Mechanism of carrier accumulation in perovskite thin-absorber solar cells

[EN] Photovoltaic conversion requires two successive steps: accumulation of a photogenerated charge and charge separation. Determination of how and where charge accumulation is attained and how this accumulation can be identified is mandatory for understanding the performance of a photovoltaic device and for its further optimization. Here we analyse the mechanism of carrier accumulation in lead halide perovskite, CH3NH3PbI3, thin-absorber solar cells by means of impedance spectroscopy. A fingerprint of the charge accumulation in high density of states of the perovskite absorber material has been observed at the capacitance of the samples. This is, as far as we know, the first observation of charge accumulation in light-absorbing material for nanostructured solar cells, indicating that it constitutes a new kind of photovoltaic device, differentiated from sensitized solar cells, which will require its own methods of study, characterization and optimization.We thank the following agencies for supporting this research: Ministerio de Educacion y Ciencia under project HOPE CSD2007-00007, Generalitat Valenciana (ISIC/2012/008) and Universitat Jaume I project 12I361.01/1. This work was also supported by the National Research Foundation of Korea (NRF) grant funded by the Ministry of Science, ICT & Future Planning (MSIP) of Korea under contracts No. NRF-2012M1A2A2671721, NRF-2010-0014992 and NRF-2012M3A6A7054861 (the Global Frontier R&D Program on Center for Multiscale Energy System). H.-S.K. is grateful for the global Ph.D. fellowship grant funded by NRF (NRF-2011-0008467). We thank Mr. Dae-Yong Son for preparation of the ZrO2 paste. We thank Prof. A. Maquieira and Dr. M.J. Banuls from the Institute of Molecular Recognition and Technological Development (Polytechnic University of Valencia) for SEM measurements of CH3NH3PbI3-xClx samples.Kim, H.; Mora-Sero, I.; González-Pedro, V.; Fabregat-Santiago, F.; Juarez-Perez, EJ.; Park, N.; Bisquert Mascarell, J. (2013). Mechanism of carrier accumulation in perovskite thin-absorber solar cells. Nature Communications. 4:1-7. https://doi.org/10.1038/ncomms3242S174Nozik, A. J. Quantum dot solar cells. Physica E 14, 115–200 (2002).O'Regan, B. & Gratzel, M. A low-cost, high-efficiency solar-cell based on dye-sensitized colloidal TiO2 films. Nature 353, 737–740 (1991).Hodes, G. Comparison of dye- and semiconductor-sensitized porous nanocrystalline liquid junction solar cells. J. Phys. Chem. C 112, 17778–17787 (2008).Mora-Seró, I. & Bisquert, J. Breakthroughs in the development of semiconductor-sensitized solar cells. J. 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Design and characterization of alkoxy-wrapped push-pull porphyrins for dye-sensitized solar cells

Three alkoxy-wrapped push-pull porphyrins were designed and synthesized for dye-sensitized solar cell (DSSC) applications. Spectral, electrochemical, photovoltaic and electrochemical impedance spectroscopy properties of these porphyrin sensitizers were well investigated to provide evidence for the molecular design

Harnessing Infrared Photons for Photoelectrochemical Hydrogen Generation. A PbS Quantum Dot Based "Quasi-Artificial Leaf"

