25 research outputs found
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Understanding macroscale functionality of metal halide perovskites in terms of nanoscale heterogeneities
Hybrid metal halide perovskites have shown an unprecedented rise as semiconductor building blocks for solar energy conversion and light-emitting applications. Currently, the field moves empirically towards more and more complex chemical compositions, including mixed halide quadruple cation compounds that allow optical properties to be tuned and show promise for better stability. Despite tremendous progress in the field, there is a need for better understanding of mechanisms of efficiency loss and instabilities to facilitate rational optimization of composition. Starting from the device level and then diving into nanoscale properties, we highlight how structural and compositional heterogeneities affect macroscopic optoelectronic characteristics. Furthermore, we provide an overview of some of the advanced spectroscopy and imaging methods that are used to probe disorder and non-uniformities. A unique feature of hybrid halide perovskite compounds is the propensity for these heterogeneities to evolve in space and time under relatively mild illumination and applied electric fields, such as those found within active devices. This introduces an additional challenge for characterization and calls for application of complimentary probes that can aid in correlating the properties of local disorder with macroscopic function, with the ultimate goal of rationally tailoring synthesis towards optimal structures and compositions
Maximizing and stabilizing luminescence from halide perovskites with potassium passivation
Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability2 (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.M.A.-J. thanks Nava Technology Limited and Nyak Technology Limited for their funding and technical support. Z.A.-G. acknowledges funding from a Winton Studentship, and ICON Studentship from the Lloyd’s Register Foundation. This project has received funding from the European Union’s Seventh Framework Programme (FP7/2007-2013) under REA grant agreement number PIOF-GA-2013-622630, the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement number 756962), and the Royal Society and Tata Group (UF150033). We thank the Engineering and Physical Sciences Research Council (EPSRC) for support. XMaS is a mid-range facility at the European Synchrotron Radiation Facility supported by the EPSRC and we are grateful to the XMaS beamline team staff for their support. We thank Diamond Light Source for access to beamline I09 and staff member T.-L. Lee as well as U. Cappel for assistance during the HAXPES measurements. S.C., C.D. and G.D. acknowledge funding from the ERC under grant number 25961976 PHOTO EM and financial support from the European Union under grant number 77 312483 ESTEEM2. M.A. thanks the president of the UAE’s Distinguished Student Scholarship Program, granted by the Ministry of Presidential Affairs. H.R. and B.P. acknowledge support from the Swedish research council (2014-6019) and the Swedish foundation for strategic research. E.M.H. and T.J.S. were supported by the Netherlands Organization for Scientific Research under the Echo grant number 712.014.007
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The Value of Watching How Materials Grow: A Multimodal Case Study on Halide Perovskites
Material synthesis is one of the most important aspects in humankinds’ endeavor to discover and create new materials for energy applications. One strategy to tailor materials with desired functions in a rational way is by knowing how functions relate to structure, synthetic variables, arrangement of atoms and molecules, and how functions evolve during synthesis. In order to accelerate materials synthesis, discovery, and optimization by 10 times it is the right time now to integrate computational tools, synthesis, and characterization. One particular barrier to realizing this concept is the understanding of when and how phases form in real time during synthesis, which is challenging to asses by existing theoretical frameworks. In addition, transient or metastable phases with positive free energy above the lowest-free energy ground state can be revealed by such real time (in situ) measurements. Metastable materials are ubiquitous in condensed matter and can show superior properties compared to their equilibrium form. This essay discusses the value of emerging multimodal in situ characterizations exemplified on hybrid halide perovskites. Finally, the ways in which the implementation of in situ measurements can advance the materials science synthesis field as well as their role to enable close-loop feedback control and autonomous synthesis are discussed
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Understanding macroscale functionality of metal halide perovskites in terms of nanoscale heterogeneities
