photogenerated electrons to the aqueous electrolyte.

The Electrochemistry of Nanostructured Titanium Dioxide Electrodes

Several of the multiple applications of titanium dioxide nanomaterials are directly related to the introduction or generation of charge carriers in the oxide. Thus, electrochemistry plays a central role in the understanding of the factors that must be controlled for the optimization of the material for each application. Herein, the main conceptual tools needed to address the study of the electrochemical properties of TiO(2) nanostructured electrodes are reviewed, as well as the electrochemical methods to prepare and modify them. Particular attention is paid to the dark electrochemical response of these nanomaterials and its direct connection with the TiO(2) electronic structure, interfacial area and grain boundary density. The physical bases for the generation of currents under illumination are also presented. Emphasis is placed on the fact that the kinetics of charge-carrier transfer to solution determines the sign and value of the photocurrent. Furthermore, methods for extracting kinetic information from open-circuit potential and photocurrent measurements are briefly presented. Some aspects of the combination of electrochemical and spectroscopic measurements are also dealt with. Finally, some of the applications of TiO(2) nanostructured samples derived from their electrochemical properties are concisely reviewed. Particular attention is paid to photocatalytic processes and, to a lesser extent, to photosynthetic reactions as well as to applications related to energy from the aspects of both saving (electrochromic layers) and accumulation (batteries). The use of TiO(2) nanomaterials in solar cells is not covered, as a number of reviews have been published addressing this issue.

Toward Antimony Selenide Sensitized Solar Cells: Efficient Charge Photogeneration at spiro-OMeTAD/Sb2Se3/Metal Oxide Heterojunctions

Photovoltaic devices comprising metal chalcogenide nanocrystals as light-harvesting components are emerging as a promising power-generation technology. Here, we report a strategy to evenly deposit Sb2Se3 nanoparticles on mesoporous TiO2 as confirmed by Raman spectroscopy, energy-dispersive X-ray spectrometry, and transmission electron microscopy. Detailed study of the interfacial charge transfer dynamics by means of transient absorption spectroscopy provides evidence of electron injection across the Sb2Se3/TiO2 interface upon illumination, which can be improved 3-fold by annealing at low temperatures. Following addition of the spiro-OMeTAD hole transporting material, regeneration yields exceeding 80% are achieved, and the lifetime of the charge separated species is found to be on the millisecond time scale (τ50% ∼ 50 ms). These findings are discussed with respect to the design of solid-state Sb2Se3 sensitized solar cells.

Trap States in TiO2 Films Made of Nanowires, Nanotubes or Nanoparticles: An Electrochemical Study

The presence of electronic traps in nanoporous TiO(2) electrodes has been studied by cyclic voltammetry in aqueous media. These simple measurements allow us to map the density of states, providing evidence for the presence of a relatively small number of discrete electron traps at the band gap. We have taken advantage of the variety of TiO(2) synthetic procedures that lead to well-defined morphologies (such as nanowires, nanocolumns, nanotubes, and nanoparticles) of anatase and rutile to investigate the nature of these electron traps. They derive from the structural disorder at the contact between neighboring crystalline nanoparticles. As expected, both their density and energetic location are highly dependent, not only on the crystalline structure (whether it is anatase or rutile), but also on the electrode morphology (i.e. the facets that meet at the grain boundaries). The trap density is also sensitive to pH changes and to the presence of some adsorbates. This variation of the number of traps with the electrolyte indicates that on one hand, an apparent electronic density of states is actually measured. On the other, it indicates that the traps are surface-related in agreement with their particular location at the perimeter of the grain boundaries. The effect of these traps on the observed electrode catalytic reactivity has also been studied. In the dark, it is found that they are directly involved in the electron transfer toward oxygen. In addition, under illumination, the trap states show a deleterious effect, favoring electron recombination.

Effect of surface fluorination on the electrochemical and photoelectrocatalytic properties of nanoporous titanium dioxide electrodes.

Titanium dioxide is a widely used photocatalyst whose properties can be modified by fluoride adsorption. This work is focused on the effect of surface fluorination on the electrochemical and photoelectrocatalytic properties of TiO(2) nanoporous thin films. Surface fluorination was achieved by simple addition of HF to the working solution (pH 3.5). Open circuit potential as well as ex situ XPS measurements verify that surface modification takes place. Fluorination triggers a significant capacitance increase in the accumulation potential region, as revealed by dark voltammetric measurements for all the TiO(2) samples studied. The photoelectrocatalytic properties (measured as photocurrents under white light illumination) depend on the substrate being oxidized and, in some cases, on the nature of the TiO(2) sample. In particular, the results obtained for electrodes prepared with a mixed phase (rutile + anatase) commercial nanopowder (PI-KEM) indicate that the processes mediated by surface trapped holes, such as the photooxidation of water or methanol, are accelerated while those occurring by direct hole capture from the adsorbed state (formic acid) are retarded. The photooxidation of catechol and phenol is also enhanced upon fluorination. In such a case, the effect can be rationalized on the basis of a diminished recombination and a surface displacement of both the oxidizable organic substrates and the poisoning species formed as a result of the organics oxidation. Photoelectrochemical and in situ infrared spectroscopic measurements support these ideas. In a more general vein, the results pave the way toward a better understanding of the photocatalysis phenomena, unravelling the importance of the reactant adsorption processes.

