RESUMO
Quantifying recombination in halide perovskites is a crucial prerequisite to control and improve the performance of perovskite-based solar cells. While both steady-state and transient photoluminescence are frequently used to assess recombination in perovskite absorbers, quantitative analyses within a consistent model are seldom reported. We use transient photoluminescence measurements with a large dynamic range of more than ten orders of magnitude on triple-cation perovskite films showing long-lived photoluminescence transients featuring continuously changing decay times that range from tens of nanoseconds to hundreds of microseconds. We quantitatively explain both the transient and steady-state photoluminescence with the presence of a high density of shallow defects and consequent high rates of charge carrier trapping, thereby showing that deep defects do not affect the recombination dynamics. The complex carrier kinetics caused by emission and recombination processes via shallow defects imply that the reporting of only single lifetime values, as is routinely done in the literature, is meaningless for such materials. We show that the features indicative for shallow defects seen in the bare films remain dominant in finished devices and are therefore also crucial to understanding the performance of perovskite solar cells.
RESUMO
Picolinate-based segmented dianionic ligands L12- (5-((4-carboxyphenyl)ethynyl)picolinate) and L22- (5,5'-(ethyne-1,2-diyl)dipicolinate) have been used in the synthesis of the highly robust and luminescent europium(III) coordination polymers [(CH3)2NH2][Eu(H2O)2(L1)2] (1) and [(CH3)2NH2][Eu(L2)2]·H2O·CH3COOH (2). Both 1 and 2 exhibit high selectivity for detection of nitroaromatic compounds since they act as quenchers of the Eu3+ emission. Stern-Volmer plots, using nitrobenzene as a quencher, yielded values of KSV = 150 M-1 and 160 M-1 for 1 and 2, respectively. Luminescence studies in the presence of different metal ions indicate a high selectivity for Fe3+ detection, with KSV values of 471 M-1 and 706 M-1 for 1 and 2, respectively. Both 1 and 2 possess extremely robust extended structures, leading to emissive properties that are stable in a wide pH range.
RESUMO
Electron transport layers (ETL) based on tin(IV) oxide (SnO2) are recurrently employed in perovskite solar cells (PSCs) by many deposition techniques. Pulsed laser deposition (PLD) offers a few advantages for the fabrication of such layers, such as being compatible with large scale, patternable, and allowing deposition at fast rates. However, a precise understanding of how the deposition parameters can affect the SnO2 film, and as a consequence the solar cell performance, is needed. Herein, we use a PLD tool equipped with a droplet trap to minimize the number of excess particles (originated from debris) reaching the substrate, and we show how to control the PLD chamber pressure to obtain surfaces with very low roughness and how the concentration of oxygen in the background gas can affect the number of oxygen vacancies in the film. Using optimized deposition conditions, we obtained solar cells in the n-i-p configuration employing methylammonium lead iodide perovskite as the absorber layer with power conversion efficiencies exceeding 18% and identical performance to devices having the more typical atomic layer deposited SnO2 ETL.
RESUMO
Vacuum processing is considered to be a promising method allowing the scalable fabrication of perovskite solar cells (PSCs). In vacuum processed PSCs, the n-i-p structure employing organic charge transport layers is less common than the p-i-n structure due to limited options to achieve an efficient electron extraction layer (EEL) on indium tin oxide (ITO) with vacuum thermal evaporation. There are a number of specific applications where an n-i-p structure is required and therefore, it is of interest to have alternative solutions for the n-type contact in vacuum processed PSCs. In this work, we report an efficient vacuum deposited EEL using a mixture of conventional organic small molecules, C60 and bathocuproine (BCP). Incorporation of BCP into C60 does not result in conventional n-doping; however, we observed enhanced charge extraction, which significantly increased the power conversion efficiency (PCE) from 13.1% to 18.1% in all-vacuum processed PSCs. The C60:BCP mixed (co-sublimated) film most likely results in shifted energy levels leading to better alignment with the electrodes.
RESUMO
Vacuum deposition methods are increasingly applied to the preparation of perovskite films and devices, in view of the possibility to prepare multilayer structures at low temperature. Vacuum-deposited, wide-bandgap solar cells based on mixed-cation and mixed-anion perovskites have been scarcely reported, due to the challenges associated with the multiple-source processing of perovskite thin films. In this work, we describe a four-source vacuum deposition process to prepare wide-bandgap perovskites of the type FA1-n Cs n Pb(I1-x Br x )3 with a tunable bandgap and controlled morphology, using FAI, CsI, PbI2, and PbBr2 as the precursors. The simultaneous sublimation of PbI2 and PbBr2 allows the relative Br/Cs content to be decoupled and controlled, resulting in homogeneous perovskite films with a bandgap in the 1.7-1.8 eV range and no detectable halide segregation. Solar cells based on 1.75 eV bandgap perovskites show efficiency up to 16.8% and promising stability, maintaining 90% of the initial efficiency after 2 weeks of operation.