Hybrid metal halide perovskites have shown an unprecedented rise as semiconductor building blocks for solar energy conversion and light-emitting applications. Currently, the field moves empirically towards more and more complex chemical compositions, including mixed halide quadruple cation compounds that allow optical properties to be tuned and show promise for better stability. Despite tremendous progress in the field, there is a need for better understanding of mechanisms of efficiency loss and instabilities to facilitate rational optimization of composition. Starting from the device level and then diving into nanoscale properties, we highlight how structural and compositional heterogeneities affect macroscopic optoelectronic characteristics. Furthermore, we provide an overview of some of the advanced spectroscopy and imaging methods that are used to probe disorder and non-uniformities. A unique feature of hybrid halide perovskite compounds is the propensity for these heterogeneities to evolve in space and time under relatively mild illumination and applied electric fields, such as those found within active devices. This introduces an additional challenge for characterization and calls for application of complimentary probes that can aid in correlating the properties of local disorder with macroscopic function, with the ultimate goal of rationally tailoring synthesis towards optimal structures and compositions
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Multi stage and illumination dependent segregation in MAPb(I,Br)3
An unsolved problem of mixed halide perovskites is the light induced compositional instability. Under illumination microscopic clusters with a higher iodide content form which act as efficient recombination centers reducing device performance. In photoluminescence measurements this leads to the development of a secondary peak at low energies that increases in intensity and shifts towards lower energies. Different theories for about the origin have been developed but the underlying key mechanisms are still under debate. In the presented study the photoluminescence evolution of MAPb(I1.5Br1.5) perovskites with varying microstructure is investigated at various excitation densities and temperatures. We find a more evolved segregation mechanism with an intermediate stage between the commonly reported mixed phase and the appearance of the I-rich clusters (Br content < 50%). In this intermediate stage perovskite domains with nearly pure iodide content form (Br content < 25%). Using low excitation densities, the interplay between the I-rich domains and the I-rich clusters leads to a blue shift of the conjunct I-rich luminescence peak. At high excitation densities the I-rich domains and the I-rich clusters are clearly distinguishable, due to a stronger PL response of the I-rich domains. With continuous illumination more I-rich cluster form acting as carrier traps and recombination centers. Due to this, the influence of the few I-rich domains on the PL signature decreases leaving only the commonly reported red shift of the I-rich clusters at later stages of the segregation. The formation of the I-rich domains is fully reversible in the dark and occurs also at elevated temperatures. Measurements on sample with varying grain size further indicate an enhanced formation of those I-rich domains on samples with high grain boundary density possibly by a faster halide mobility along them
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Flash Formation of I-Rich Clusters during Multistage Halide Segregation Studied in MAPbI1.5Br1.5
Wide band gap mixed halide perovskites such as MAPb(I1-xBrx)3 sparked great research interest because of their outstanding optoelectronic properties, ease of fabrication, and band gap tunability. Their application thus far is however limited by light-induced halide segregation in which microscopic clusters with a high iodide content are formed and act as recombination centers. The key mechanism(s) underlying this halide segregation process are still debated. Here, we present a study on the photoluminescence evolution in MAPb(I1.5Br1.5) perovskites with varying microstructures under constant illumination at room temperature and at elevated temperature. Our findings reveal a more complicated picture of the segregation mechanism occurring in three stages instead of two as commonly reported. The process starts with a flash formation of I-rich domains. Following is a rapid blue shift before the gradual and typically observed red shift occurs. The evolution of the three stages is fully reversible in the dark and is also present at elevated temperatures (50 °C). We explain the existence of multiple stages during light-induced halide segregation by natural compositional fluctuations of the halides and the formation of halide clusters with a dynamically changing distribution in I-Br content. The variation in the I-Br ratio depends on the grain size and film heterogeneity. These findings add further details in the quest of unraveling the underlying segregation mechanism(s), which need to be identified to stabilize halides in wide band gap perovskites
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Impact of processing conditions on the film formation of lead-free halide double perovskite Cs2AgBiBr6
Lead-free halide double perovskites with enhanced stability have gained attention as a promising environmentally friendly alternative to lead-based halide perovskites. Amongst different halide double perovskites, Cs2AgBiBr6 has shown attractive optoelectronic properties and stability, making it a promising candidate for stable high-efficiency optoelectronic devices. Motivated by a data mining effort, we present here the effects of different processing strategies on the microstructure and thin-film formation dynamics of Cs2AgBiBr6. We apply some of the most successfully used solvent engineering approaches from the halide perovskite research to halide double perovskites, namely antisolvent- and additive-assisted synthesis. Using in situ spectroscopy and diffraction, the film formation of Cs2AgBiBr6 is investigated during spin coating, and the subsequent post-deposition thermal annealing. Dropping antisolvents during spin coating induces immediate supersaturation and crystallization of the wet film, whereas the time of dropping the antisolvent has implications on the film formation dynamics and the final microstructure. For additive (HBr)-assisted synthesis, we show how the addition of HBr affects colloid formation in solution and thus influences the crystallization pathway during thin-film processing. Finally, HBr additive simplifies synthesis in that it doesn't require solution and substrate preheating to obtain pinhole-free films even with higher thickness