[EN] Hydrogen generation by using quantum dot (QD) based heterostructures has emerged as a promising strategy to develop artificial photosynthesis devices. In the present study, we sensitize mesoporous TiO2 electrodes with in-situ-deposited PbS/CdS QDs, aiming at harvesting light in both the visible and the near-infrared for hydrogen generation. This heterostructure exhibits a remarkable photocurrent of 6 mA.cm(-2), leading to 60 mL.cm(-2).day(-1) hydrogen generation. Most importantly, confirmation of the contribution of infrared photons to H-2 generation was provided by the incident-photon-to-current-efficiency (IPCE), and the integrated current was in excellent agreement with that obtained through cyclic voltammetry. The main electronic processes (accumulation, transport, and recombination) were identified by impedance spectroscopy, which appears as a simple and reliable methodology to evaluate the limiting factors of these photoelectrodes. On the basis of this TiO2/PbS/CdS heterostructrure, a "quasi-artificial leaf' has been developed, which has proven to produce hydrogen under simulated solar illumination at (4.30 +/- 0.25) mL.cm(-2).day(-1).We acknowledge support by projects from Ministerio de Economia y Competitividad (MINECO) of Spain (Consolider HOPE CSD2007-00007, MAT2010-19827), Generalitat Valenciana (PROMETEO/2009/058 and Project ISIC/2012/008 "Institute of Nanotechnologies for Clean Energies"), and Fundacio Bancaixa (P1.1B2011-50). S.G. acknowledges support by MINECO of Spain under the Ramon y Cajal programme. The SCIC of the University Jaume I de Castello is also acknowledged for the gas analysis measurements. C.S. acknowledges the POSDRU/89/1.5/S/58852 Project "Postdoctoral programme for training scientific researchers", co-financed by the European Social Fund within the Sectorial Operational Program Human Resources Development 2007-2013. We want to acknowledge Prof. J. Bisquert for the fruitful discussions related to this manuscript.Trevisan, R.; Rodenas, P.; González-Pedro, V.; Sima, C.; Sánchez, RS.; Barea, EM.; Mora-Sero, I.... (2013). Harnessing Infrared Photons for Photoelectrochemical Hydrogen Generation. A PbS Quantum Dot Based "Quasi-Artificial Leaf". Journal of Physical Chemistry Letters. 4(1):141-146. https://doi.org/10.1021/jz301890mS1411464

Water oxidation at hematite photoelectrodes: the role of surface states

Hematite (α-Fe2O3) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical–chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement

Growth of Comb-like ZnO Nanostructures for Dye-sensitized Solar Cells Applications

Dye-sensitized solar cells (DSSCs) were fabricated by using well-crystallized ZnO nanocombs directly grown onto the fluorine-doped tin oxide (FTO) via noncatalytic thermal evaporation process. The thin films of as-grown ZnO nanocombs were used as photoanode materials to fabricate the DSSCs, which exhibited an overall light to electricity conversion efficiency of 0.68% with a fill factor of 34%, short-circuit current of 3.14 mA/cm2, and open-circuit voltage of 0.671 V. To the best of our knowledge, this is first report in which thin film of ZnO nanocombs was used as photoanode materials to fabricate the DSSCs

A cobalt complex redox shuttle for dye-sensitized solar cells with high open-circuit potentials

Dye-sensitized solar cells are a promising alternative to traditional inorganic semiconductor-based solar cells. Here we report an open-circuit voltage of over 1,000 mV in mesoscopic dye-sensitized solar cells incorporating a molecularly engineered cobalt complex as redox mediator. Cobalt complexes have negligible absorption in the visible region of the solar spectrum, and their redox properties can be tuned in a controlled fashion by selecting suitable donor/acceptor substituents on the ligand. This approach offers an attractive alternate to the traditional I3−/I− redox shuttle used in dye-sensitized solar cells. A cobalt complex using tridendate ligands [Co(bpy-pz)2]3+/2+(PF6)3/2 as redox mediator in combination with a cyclopentadithiophene-bridged donor-acceptor dye (Y123), adsorbed on TiO2, yielded a power conversion efficiency of over 10% at 100 mW cm−2. This result indicates that the molecularly engineered cobalt redox shuttle is a legitimate alternative to the commonly used I3−/I− redox shuttle

Layer-by-layer deposition of open-pore mesoporous TiO 2- Nafion® film electrodes

The formation of variable thickness TiO2 nanoparticle-Nafion® composite films with open pores is demonstrated via a layer-by-layer deposition process. Films of about 6 nm diameter TiO2 nanoparticles grow in the presence of Nafion® by “clustering” of nanoparticles into bigger aggregates, and the resulting hierarchical structure thickens with about 25 nm per deposition cycle. Film growth is characterized by electron microscopy, atomic force microscopy, and quartz crystal microbalance techniques. Simultaneous small-angle X-ray scattering and wide-angle X-ray scattering measurements for films before and after calcination demonstrate the effect of Nafion® binder causing aggregation. Electrochemical methods are employed to characterize the electrical conductivity and diffusivity of charge through the TiO2-Nafion® composite films. Characteristic electrochemical responses are observed for cationic redox systems (diheptylviologen2+/+, Ru(NH3)3+/2+6, and ferrocenylmethyl-trimethylammonium2+/+) immobilized into the TiO2-Nafion® nanocomposite material. Charge conduction is dependent on the type of redox system and is proposed to occur either via direct conduction through the TiO2 backbone (at sufficiently negative potentials) or via redox-center-based diffusion/electron hopping (at more positive potentials)

