Cristina Momblona

Trap-Assisted Non-Radiative Recombination in Organic-Inorganic Perovskite Solar Cells

Zernike Institute for Advanced Materials University of Groningen Nijenborgh 4, 9747 AG , Groningen , The Netherlands E-mail: wetzelaer@mpip-mainz.mpg.de M. Scheepers, A. Miquel Sempere, C. Momblona, J. Ávila, Dr. H. J. Bolink Instituto de Ciencia Molecular Universidad de Valencia C/J. Beltran 2, 46980 Paterna , Spain E-mail: henk.bolink@uv.es [+] Present address: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz Germany

High efficiency single-junction semitransparent perovskite solar cells

Semitransparent perovskite solar cells with a high power conversion efficiency (PCE) above 6% and 30% full device transparency have been achieved by implementing a thin perovskite layer and a simple foil compatible layout.

Efficient vacuum deposited p-i-n and n-i-p perovskite solar cells employing doped charge transport layers

Methylammonium lead halide perovskites have emerged as high performance photovoltaic materials. Most of these solar cells are prepared via solution-processing and record efficiencies (>20%) have been obtained employing perovskites with mixed halides and organic cations on (mesoscopic) metal oxides. Here, we demonstrate fully vacuum deposited planar perovskite solar cells by depositing methylammonium lead iodide in between intrinsic and doped organic charge transport molecules. Two configurations, one inverted with respect to the other, p-i-n and n-i-p, are prepared and optimized leading to planar solar cells without hysteresis and very high efficiencies, 16.5% and 20%, respectively. It is the first time that a direct comparison between these two opposite device configurations has been reported. These fully vacuum deposited solar cells, employing doped organic charge transport layers, validate for the first time vacuum based processing as a real alternative for perovskite solar cell preparation.

Persistent photovoltage in methylammonium lead iodide perovskite solar cells

We herein perform open circuit voltage decay (OCVD) measurements on methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells to increase the understanding of the charge carrier recombination dynamics in this emerging technology. Optically pulsed OCVD measurements are conducted on CH3NH3PbI3 solar cells and compared to results from another type of thin-film photovoltaics, namely, the two reference polymer–fullerene bulk heterojunction solar cell devices based on P3HT:PC60BM and PTB7:PC70BM blends. We observe two very different time domains of the voltage transient in the perovskite solar cell with a first drop on a short time scale that is similar to the decay in the studied organic solar cells. However, 65%–70% of the maximum photovoltage persists on much longer timescales in the perovskite solar cell than in the organic devices. In addition, we find that the recombination dynamics in all time regimes are dependent on the starting illumination intensity, which is also not observed in the organic dev...

Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 to 900 nm

Efficient methylammonium lead iodide perovskite-based solar cells have been prepared in which the perovskite layer is sandwiched in between two organic charge transporting layers that block holes and electrons, respectively. This configuration leads to stable and reproducible devices that do not suffer from strong hysteresis effects and when optimized lead to efficiencies close to 15%. The perovskite layer is formed by using a dual-source thermal evaporation method, whereas the organic layers are processed from solution. The dual-source thermal evaporation method leads to smooth films and allows for high precision thickness variations. Devices were prepared with perovskite layer thicknesses ranging from 160 to 900 nm. The short-circuit current observed for these devices increased with increasing perovskite layer thickness. The main parameter that decreases with increasing perovskite layer thickness is the fill factor and as a result optimum device performance is obtained for perovskite layer thickness aro...

Efficient Monolithic Perovskite/Perovskite Tandem Solar Cells

Thin-film solar cells suffer from various types of recombination, of which leakage current usually dominates at lower voltages. Herein, we demonstrate first a three-order reduction of the shunt loss mechanism in planar methylammonium lead iodide perovskite solar cells by replacing the commonly used hole transport layer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with a better hole-selective polyarylamine. As a result, these cells exhibit superior operation under reduced light conditions, which we demonstrate for the extreme case of moonlight irradiance, at which open-circuit voltages of 530 mV can still be obtained. By the shunt removal we also observe the VOC to drop to zero after as long as 2 h after the light has been switched off. Second, at higher illumination intensities the dominant losses in the PEDOT:PSS-based cell are ascribed to surface recombination and are also proven to be substantially minimized by instead employing the polyarylamine. We attribute the reduced shunt and surface recombination to the far better suited semiconductor character of the polyarylamine, compared to that of PEDOT:PSS, efficiently blocking electrons from recombining at this electrode. Solar cells are generally developed for operation under intense illumination such as direct sunlight or even using light concentrators. There are, however, numerous conditions in which the light intensity is lower because of nonideal orientation, sunrise or sunset, cloudy days, or indoor conditions. Importantly, to fully understand recombination mechanisms in solar cells, it is essential to also evaluate them under as large a range of illumination intensities as possible to assess which recombination pathway becomes dominant under each corresponding carrier concentration. Because recombination of excited charge carriers in photovoltaic devices are to various extents dependent on the charge carrier concentration, the rates accordingly depend on the illumination intensity itself. The general Shockley diode equation is of vital importance for solar cells because it defines how the total recombination processes depend on the internal voltage in a device. The relation between recombination current and voltage is usually described more accurately by the inclusion of an ideality factor (n), which varies depending on the dominant recombination mechanism. However, the Shockley diode equation is, even with the inclusion of an ideality factor, usually not sufficient to describe all processes that contribute to the overall recombination current dependency on the actual external voltage, V. Therefore, a more generalized Shockley equation (eq 1) accounting for both series and shunt resistances (RSeries and RShunt, respectively) is required: = − − + − − J J q V JR nkT V JR R J (exp[ ( )/ ] 1) 0 Series Series