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Synthetic approaches for thin-film halide double perovskites
Inspired by the fascinating class of hybrid organic-inorganic halide perovskite materials, halide double perovskites have emerged as non-toxic Pb-free contenders for application as active layers in optoelectronic devices. Heterovalent substitution of Pb2+ by non-toxic metal cations yields the double-perovskite structure, which allows for compositional flexibility. In fact, the compositional space is large, given that multiple cations and halides can be combined, resulting in >106 perovskite combinations. A starkly increasing number of stable halide double-perovskite compositions are theoretically predicted. The synthesis, however, lags behind, and many double perovskites are primarily synthesized as powder samples instead of thin films. The latter, however, are needed for thin-film devices such as solar cells, light-emitting devices, and thin-film transistors. Comparing the synthetic approaches successfully applied to hybrid perovskites to methods used for the fabrication of double perovskites, the latter are clearly in their very infancy. The question is whether solution engineering and compositional modification strategies can be exploited to match the exceptional optoelectronic properties of hybrid perovskites. This review is motivated by a text mining effort that illustrates not only the prevalence of powder over thin-film synthesis but also the discrepancy between the number of compositions experimentally realized and studied and the many predicted compositions. Here we summarize the synthesis aspects of halide double perovskites, and in particular of thin films, including deposition techniques and synthetic modifications to alter film properties
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Synthetic approaches for thin-film halide double perovskites
Inspired by the fascinating class of hybrid organic-inorganic halide perovskite materials, halide double perovskites have emerged as non-toxic Pb-free contenders for application as active layers in optoelectronic devices. Heterovalent substitution of Pb2+ by non-toxic metal cations yields the double-perovskite structure, which allows for compositional flexibility. In fact, the compositional space is large, given that multiple cations and halides can be combined, resulting in >106 perovskite combinations. A starkly increasing number of stable halide double-perovskite compositions are theoretically predicted. The synthesis, however, lags behind, and many double perovskites are primarily synthesized as powder samples instead of thin films. The latter, however, are needed for thin-film devices such as solar cells, light-emitting devices, and thin-film transistors. Comparing the synthetic approaches successfully applied to hybrid perovskites to methods used for the fabrication of double perovskites, the latter are clearly in their very infancy. The question is whether solution engineering and compositional modification strategies can be exploited to match the exceptional optoelectronic properties of hybrid perovskites. This review is motivated by a text mining effort that illustrates not only the prevalence of powder over thin-film synthesis but also the discrepancy between the number of compositions experimentally realized and studied and the many predicted compositions. Here we summarize the synthesis aspects of halide double perovskites, and in particular of thin films, including deposition techniques and synthetic modifications to alter film properties
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Band tailing and deep defect states in CH3NH3Pb(I1-xBrx)3 perovskites as revealed by sub-bandgap photocurrent
Organometal halide perovskite semiconductors have emerged as promising candidates for optoelectronic applications because of the outstanding charge carrier transport properties, achieved with low-temperature synthesis. Here, we present highly sensitive sub-bandgap external quantum efficiency (EQE) measurements of Au/spiro-OMeTAD/CH3NH3Pb(I1-xBrx)3/TiO2/FTO/glass photovoltaic devices. The room-temperature spectra show exponential band tails with a sharp onset characterized by low Urbach energies (Eu) over the full halide composition space. The Urbach energies are 15-23 meV, lower than those for most semiconductors with similar bandgaps (especially with Eg > 1.9 eV). Intentional aging of CH3NH3Pb(I1-xBrx)3 for up to 2300 h, reveals no change in Eu, despite the appearance of the PbI2 phase due to decomposition, and confirms a high degree of crystal ordering. Moreover, sub-bandgap EQE measurements reveal an extended band of sub-bandgap electronic states that can be fit with one or two point defects for pure CH3NH3PbI3 or mixed CH3NH3Pb(I1-xBrx)3 compositions, respectively. The study provides experimental evidence of defect states close to the midgap that could impact photocarrier recombination and energy conversion efficiency in higher bandgap CH3NH3Pb(I1-xBrx)3 alloys