Hybrid organic-inorganic semiconductors feature complex lattice dynamics due to the ionic character of the crystal and the softness arising from non-covalent bonds between molecular moieties and the ...inorganic network. Here we establish that such dynamic structural complexity in a prototypical two-dimensional lead iodide perovskite gives rise to the coexistence of diverse excitonic resonances, each with a distinct degree of polaronic character. By means of high-resolution resonant impulsive stimulated Raman spectroscopy, we identify vibrational wavepacket dynamics that evolve along different configurational coordinates for distinct excitons and photocarriers. Employing density functional theory calculations, we assign the observed coherent vibrational modes to various low-frequency (≲50 cm
) optical phonons involving motion in the lead iodide layers. We thus conclude that different excitons induce specific lattice reorganizations, which are signatures of polaronic binding. This insight into the energetic/configurational landscape involving globally neutral primary photoexcitations may be relevant to a broader class of emerging hybrid semiconductor materials.
Metal‐halide perovskites present exceptional optoelectronic properties such as large light absorption coefficients, long free charge carrier diffusion lengths with ambipolar character. They are ...apparently protected by what is often described as a “defect tolerance” which has allowed to achieve, relatively quickly, highly performing devices. Nevertheless, there also exists a “defect intolerance” when it is dealt with stability. Further rationalization of the passivation strategies, especially for complex chemical systems, will be beneficial to achieve a full materials library which can be the platform for an efficient and reliable technology.
Defect tolerance of metal‐halide perovskites is a commonly evoked concept to explain the development of high efficiency solar cells upon solution processing. However, moving the attention to solar cell stability, these materials seem to be defect intolerant. Further material engineering is needed to obtain a 100% defect tolerant materials platform.
Metal halide perovskites have become a popular material system for fabricating photovoltaics and various optoelectronic devices. However, long-term reliability must be assured. Instabilities are ...manifested as light-induced ion migration and segregation, which can lead to material degradation. Discordant reports have shown a beneficial role of ion migration under illumination, leading to defect healing. By combining ab initio simulations with photoluminescence measurements under controlled conditions, we demonstrate that photo-instabilities are related to light-induced formation and annihilation of defects acting as carrier trap states. We show that these phenomena coexist and compete. In particular, long-living carrier traps related to halide defects trigger photoinduced material transformations, driving both processes. Defect formation can be controlled by blocking under-coordinated surface sites, which act as a defect reservoir. By use of a passivation strategy we are thus able to stabilize the perovskite layer, leading to improved optoelectronic material quality and enhanced photostability in solar cells.The photo-instability of perovskite solar cells is investigated and controlled by the use of a passivation strategy.
A major efficiency limit for solution-processed perovskite optoelectronic devices, for example light-emitting diodes, is trap-mediated non-radiative losses. Defect passivation using organic molecules ...has been identified as an attractive approach to tackle this issue. However, implementation of this approach has been hindered by a lack of deep understanding of how the molecular structures influence the effectiveness of passivation. We show that the so far largely ignored hydrogen bonds play a critical role in affecting the passivation. By weakening the hydrogen bonding between the passivating functional moieties and the organic cation featuring in the perovskite, we significantly enhance the interaction with defect sites and minimize non-radiative recombination losses. Consequently, we achieve exceptionally high-performance near-infrared perovskite light-emitting diodes with a record external quantum efficiency of 21.6%. In addition, our passivated perovskite light-emitting diodes maintain a high external quantum efficiency of 20.1% and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm−2, making them more attractive than the most efficient organic and quantum-dot light-emitting diodes at high excitations.Improved understanding of passivation leads to near-infrared perovskite light-emitting diodes with 21.6% external quantum efficiency.
