Ramón Tena-Zaera

Determination of carrier density of ZnO nanowires by electrochemical techniques

The carrier density of ZnO nanowires has been determined by means of electrochemical impedance spectroscopy. A model taking into account the geometry of ZnO nanowires has been developed and the differences with the standard flat model, as curved Mott-Schottky plots, are discussed. The as-grown electrodeposited samples present a high donor density of 6.2×1019cm−3, dramatically reduced by two orders of magnitude after an annealing in air at 450°C during 1h. The results show that the surface of the ZnO nanowires is active; therefore this system appears as a useful structure to support a functionalized nanostructured devices.

A sulfide/polysulfide-based ionic liquid electrolyte for quantum dot-sensitized solar cells.

Further development of quantum dot-sensitized solar cells (QDSCs) will require long-term stability in addition to the continuous increase of photovoltaic (PV) conversion efficiency achieved in the last years. We report a robust S(2-)/S(n)(2-) electrolyte that has been specifically designed for compatibility with CdSe quantum dots in sensitized solar cells. The new pyrrolidinium ionic liquid reaches 1.86% efficiency and a short-circuit current close to 14 mA·cm(-2) under air-mass 1.5 global illumination and improves the device lifetime with good photoanode stability over 240 h. PV characterization showed that the solar cell limitations relate to poor catalysis of regeneration at the counter electrode and high recombination. Further improvement of these factors in the robust electrolyte configuration may thus have a significant impact for advancing the state-of-the-art in QDSCs.

Organo-metal halide perovskite-based solar cells with CuSCN as the inorganic hole selective contact

CuSCN is proposed as a cost-competitive hole selective contact for the emerging organo-metal halide perovskite-based solar cells. The CuSCN films have been deposited by a solution casting technique, which has proven to be compatible with the perovskite films, obtaining planar-like heterojunction-based glass/FTO/TiO2/CH3NH3PbI3−xClx/CuSCN/Au solar cells with a power conversion efficiency of 6.4%. Among the photovoltaic parameters, the fill factor (i.e. 62%) suggests good carrier selectivity and, therefore, efficient functionality of the TiO2 and CuSCN charge carrier selective contacts. However, the open-circuit voltage (Voc), which remains low in comparison with the state of the art perovskite-based solar cells, appears to be the main limiting parameter. This is attributed to the short diffusion length as determined by impedance spectroscopy. However, the recombination losses are not only affected by the CuSCN, but also by the perovskite film. Indeed, variations of 20 °C in the thermal annealing of the perovskite films result in changes larger than 200 mV in the Voc. Furthermore, a detailed analysis of the quantum efficiency spectra contributes significant insights into the influence of the selective contacts on the photocurrent of the planar heterojunction perovskite solar cells.

ZnO nanowire arrays: Optical scattering and sensitization to solar light

Arrays of ZnO nanowires with different lengths (0.5–2 μm) and diameters (100–330 nm) were electrodeposited to study the influence of the nanowire dimensions on light scattering. The nanowire length and diameter were found to be major parameters in modifying the intensity and the wavelength of the scattered radiation, respectively. A significant scattering for the whole visible wavelength range was attained in arrays of ZnO nanowires of ∼1.5 μm in length and ∼330 nm in diameter. ZnO nanowire arrays were sensitized to solar light with a conformally deposited thin CdSe layer. A clear correlation between light scattering before coating and absorption in the resulting ZnO/CdSe core-shell nanostructures was found. The enhancement in the scattering for wavelengths where CdSe exhibits a relatively low absorption coefficient resulted in an effective absorption, in the 400–725 nm range of the AM1.5 solar spectrum, as high as 88% with a CdSe shell thickness of ∼20 nm only.

ZnO solar cells with an indoline sensitizer: a comparison between nanoparticulate films and electrodeposited nanowire arrays

The photovoltaic properties of nanostructured ZnO films sensitized with the indoline derivative dye D149 were studied. The performance of dye-sensitized solar cells built from ZnO building blocks with different morphology, (a) randomly oriented nanoparticle network and (b) nanowire arrays, was compared. The nanoparticle networks were prepared by the standard doctor blade technique from commercial ZnO powders and the nanowire arrays were electrodeposited in aqueous media. Two different lengths for the nanowire arrays (2.5 and 5 µm) were considered. The characterization included electron microscopy, adsorption measurements, optical spectroscopy, current–voltage characteristics, open-circuit voltage versus light intensity, incident-photon-to-current efficiency, open circuit voltage decay and impedance spectroscopy under illumination. In spite of the smaller dye loadings of the nanowires with respect to the nanoparticles, the former showed a remarkably effective integrated optical absorption (in the range from 370 to 700 nm, 57% versus 69% for the latter). However the photocurrents for nanowires were lower than expected from this good absorption, which suggests that recombination rather than solar light harvesting can be the limiting factor in these nanowire-based solar cells. The impedance analysis and the open-circuit voltage decays showed smaller recombination resistances and shorter lifetimes for the nanowire-based solar cells. However, the interpretation of the recombination resistances, capacitances and lifetimes in the case of the nanowires is likely affected by space-charge effects and back-reaction through the substrate. An understanding of the effects discovered in this study is very valuable for the development of strategies to enhance the energy conversion efficiency for the ZnO nanowire array based solar cells.

