Properties of Contact and Bulk Impedances in Hybrid Lead Halide Perovskite Solar Cells Including Inductive Loop Elements

Impedance spectroscopy offers access to all the different electronic and ionic processes taking place simultaneously in an operating solar cell. To date, its use on perovskite solar cells has been challenging because of the richness of the physical processes occurring within similar time domains. The aim of this work is to understand the general impedance response and propose a general equivalent circuit model that accounts for the different processes and gives access to quantitative analysis. When the electron-selective contacts and the thickness of the perovskite film are systematically modified, it is possible to distinguish between the characteristic impedance signals of the perovskite layer and those arising from the contacts. The study is carried out using mixed organic lead halogen perovskite (FA(0.85)MA(0.15)Pb(I0.85Br0.15)(3)) solar cells with three different electron-selective contacts: SnO2, TiO2, and Nb2O5. The contacts have been deposited by atomic layer deposition (ALD), which provides pinhole-free films and excellent thickness control in the absence of a mesoporous layer to simplify the impedance analysis. It was found that the interfacial impedance has a rich structure that reveals different capacitive processes, serial steps for electron extraction, and a prominent inductive loop related to negative capacitance at intermediate frequencies. Overall, the present report provides insights into the impedance response of perovskite solar cells which enable an understanding of the different electronic and ionic processes taking place during device operation.The work at INAM-UJI was supported by Generalitat Valenciana project PROMETEO/2014/020 and MINECO of Spain under Project MAT2013-47192-C3-1-R. A.G. thanks the Spanish Ministerio de Economía y Competitividad for a Ramón y Cajal Fellowship (RYC-2014-16809). T.J.J. gratefully acknowledges the GRAPHENE project supported by the European Commission Seventh Framework Program under Contract 604391

Reducing Detrimental Defects for High‐Performance Metal Halide Perovskite Solar Cells

In several photovoltaic (PV) technologies, the presence of electronic defects within the semiconductor band gap limit the efficiency, reproducibility, as well as lifetime. Metal halide perovskites (MHPs) have drawn great attention because of their excellent photovoltaic properties that can be achieved even without a very strict film‐growth control processing. Much has been done theoretically in describing the different point defects in MHPs. Herein, we discuss the experimental challenges in thoroughly characterizing the defects in MHPs such as, experimental assignment of the type of defects, defects densities, and the energy positions within the band gap induced by these defects. The second topic of this Review is passivation strategies. Based on a literature survey, the different types of defects that are important to consider and need to be minimized are examined. A complete fundamental understanding of defect nature in MHPs is needed to further improve their optoelectronic functionalities

Zonage du Bresil a partir d'une serie temporelle d'images modis.

Zoneamento do Brasil a partir de uma série temporal de imagens MODIS . A cartografia das paisagens envolvem geralmente a combinação de informações ambientais e informações sobre as atividades humanas. A qualidade da carta de paisagem resultante depende fortemente da expertise e do método utilizado, assim como da qualidade dos dados que foram usados na sua elaboração. As séries temporais das imagens de satélite aportam uma visão objetiva do território a diferentes datas. Estas imagens podem ser segmentadas para estratificar o espaço em zonas radiometricamente homogêneas. O objetivo deste trabalho é testar este método de estratificação a diferentes escalas espaciais, no Brasil e na região do estado do Maranhão e avaliar as estratificações de forma não supervisionada. Para tanto, uma segmentação orientada à objeto foi realizada utilizando-se o software eCognition a partir de valores dos índices de vegetação EVI (Enhaced Vegetation Index) e de índices de textura advindos de uma série temporal de imagens MODIS com resolução espacial de 250m. Diferentes variáveis radiométricas e diferentes escalas de segmentação foram testadas e avaliadas através de dois indicadores estatísticos. A segmentação obtida foi, então, comparada visualmente aos zoneamentos existentes (GAEZ da FAO e zoneamento agroecológico da Embrapa)

On Mott-Schottky analysis interpretation of capacitance measurements in organometal perovskite solar cells