Long-term device stability is one of the most critical issues that impede perovskite solar cell commercialization. Here we show that a thin layer of a functional hygroscopic polymer, poly(ethylene ...oxide), PEO, on top of the perovskite thin film, can make perovskite-based solar cells highly stable during operation and in a humid atmosphere. We prove that PEO chemically interacts with lead ions on the perovskite surface, and thus passivates undercoordinated defect sites. Importantly, defect healing by PEO not only results in an improvement of the photo-voltage but also makes the perovskite thin film stable. We demonstrate that the hygroscopic PEO thin film can prevent water inclusion into the perovskite film by screening water molecules, thus having a multi-functional role. Overall, such interface engineering leads to highly durable perovskite solar cells, which, in the presence of PEO passivation, retained more than 95% of their initial power conversion efficiency over 15 h illumination, under load, in ambient atmosphere without encapsulation. Our findings experimentally reveal the role of interface engineering in mastering the instability of perovskite materials and propose a general approach for improving the reliability of perovskite-based optoelectronic devices.
We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized ...colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.
The presence of various types of chemical interactions in metal‐halide perovskite semiconductors gives them a characteristic “soft” fluctuating structure, prone to a wide set of defects. ...Understanding of the nature of defects and their photochemistry is summarized, which leverages the cooperative action of density functional theory investigations and accurate experimental design. This knowledge is used to describe how defect activity determines the macroscopic properties of the material and related devices. Finally, a discussion of the open questions provides a path towards achieving an educated prediction of device operation, necessary to engineer reliable devices.
The photochemistry of halide‐related defects affects the optoelectronic properties of lead–halide perovskite semiconductors and their reactivity to external stimuli such as light and environmental molecules.
We report about the relationship between the morphology and luminescence properties of methylammonium lead trihalide perovskite thin films. By tuning the average crystallite dimension in the film ...from tens of nanometers to a few micrometers, we are able to tune the optical band gap of the material along with its photoluminescence lifetime. We demonstrate that larger crystallites present smaller band gap and longer lifetime, which correlates to a smaller radiative bimolecular recombination coefficient. We also show that they present a higher optical gain, becoming preferred candidates for the realization of CW lasing devices.
Metal halide perovskites (MHPs) constitute a rich library of materials with huge potential for disruptive optoelectronic technologies. Their main strength comes from the possibility of easily tuning ...their bandgap to integrate them in devices with different functionalities — in principle. In reality, this cannot be achieved yet. In fact, whereas defect tolerance can be claimed for MHPs with a bandgap of about 1.6 eV, the model system that is the object of intense investigations, MHPs with lower and higher bandgaps are far from being defect-tolerant. These materials show various forms of instabilities that are mainly driven by strong defect activity. Here we critically assess the most recent advances in elucidating the physical and chemical activity of defects in both high-bandgap and low-bandgap MHPs, while correlating it to performance and stability losses, especially for solar cells, the driving application for these materials. We also provide an overview of the strategies so far implemented to eventually overcome the remaining materials-based and device-based challenges.Metal halide perovskites (MHPs) have substantial potential for solar cell applications. This Review critically assesses recent advances in elucidating the physical and chemical activity of defects in both high-bandgap and low-bandgap MHPs, and correlates it to performance and stability losses.
Metal-halide perovskites are outstanding materials for photovoltaics. Their long carrier lifetimes and diffusion lengths favor efficient charge collection, leading to efficiencies competing with ...established photovoltaics. These observations suggest an apparently low density of traps in the prototype methylammonium lead iodide (MAPbI 3 ) contrary to the expected high defect density of a low-temperature, solution-processed material. Combining first-principles calculations and spectroscopic measurements we identify less abundant iodine defects as the source of photochemically active deep electron and hole traps in MAPbI 3 . The peculiar iodine redox chemistry leads, however, to kinetic deactivation of filled electron traps, leaving only short-living hole traps as potentially harmful defects. Under mild oxidizing conditions the amphoteric hole traps can be converted into kinetically inactive electron traps, providing a rationale for the defect tolerance of metal-halide perovskites. Bromine and chlorine doping of MAPbI 3 also inactivate hole traps, possibly explaining the superior optoelectronic properties of mixed-halide perovskites.
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