Inverted ITO-free organic solar cells based on p and n semiconducting oxides. New designs for integration in tandem cells, top or bottom detecting devices, and photovoltaic windows

We report organic photovoltaic devices in which the standard ITO transparent electric contact has been substituted by lower cost ultrathin metallic electrodes. Solution and vacuum processable n and p-type semiconductors provide the electrode with the rectifying behavior of the diode. We are in this way able to invert the built-in electric field at wish and make the device deliberately either top or bottom sensitive with the same efficiency depending on the application. Taking advantage of these new generation electrodes we furthermore report devices with fill factors over 70%—to our knowledge, the largest published to date for an organic photovoltaic cell—and power conversion efficiencies over the state-of-art with 3.5% in inverted P3HT:PCBM devices, ITO free designs over 2.5% and (semi)transparent photovoltaic devices with conversion efficiencies close to 2.6%. This breakthrough could once and for all trigger the fabrication of organic tandem solar cells and photovoltaic windows.

Electrodeposition of antimony selenide thin films and application in semiconductor sensitized solar cells.

Sb2Se3 thin films are proposed as an alternative light harvester for semiconductor sensitized solar cells. An innovative electrodeposition route, based on aqueous alkaline electrolytes, is presented to obtain amorphous Sb2Se3. The amorphous to crystalline phase transition takes place during a soft thermal annealing in Ar atmosphere. The potential of the Sb2Se3 electrodeposited thin films in semiconductor sensitized solar cells is evaluated by preparing TiO2/Sb2Se3/CuSCN planar heterojunction solar cells. The resulting devices generate electricity from the visible and NIR photons, exhibiting the external quantum efficiency onset close to 1050 nm. Although planar architecture is not optimized in terms of charge carrier collection, photocurrent as high as 18 mA/cm(2), under simulated (AM1.5G) solar light, is achieved. Furthermore, the effect of the Sb2Se3 thickness and microstructural properties on the photocurrent is analyzed, suggesting the hole transport is the main limiting mechanism. The present findings provide significant insights to design efficient semiconductor sensitized solar cells based on advanced architectures (e.g., nanostructured and tandem), opening wide possibilities for progresses in this emerging photovoltaics technology.

Efficient Regular Perovskite Solar Cells Based on Pristine [70]Fullerene as Electron-Selective Contact

[70]Fullerene is presented as an efficient alternative electron-selective contact (ESC) for regular-architecture perovskite solar cells (PSCs). A smart and simple, well-described solution processing protocol for the preparation of [70]- and [60]fullerene-based solar cells, namely the fullerene saturation approach (FSA), allowed us to obtain similar power conversion efficiencies for both fullerene materials (i.e., 10.4 and 11.4 % for [70]- and [60]fullerene-based devices, respectively). Importantly, despite the low electron mobility and significant visible-light absorption of [70]fullerene, the presented protocol allows the employment of [70]fullerene as an efficient ESC. The [70]fullerene film thickness and its solubility in the perovskite processing solutions are crucial parameters, which can be controlled by the use of this simple solution processing protocol. The damage to the [70]fullerene film through dissolution during the perovskite deposition is avoided through the saturation of the perovskite processing solution with [70]fullerene. Additionally, this fullerene-saturation strategy improves the performance of the perovskite film significantly and enhances the power conversion efficiency of solar cells based on different ESCs (i.e., [60]fullerene, [70]fullerene, and TiO2 ). Therefore, this universal solution processing protocol widens the opportunities for the further development of PSCs.

Multicolor Electrochromics: Rainbow-Like Devices

Stimuli-responsive reversible coloration-change materials represent a highly demanded type of smart systems useful for a wide variety of applications, with a significant growing interest in multicolor abilities. In particular, electrochromic materials have received a great deal of attention due to their versatility and broad range of industrial uses. However, most of the existing electrochromic technologies provide a single coloration, while achieving multiple colors based on simple approaches remains a challenge. The present article reports on PVA gel-based electrochromic devices, containing a single viologen, providing a colorless and two different well-defined colored states. The successful fabrication of a device, based on two viologens (multi-EC gel) with a simple architecture (glass/TCO/multi-EC gel/TCO/glass), with five different multiswitchable colors based on four-zoned electrodes (rainbow-like ECD) is also demonstrated. This novel easy-to-make multichromic system represents a significant breakthrough toward the generation of full-color devices, expanding the potential of electrochromic technology.

Electron Transport Layer-Free Solar Cells Based on Perovskite-Fullerene Blend Films with Enhanced Performance and Stability.

The solution processing of pinhole-free methylammonium lead triiodide perovskite-C70 fullerene (MAPbI3 :C70 ) blend films on fluorine-doped tin oxide (FTO)-coated glass substrates is presented. Based on this approach, a simplified and robust protocol for the preparation of efficient electron-transport layer (ETL)-free perovskite solar cells is described. Power conversion efficiency (PCE) of 13.6 % under AM 1.5 G simulated sunlight is demonstrated for these devices. Comparative impedance spectroscopy and photostability analysis of the MAPbI3 :C70 and single MAPbI3 films compared with conventional compact TiO2 ETL-based devices are shown. The beneficial impact of using MAPbI3 :C70 blend films is emphasized.