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.
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.
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.
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.
Abstract
Mixed halide perovskites can provide optimal bandgaps for tandem solar cells which are key to improved cost-efficiencies, but can still suffer from detrimental illumination-induced phase ...segregation. Here we employ optical-pump terahertz-probe spectroscopy to investigate the impact of halide segregation on the charge-carrier dynamics and transport properties of mixed halide perovskite films. We reveal that, surprisingly, halide segregation results in negligible impact to the THz charge-carrier mobilities, and that charge carriers within the I-rich phase are not strongly localised. We further demonstrate enhanced lattice anharmonicity in the segregated I-rich domains, which is likely to support ionic migration. These phonon anharmonicity effects also serve as evidence of a remarkably fast, picosecond charge funnelling into the narrow-bandgap I-rich domains. Our analysis demonstrates how minimal structural transformations during phase segregation have a dramatic effect on the charge-carrier dynamics as a result of charge funnelling. We suggest that because such enhanced recombination is radiative, performance losses may be mitigated by deployment of careful light management strategies in solar cells.
We study the nature of photoexcited charge carriers in CsPbBr_{3} nanocrystal thin films by ultrafast optical pump-THz probe spectroscopy. We observe a deviation from a pure Drude dispersion of the ...THz dielectric response that is ascribed to the polaronic nature of carriers; a transient blueshift of observed phonon frequencies is indicative of the coupling between photogenerated charges and stretching-bending modes of the deformed inorganic sublattice, as confirmed by DFT calculations.
The addition of large hydrophobic cations to lead halide perovskites has significantly enhanced the environmental stability of photovoltaic cells based on these materials. However, the associated ...formation of two-dimensional structures inside the material can lead to dielectric confinement, higher exciton binding energies, wider bandgaps and limited charge-carrier mobilities. Here we show that such effects are not detrimental to the charge transport for carefully processed films comprising a self-assembled thin layer of quasi-two-dimensional (2D) perovskite interfaced with a 3D MAPbI3 perovskite layer. We apply a combination of time-resolved photoluminescence and photoconductivity spectroscopy to reveal the charge-carrier recombination and transport through the film profile, when either the quasi-2D or the 3D layers are selectively excited. Through modeling of the recorded dynamics, we demonstrate that while the charge-carrier mobility is lower within the quasi-2D region, charge-carrier diffusion to the 3D phase leads to a rapid recovery in photoconductivity even when the quasi-2D region is initially photoexcited. In addition, the blue-shifted emission originating from quasi-2D regions overlaps significantly with the absorption spectrum of the 3D perovskite, allowing for highly effective “heterogeneous photon recycling”. We show that this combination fully compensates for the adverse effects of electronic confinement, yielding quasi-2D perovskites with highly efficient charge transporting properties.
With power conversion efficiencies of perovskite-on-silicon and all-perovskite tandem solar cells increasing at rapid pace, wide bandgap (>1.7 eV) metal-halide perovskites (MHPs) are becoming a major ...focus of academic and industrial photovoltaic research. Compared to their lower bandgap (≤1.6 eV) counterparts, these types of perovskites suffer from higher levels of non-radiative losses in both the bulk material and in device configurations, constraining their efficiencies far below their thermodynamic potential. In this work, we investigate the energy losses in methylammonium (MA) free high-Br-content wide bandgap perovskites by using a combination of THz spectroscopy, steady-state and time-resolved photoluminescence, coupled with drift-diffusion simulations. The investigation of this system allows us to study charge-carrier recombination in these materials and devices in the absence of halide segregation due to the photostabilty of formamidinium-cesium based lead halide perovskites. We find that these perovskites are characterised by large non-radiative recombination losses in the bulk material and that the interfaces with transport layers in solar cell devices strongly limit their open-circuit voltage. In particular, we discover that the interface with the hole transport layer performs particularly poorly, in contrast to 1.6 eV bandgap MHPs which are generally limited by the interface with the electron-transport layer. To overcome these losses, we incorporate and investigate the recombination mechanisms present with perovskites treated with the ionic additive 1-butyl-1-methylpipiderinium tetrafluoroborate. We find that this additive not only improves the radiative efficiency of the bulk perovskite, but also reduces the non-radiative recombination at both the hole and electron transport layer interfaces of full photovoltaic devices. In addition to unravelling the beneficial effect of this specific treatment, we further optimise our solar cells by introducing an additional LiF interface treatment at the electron transport layer interface. Together these treatments enable MA-free 1.79 eV bandgap perovskite solar cells with open-circuit voltages of 1.22 V and power conversion efficiencies approaching 17%, which is among the highest reported for this material system.
We identify the limiting factors of wide bandgap metal halide perovskite solar cells. To overcome these losses, we developed an efficient optimisation strategy and outline the necessary steps for the continued development of these perovskites.
A large number of graphene molecules, or large polycyclic aromatic hydrocarbons (PAHs), have been synthesized and display various optoelectronic properties. Nevertheless, their potential for ...application in photonics has remained largely unexplored. Herein, we describe the synthesis of a highly luminescent and stable graphene molecule, namely a substituted dibenzohi,stovalene (DBO 1), with zigzag edges and elucidate its promising optical‐gain properties by means of ultrafast transient absorption spectroscopy. Upon incorporation of DBO into an inert polystyrene matrix, amplified stimulated emission can be observed with a relatively low power threshold (ca. 60 μJ cm−2), thus highlighting its high potential for lasing applications.
Graphene molecules as nanoscale and structurally precise fragments of graphene have recently emerged as promising optoelectronic materials. A novel, highly luminescent, and stable graphene molecule based on dibenzohi,stovalene features remarkable optical‐gain properties, thus holding great potential for applications in laser devices.
Metal halide perovskite (MHP) semiconductors have driven a revolution in optoelectronic technologies over the last decade, in particular for high‐efficiency photovoltaic applications. Low‐dimensional ...MHPs presenting electronic confinement have promising additional prospects in light emission and quantum technologies. However, the optimisation of such applications requires a comprehensive understanding of the nature of charge carriers and their transport mechanisms. This study employs a combination of ultrafast optical and terahertz spectroscopy to investigate phonon energies, charge‐carrier mobilities, and exciton formation in 2D (PEA)2PbI4 and (BA)2PbI4 (where PEA is phenylethylammonium and BA is butylammonium). Temperature‐dependent measurements of free charge‐carrier mobilities reveal band transport in these strongly confined semiconductors, with surprisingly high in‐plane mobilities. Enhanced charge‐phonon coupling is shown to reduce charge‐carrier mobilities in (BA)2PbI4 with respect to (PEA)2PbI4. Exciton and free charge‐carrier dynamics are disentangled by simultaneous monitoring of transient absorption and THz photoconductivity. A sustained free charge‐carrier population is observed, surpassing the Saha equation predictions even at low temperature. These findings provide new insights into the temperature‐dependent interplay of exciton and free‐carrier populations in 2D MHPs. Furthermore, such sustained free charge‐carrier population and high mobilities demonstrate the potential of these semiconductors for applications such as solar cells, transistors, and electrically driven light sources.
Temperature‐dependent charge‐carrier mobilities and exciton formation dynamics in 2D Ruddlesden‐Popper perovskite semiconductors are recorded by femtosecond optical and THz spectroscopy. The results reveal efficient band transport of free charge carriers, greatly surpassing the theoretical expectations for these materials in spite of strong quantum confinement.
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