Recombination in Perovskite Solar Cells: Significance of Grain Boundaries, Interface Traps, and Defect Ions

Trap-assisted recombination, despite being lower as compared with traditional inorganic solar cells, is still the dominant recombination mechanism in perovskite solar cells (PSCs) and limits their efficiency. We investigate the attributes of the primary trap-assisted recombination channels (grain boundaries and interfaces) and their correlation to defect ions in PSCs. We achieve this by using a validated device model to fit the simulations to the experimental data of efficient vacuum-deposited p–i–n and n–i–p CH3NH3PbI3 solar cells, including the light intensity dependence of the open-circuit voltage and fill factor. We find that, despite the presence of traps at interfaces and grain boundaries (GBs), their neutral (when filled with photogenerated charges) disposition along with the long-lived nature of holes leads to the high performance of PSCs. The sign of the traps (when filled) is of little importance in efficient solar cells with compact morphologies (fused GBs, low trap density). On the other hand, solar cells with noncompact morphologies (open GBs, high trap density) are sensitive to the sign of the traps and hence to the cell preparation methods. Even in the presence of traps at GBs, trap-assisted recombination at interfaces (between the transport layers and the perovskite) is the dominant loss mechanism. We find a direct correlation between the density of traps, the density of mobile ionic defects, and the degree of hysteresis observed in the current–voltage (J–V) characteristics. The presence of defect states or mobile ions not only limits the device performance but also plays a role in the J–V hysteresis.

Fullerene imposed high open-circuit voltage in efficient perovskite based solar cells

Five different commercially available fullerenes are evaluated as hole blocking/electron transporting materials in p–i–n methylammonium lead iodide perovskite solar cells using a vacuum deposited perovskite absorber layer. A significant enhancement of the solar cell performance can be obtained by selecting a suitable fullerene derivative. Open-circuit voltages as high as 1.11 volts are obtained leading to a power conversion efficiency of 14.6%.

Quantification of spatial inhomogeneity in perovskite solar cells by hyperspectral luminescence imaging

Vacuum evaporated perovskite solar cells with a power conversion efficiency of 15% have been characterized using hyperspectral luminescence imaging. Hyperspectral luminescence imaging is a novel technique that offers spectrally resolved photoluminescence and electroluminescence maps (spatial resolution is 2 micrometer) on an absolute scale. This allows, using the generalized Planck’s law, the construction of absolute maps of the depth-averaged quasi-Fermi level splitting (Δμ), which determines the maximum achievable open circuit voltage (Voc) of the solar cells. In a similar way, using the generalized reciprocity relations the charge transfer efficiency of the cells can be obtained from the hyperspectral images. Very strong inhomogeneity, both in quasi-Fermi level splitting (Δμ) and in charge transfer efficiency, are found in these vacuum deposited perovskite solar cells. This implies that these efficient solar cells are still far from perfect as many areas in the device do not or only partially participate in the photon to electron conversion processes.

Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands

The structure–property relationship study of a series of cationic Ir(III) complexes in the form of [Ir(C^N)2(dtBubpy)]PF6 [where dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = cyclometallating ligand bearing an electron-withdrawing group (EWG) at C4 of the phenyl substituent, i.e., −CF3 (1), −OCF3 (2), −SCF3 (3), −SO2CF3 (4)] has been investigated. The physical and optoelectronic properties of the four complexes were comprehensively characterized, including by X-ray diffraction analysis. All the complexes exhibit quasireversible dtBubpy-based reductions from −1.29 to −1.34 V (vs SCE). The oxidation processes are likewise quasireversible (metal + C^N ligand) and are between 1.54 and 1.72 V (vs SCE). The relative oxidation potentials follow a general trend associated with the Hammett parameter (σ) of the EWGs. Surprisingly, complex 4 bearing the strongest EWG does not adhere to the expected Hammett behavior and was found to exhibit red-shifted absorption and emission maxima. Nevertheless, the concept of introducing EWGs was found to be generally useful in blue-shifting the emission maxima of the complexes (λem = 484–545 nm) compared to that of the prototype complex [Ir(ppy)2(dtBubpy)]PF6 (where ppy = 2-phenylpyridinato) (λem = 591 nm). The complexes were found to be bright emitters in solution at room temperature (ΦPL = 45–66%) with microsecond excited-state lifetimes (τe = 1.14–4.28 μs). The photophysical properties along with density functional theory (DFT) calculations suggest that the emission of these complexes originates from mixed contributions from ligand-centered (LC) transitions and mixed metal-to-ligand and ligand-to-ligand charge transfer (LLCT/MLCT) transitions, depending on the EWG. In complexes 1, 3, and 4 the 3LC character is prominent over the mixed 3CT character, while in complex 2, the mixed 3CT character is much more pronounced, as demonstrated by DFT calculations and the observed positive solvatochromism effect. Due to the quasireversible nature of the oxidation and reduction waves, fabrication of light-emitting electrochemical cells (LEECs) using these complexes as emitters was possible with the LEECs showing moderate efficiencies.