Nanostructured semiconductor materials for dye-sensitized solar cells

Since O'Regan and Grätzel's first report in 1991, dye-sensitized solar cells (DSSCs) appeared immediately as a promising low-cost photovoltaic technology. In fact, though being far less efficient than conventional silicon-based photovoltaics (being the maximum, lab scale prototype reported efficiency around 13%), the simple design of the device and the absence of the strict and expensive manufacturing processes needed for conventional photovoltaics make them attractive in small-power applications especially in low-light conditions, where they outperform their silicon counterparts. Nanomaterials are at the very heart of DSSC, as the success of its design is due to the use of nanostructures at both the anode and the cathode. In this review, we present the state of the art for both n-type and p-type semiconductors used in the photoelectrodes of DSSCs, showing the evolution of the materials during the 25 years of history of this kind of devices. In the case of p-type semiconductors, also some other energy conversion applications are touched upon. © 2017 Carmen Cavallo et al

Solid solutions of rare earth cations in mesoporous anatase beads and their performances in dye-sensitized solar cells

Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1-0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J-V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms. © 2015, Nature Publishing Group. All rights reserved

Elaboration and characterization of nanoplate structured alpha-Fe2O3 films by Ag3PO4

A new strategy for surface treatment of hematite nanoplates for efficient photoelectrochemical (PEC) performances is proposed. Silver orthophosphate (Ag₃PO₄) has been adopted to mediate the formation of α-Fe₂O₃ films. Phosphate ions in Ag₃PO₄ is found to cause a significant morphology change during annealing process, from β-FeOOH nanorod arrays to hematite nanoplates. Meanwhile, Ag ions is doped into α-Fe₂O₃ film. The obtained nanoplate structured Fe₂O₃ –Ag–P films demonstrate much higher photoelectrochemical performance as photoanodes than the bare Fe₂O₃ nanorod thin films. The effects of phosphate and silver ions on the morphology, surface characteristics and the PEC properties of the photoanodes are investigated

Water splitting with polyoxometalate-treated photoanodes: Enhancing performance through sensitizer design

Visible light driven water oxidation has been demonstrated at near-neutral pH using photoanodes based on nanoporous films of TiO2, polyoxometalate (POM) water oxidation catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10- (1), and both known photosensitizer [Ru(bpy)2(H4dpbpy)]2+ (P2) and the novel crown ether functionalized dye [Ru(5-crownphen)2(H2dpbpy)] (H22). Both triads, containing catalyst 1, and catalyst-free dyads, produce O2 with high faradaic efficiencies (80 to 94%), but presence of catalyst enhances quantum yield by up to 190% (maximum 0.39%). New sensitizer H22 absorbs light more strongly than P2, and increases O2 quantum yields by up to 270%. TiO2-2 based photoelectrodes are also more stable to desorption of active species than TiO2-P2: losses of catalyst 1 are halved when pH > TiO2 point-of-zero charge (pzc), and losses of sensitizer reduced below the pzc (no catalyst is lost when pH < pzc). For the triads, quantum yields of O2 are higher at pH 5.8 than at pH 7.2, opposing the trend observed for 1 under homogeneous conditions. This is ascribed to lower stability of the dye oxidized states at higher pH, and less efficient electron transfer to TiO2, and is also consistent with the 4th 1-to-dye electron transfer limiting performance rather than catalyst TOFmax. Transient absorption reveals that TiO2-2-1 has similar 1st electron transfer dynamics to TiO2-P2-1, with rapid (ps timescale) formation of long-lived TiO2(e-)-2-1(h+) charge separated states, and demonstrates that metallation of the crown ether groups (Na+/Mg2+) has little or no effect on electron transfer from 1 to 2. The most widely relevant findings of this study are therefore: (i) increased dye extinction coefficients and binding stability significantly improve performance in dye-sensitized water splitting systems; (ii) binding of POMs to electrode surfaces can be stabilized through use of recognition groups; (iii) the optimal homogeneous and TiO2-bound operating pHs of a catalyst may not be the same; and (iv) dye-sensitized TiO2 can oxidize water without a catalyst

Implicating the Contributions of Surface and Bulk States on Carrier Trapping and Photocurrent Performance of BiVO\u3csub\u3e4\u3c/sub\u3e Photoanodes

Monoclinic-scheelite BiVO4 has been widely studied as a promising oxygen evolution reaction (OER) catalyst in artificial photosynthesis. Though significant progress to improve or augment its catalysis performance has been made, fundamental understanding of its relatively poor performance as a bare material is lacking. In this paper, we report the correlation of the surface structure and trap states with charge separation efficiency and OER performance of bare BiVO4 photoanodes viavarying the sample thickness. Using X-ray absorption spectroscopy (XAS), we observed a more compacted, symmetric Bi center in the surface state. Using transient absorption (TA) spectroscopy, we show that the structural properties of the surface lead to shallow and deep hole trap states and electron trapping that occurs at the surface of the material. Despite more severe carrier trapping on the surface, our OER measurements demonstrate that a significant bulk structure is required for light absorption but is only beneficial until the carrier mobility becomes the limiting factor in photoelectrochemical cell studies

Growth, Characterization, and Electrochemical Properties of Doped n-Type KTaO_3 Photoanodes

The effects of compositionally induced changes on the semiconducting properties, optical response, chemical stability, and overall performance of KTaO_3 photoanodes in photoelectrochemical (PEC) cells have been investigated. Single crystals of n-type Ca- and Ba-doped KTaO_3 with carrier concentrations ranging from 0.45 to 11.5×10^(19) cm^(−3) were grown and characterized as photoanodes in basic aqueous electrolyte PEC cells. The PEC properties of the crystals, including the photocurrent, photovoltage, and flatband potential in contact with 8.5 M NaOH(aq) were relatively independent of whether Ca or Ba was used to produce the semiconducting form of KTaO_3. All of the Ca- or Ba-doped KTaO_3 single-crystal photoanodes were chemically stable in the electrolyte and, based on the open-circuit potential and the band-edge positions, were capable of unassisted photochemical H_2 and O_2 evolution from H_2O. The minority-carrier diffusion lengths values were small and comparable to the depletion region width. Photoanodic currents were only observed for photoanode illumination with light above the bandgap (i.e., λ<340 nm). The maximum external quantum yield occurred at λ=255 nm (4.85 eV), and the depletion width plus the minority-carrier diffusion length ranged from 20 to 65 nm for the various KTaO_3-based photoanode materials

Combinatorial screening yields discovery of 29 metal oxide photoanodes for solar fuel generation

Combinatorial synthesis combined with high throughput electrochemistry enabled discovery of 29 ternary oxide photoanodes, 15 with visible light response for oxygen evolution. Y₃Fe₅O₁₂ and trigonal V₂CoO₆ emerge as particularly promising candidates due to their photorepsonse at sub-2.4 eV illumination