RESUMO
In perovskite solar cells, the choice of appropriate transport layers and electrodes is of great importance to guarantee efficient charge transport and collection, minimizing recombination losses. The possibility to sequentially process multiple layers by vacuum methods offers a tool to explore the effects of different materials and their combinations on the performance of optoelectronic devices. In this work, the effect of introducing interlayers and altering the electrode work function has been evaluated in fully vacuum-deposited perovskite solar cells. We compared the performance of solar cells employing common electron buffer layers such as bathocuproine (BCP), with other injection materials used in organic light-emitting diodes, such as lithium quinolate (Liq), as well as their combination. Additionally, high voltage solar cells were obtained using low work function metal electrodes, although with compromised stability. Solar cells with enhanced photovoltage and stability under continuous operation were obtained using BCP and BCP/Liq interlayers, resulting in an efficiency of approximately 19%, which is remarkable for simple methylammonium lead iodide absorbers.
RESUMO
Methylammonium lead triiodide (MAPI) has emerged as a high-performance photovoltaic material. Common understanding is that at room temperature, it adopts a tetragonal phase and it only converts to the perfect cubic phase around 50-60 °C. Most MAPI films are prepared using a solution-based coating process, yet they can also be obtained by vapor-phase deposition methods. Vapor-phase-processed MAPI films have significantly different characteristics than their solvent-processed analogous, such as relatively small crystal-grain sizes and short excited-state lifetimes. However, solar cells based on vapor-phase-processed MAPI films exhibit high power-conversion efficiencies. Surprisingly, after detailed characterization it is found that the vapor-phase-processed MAPI films adopt a cubic crystal structure at room temperature that is stable for weeks, even in ambient atmosphere. Furthermore, it is demonstrated that by tuning the deposition rates of both precursors during codeposition it is possible to vary the perovskite phase from cubic to tetragonal at room temperature. These findings challenge the common belief that MAPI is only stable in the tetragonal phase at room temperature.
RESUMO
A variety of experiments on vacuum-deposited methylammonium lead iodide perovskite solar cells are presented, including JV curves with different scan rates, light intensity-dependent open-circuit voltage, impedance spectra, intensity-modulated photocurrent spectra, transient photocurrents, and transient voltage step responses. All these experimental data sets are successfully reproduced by a charge drift-diffusion simulation model incorporating mobile ions and charge traps using a single set of parameters. While previous modeling studies focused on a single experimental technique, we combine steady-state, transient, and frequency-domain simulations and measurements. Our study is an important step toward quantitative simulation of perovskite solar cells, leading to a deeper understanding of the physical effects in these materials. The analysis of the transient current upon voltage turn-on in the dark reveals that the charge injection properties of the interfaces are triggered by the accumulation of mobile ionic defects. We show that the current rise of voltage step experiments allow for conclusions about the recombination at the interface. Whether one or two mobile ionic species are used in the model has only a minor influence on the observed effects. A delayed current rise observed upon reversing the bias from +3 to -3 V in the dark cannot be reproduced yet by our drift-diffusion model. We speculate that a reversible chemical reaction of mobile ions with the contact material may be the cause of this effect, thus requiring a future model extension. A parameter variation is performed in order to understand the performance-limiting factors of the device under investigation.
RESUMO
In genome analysis, k-mer-based comparison methods have become standard tools. However, even though they are able to deliver reliable results, other algorithms seem to work better in some cases. To improve k-mer-based DNA sequence analysis and comparison, we successfully checked whether adding positional resolution is beneficial for finding and/or comparing interesting organizational structures. A simple but efficient algorithm for extracting and saving local k-mer spectra (frequency distribution of k-mers) was developed and used. The results were analyzed by including positional information based on visualizations as genomic maps and by applying basic vector correlation methods. This analysis was concentrated on small word lengths (1 ≤ k ≤ 4) on relatively small viral genomes of Papillomaviridae and Herpesviridae, while also checking its usability for larger sequences, namely human chromosome 2 and the homologous chromosomes (2A, 2B) of a chimpanzee. Using this alignment-free analysis, several regions with specific characteristics in Papillomaviridae and Herpesviridae formerly identified by independent, mostly alignment-based methods, were confirmed. Correlations between the k-mer content and several genes in these genomes have been found, showing similarities between classified and unclassified viruses, which may be potentially useful for further taxonomic research. Furthermore, unknown k-mer correlations in the genomes of Human Herpesviruses (HHVs), which are probably of major biological function, are found and described. Using the chromosomes of a chimpanzee and human that are currently known, identities between the species on every analyzed chromosome were reproduced. This demonstrates the feasibility of our approach for large data sets of complex genomes. Based on these results, we suggest k-mer analysis with positional resolution as a method for closing a gap between the effectiveness of alignment-based methods (like NCBI BLAST) and the high pace of standard k-mer analysis.