Energy transfer versus charge separation in hybrid systems of semiconductor quantum dots and Ru-dyes as potential co-sensitizers of TiO2-based solar cells

Hybrid structures of colloidal quantum dots (QDs) with Ru-dyes have been studied as candidates for panchromatic sensitizers for TiO2-based solar cells. Steady-state and time resolved photoluminescence spectroscopy and photocurrent measurements have been employed to identify the prevailing transfer mechanisms for photogenerated excitons between CdSe QDs capped with a traditional bulky organic ligand trioctylphosphine and Ru-dyes (N3 or Ru505) deposited onto inert glass or mesoporous TiO2 substrates. The type II energy level alignment between the QDs and both N3 and Ru505 offers a possibility for the directional charge separation, with electrons transferred to the QDs and holes to the dye. This scenario is indeed valid for the QD/Ru505 and TiO2/QD/Ru505 hybrid systems, with the negligible spectral overlap between the emission of the QDs and the absorption of the Ru505 dye. For the QD/N3 and TiO2/QD/N3 hybrid systems, the spectral overlap favors the longer range energy transfer from the QDs to N3, independen...

Determination of limiting factors of photovoltaic efficiency in quantum dot sensitized solar cells: Correlation between cell performance and structural properties

Semiconductor quantum dots (QDs) are important candidates as light absorbing materials in low cost and high efficiency sensitized solar cells (SCs). We present a combination of structural, chemical, electrical, and optical characterization that provides insight to the photovoltaic efficiencies of devices formed by TiO2 electron conducting oxide network sensitized with CdSe. In devices using colloidal QDs the collection efficiency under short circuit conditions (CESCs) for photoinjected electrons is rather high (∼90%) but the photovoltaic performance is limited by the low loading of QDs into the mesoporous TiO2 structure. On the other hand, chemical bath deposited (CBD) QDSCs exhibit a remarkably high optical density, but only slightly higher short circuit current and efficiency. It is observed that CESC is ∼50% due to the high recombination rates of the closed packed QDs structure. Our results indicate routes for improvement of QDSCs performance by the increase in colloidal QDs loading and the reduction i...

Synthesis of TiO2/WO3 nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination

Through an ultrasound assisted method, TiO2/WO3 nanoparticles were synthesized at room temperature. The XRD pattern of as-prepared TiO2/WO3 nanoparticles matches well with that of pure monoclinic WO3 and rutile TiO2 nanoparticles. TEM images show that the prepared TiO2/WO3 nanoparticles consist of mixed square and hexagonal shape particles about 8-12nm in diameter. The photocatalytic activity of TiO2/WO3 nanoparticles was tested for the degradation of a wastewater containing methylene blue (MB) under visible light illumination. The TiO2/WO3 nanoparticles exhibits a higher degradation rate constant (6.72×10(-4)s(-1)) than bare TiO2 nanoparticles (1.72×10(-4)s(-1)) under similar experimental conditions.

Photogeneration of Hydrogen from Water by Hybrid Molybdenum Sulfide Clusters Immobilized on Titania

Two new hybrid molybdenum(IV) Mo3 S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3 S7 Br6 ](2-) by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3 S7 Br4 (diimino) complexes. Adsorption of the Mo3 S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3 S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.3 V (for 1 mA cm(-2) ) with a turnover frequency as high as 1.4 s(-1) . The nature of the actual active molybdenum sulfide species has been investigated by X-ray photoelectron spectroscopy. In agreement with the electrochemical results, the modified TiO2 nanoparticles show a high photocatalytic activity for H2 production in the presence of Na2 S/Na2 SO3 as a sacrificial electron donor system.

Photoelectrochemical behaviour of anatase nanoporous films: effect of the nanoparticle organization

The photoelectrochemical behaviour of anatase thin films with different nanoarchitectures and the same active surface area (or thickness) has been studied in acidic media in the absence and in the presence of formic acid. The electrodes were composed of either wire-like nanocrystal aggregates or commercial TiO(2) nanoparticles. Cyclic voltammetry in the dark reveals a larger trap concentration in the band gap for the nanoparticulate (NP) electrodes, which can be ascribed to a larger number of intergrain boundaries. Also under illumination, the behaviour for both types of anatase structures significantly differs: water photooxidation arises at more negative potentials for the nanocolumnar (NC) electrodes. In the presence of an efficient hole acceptor such as HCOOH, significantly larger photocurrents were noted for the NC films as compared with those for the NP electrodes, with the photocurrent onset also shifted towards more positive potentials for the latter. These results point to a diminished electron recombination, which can be related with a smaller concentration of intergrain boundaries, together with a more efficient HCOOH hole transfer for the wire-like nanocrystal aggregate architecture. In addition, the oxygen reduction reaction is also favoured in the case of NC electrodes.