Capacitance response of perovskite-based solar cells (PSCs) can be exploited to infer underlying physical mechanisms, both in the materials bulk and at outer interfaces. Particularly interesting is applying the depletion layer capacitance theory to PSCs, following common procedures used with inorganic and organic photovoltaic devices. Voltage-modulation of the depletion layer width allows extracting relevant parameters as the absorber defect density and built-in potential by means of the Mott-Schottky (MS) analysis. However, the uncritical use of the MS technique may be misleading and yields incorrect outcomes as a consequence of masking effects that accumulation capacitances, commonly observed in PSCs, produce on the measured capacitance value. Rules are provided here to select the measuring frequency that allows extracting depletion layer capacitance, and the voltage range in which it dominates, avoiding accumulation capacitive parasitic contributions. It is noted that the distinction of the depletion capacitance from the accumulation capacitance is only feasible in the case of perovskite layers containing significant defect density (∼1017 cm−3). It is confirmed that MS reproducibility is assured by hysteresis reduction at slow scan rates, and positive bias starting polarization. A complete procedure with specific checking points is provided here for consistent MS measurement and interpretation.We thank the Ministerio de Economía y Competitividad (MINECO) of Spain for financial support under Projects (MAT2013-47192-C3-1-R and MAT2016-76892-C3-1-R), and Generalitat Valenciana (Prometeo/2014/020). O.A. acknowledges Generalitat Valenciana for a Grant (GRISOLIAP2014/035). E.M.-M. thanks the Ramón y Cajal program from MINECO of Spain. SCIC at UJI are also acknowledged

Millisecond radiative recombination in poly(phenylene vinylene)-based light-emitting diodes from transient electroluminescence

The current and electroluminescence transient responses of standard poly(phenylene vinylene)-based light-emitting devices have been investigated. The electroluminescence time response is longer (milliseconds scale) than the current switch-off time by more than one order of magnitude, in the case of small area devices (<0.1 cm2). For large area devices ( ∼ 6 cm2) the electroluminescence decay time decreases from 1.45 ms to  ∼ 100 μs with increasing bias voltage. The fast current decay limits the electroluminescence decay at higher voltages. Several approaches are discussed to interpret the observed slow decrease of electroluminescence after turning off the bias. One relies upon the Langevin-type bimolecular recombination kinetics which is governed by the minority carriers (electrons), and another focuses on the slow release of trapped electrons as possible explanations. Additionally, we show that the device current density is mainly determined by the transport of the fastest carriers (holes)[email protected]

Electrical field profile and doping in planar lead halide perovskite solar cells

Hybrid lead halide perovskites (PVKs) have emerged as novel materials for photovoltaics and have rapidly reached very large solar to electricity power conversion efficiencies. As occurring with other kind of solar technologies establishing the working energy-band diagram constitutes a primary goal for device physics analysis. Here, the macroscopic electrical field distribution is experimentally determined using capacitance-voltage and Kelvin probe techniques. Planar struc- tures comprising CH3NH3PbI3�����xClx PVK exhibit p-doping character and form a p-n heterojunc- tion with n-doped TiO2 compact layers. Depletion width at equilibrium within the PVK bulk has an extent about 300 nm (approximately half of the layer thickness), leaving as a consequence a significant neutral zone towards the anode contact. Charge collection properties are then accessi- ble relying on the relative weight that diffusion and drift have as carrier transport driven forces

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

Localized versus delocalized states: Photoluminescence from electrochemically synthesized ZnO nanowires

We analyze the near-band-edge photoluminescence of electrochemically deposited ZnO nanowires and directly correlate the photoluminescence properties with the carrier concentration in the nanowires as determined from electrochemical impedance spectroscopy. We find a donor density of 81019 cm−3 in the as-deposited nanowires and show that the near-band-edge emission results from band-to-band recombination processes delocalized states. A photoluminescence band centered at 3.328 eV scales with the diameter of the nanowires and is assigned to recombination processes involving surface states. We show that annealing at 500 °C in air reduces the donor density in the nanowires by more than one order of magnitude, leading to sharp excitonic transitions in the electrochemically deposited nanowire