Accurate and homogeneous abundance patterns in solar-type stars of the solar neighbourhood: a chemo-chronological analysis

We report the abundances of C, Na, Mg, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Ba, Ce, Nd, and Sm in 25 solar-type stars in the solar neighbourhood, and their correlations with ages, kinematics, and orbital parameters. The spectroscopic analysis, based high resolution and high S/N ratio data, was differential to the Sun and applied to atomic line EWs and to C and C2 spectral synthesis. We performed a statistical study using a tree clustering analysis, searching for groups of stars sharing similar abundance patterns. We derived Teff, log(g), and [Fe/H] with errors of 30 K, 0.13 dex, and 0.05 dex, respectively. The average error in [X/Fe] is 0.06 dex. Ages were derived from theoretical HR diagrams and memberships in kinematical moving groups. We identified four stellar groups: with over-solar abundances ( = +0.26 dex), under-solar abundances ( = -0.24 dex), and intermediate values ( = -0.06 and +0.06 dex) but with distinct chemical patterns. Stars sharing solar metallicity, age, and Galactic orbit possibly have non-solar abundance, an effect either of chemical heterogeneity in their natal clouds or migration. A trend of [Cu/Fe] with [Ba/Fe] seems to exist, in agreement with previous claims in the literature, and maybe also of [Sm/Fe] with [Ba/Fe]. No such correlation involving C, Na, Mn, and Zn is observed. [Mg/Fe], [Sc/Fe], and [Ti/Fe] increase with age. [Mn/Fe] and [Cu/Fe] first increase towards younger stars up to the solar age, and then decrease, a result we interpret as possibly related to time-varying yields of SN Ia and the weak s-process. [Sr/Fe], [Y/Fe], [Sr/Mg], [Y/Mg], [Sr/Zn], and [Y/Zn] linearly increase towards younger stars. [Zr/Fe], [Ce/Fe], [Nd/Fe], [Ba/Mg], [Ba/Zn], and [Sr,Y,Ba/Sm] increase but only for stars younger than the Sun. The steepest negative age relation is due to [Ba/Fe], but only for stars younger than the Sun.Comment: 27 pages, 11 figures, 10 table

Mass segregation in young compact star clusters in the Large Magellanic Cloud: II. Mass Functions

We review the complications involved in the conversion of stellar luminosities into masses and apply a range of mass-to-luminosity relations to our Hubble Space Telescope observations of the young LMC star clusters NGC 1805 and NGC 1818. Both the radial dependence of the mass function (MF) and the dependence of the cluster core radii on mass indicate clear mass segregation in both clusters at radii r <= 20-30'', for masses in excess of ~1.6-2.5 Msun. This result does not depend on the mass range used to fit the slopes or the metallicity assumed. It is clear that the cluster MFs, at any radius, are not simple power laws. The global and the annular MFs near the core radii appear to be characterised by similar slopes in the mass range (-0.15 <= log m/Msun <= 0.85), the MFs beyond r >= 30'' have significantly steeper slopes. We estimate that while the NGC 1818 cluster core is between ~5 and ~30 crossing times old, the core of NGC 1805 is likely $\lesssim 3-4$ crossing times old. However, since strong mass segregation is observed out to ~6 Rcore and ~3 Rcore in NGC 1805 and NGC 1818, respectively, it is most likely that significant primordial mass segregation was present in both clusters, particularly in NGC 1805.Comment: 16 pages, incl. 9 embedded postscript figures, MNRAS, resubmitted (referee's comments included