Organic solvent free PbI₂ recycling from perovskite solar cells using hot water

Perovskite solar cells represent an emerging and highly promising renewable energy technology. However, the most efficient perovskite solar cells critically depend on the use of lead. This represents a possible environmental concern potentially limiting the technologiesâEurotm commercialization. Here, we demonstrate a facile recycling process for PbI2, the most common lead-based precursor in perovskite absorber material. The process uses only hot water to effectively extract lead from synthetic precursor mixes, plastic- and glass-based perovskites (92.6 âEuro" 10

Understanding the degradation of methylenediammonium and its role in phase-stabilizing formamidinium lead triiodide

Formamidinium lead triiodide (FAPbI3) is the leading candidate for single-junction metal–halide perovskite photovoltaics, despite the metastability of this phase. To enhance its ambient-phase stability and produce world-record photovoltaic efficiencies, methylenediammonium dichloride (MDACl2) has been used as an additive in FAPbI3. MDA2+ has been reported as incorporated into the perovskite lattice alongside Cl–. However, the precise function and role of MDA2+ remain uncertain. Here, we grow FAPbI3 single crystals from a solution containing MDACl2 (FAPbI3-M). We demonstrate that FAPbI3-M crystals are stable against transformation to the photoinactive δ-phase for more than one year under ambient conditions. Critically, we reveal that MDA2+ is not the direct cause of the enhanced material stability. Instead, MDA2+ degrades rapidly to produce ammonium and methaniminium, which subsequently oligomerizes to yield hexamethylenetetramine (HMTA). FAPbI3 crystals grown from a solution containing HMTA (FAPbI3-H) replicate the enhanced α-phase stability of FAPbI3-M. However, we further determine that HMTA is unstable in the perovskite precursor solution, where reaction with FA+ is possible, leading instead to the formation of tetrahydrotriazinium (THTZ-H+). By a combination of liquid- and solid-state NMR techniques, we show that THTZ-H+ is selectively incorporated into the bulk of both FAPbI3-M and FAPbI3-H at ∼0.5 mol % and infer that this addition is responsible for the improved α-phase stability

Excellent long-range charge-carrier mobility in 2D perovskites

The use of layered, 2D perovskites can improve the stability of metal halide perovskite thin films and devices. However, the charge carrier transport properties in layered perovskites are still not fully understood. Here, the sum of the electron and hole mobilities (Σμ) in thin films of the 2D perovskite PEA2PbI4, through transient electronically contacted nanosecond-to-millisecond photoconductivity measurements, which are sensitive to long-time, long-range (micrometer length scale) transport processes is investigated. After careful analysis, accounting for both early-time recombination and the evolution of the exciton-to-free-carrier population, a long-range mobility of 8.0 +/− 0.6 cm2 (V s)–1, which is ten times greater than the long-range mobility of a comparable 3D material FA0.9Cs0.1PbI3 is determined. These values are compared to ultra-fast transient time-resolved THz photoconductivity measurements, which are sensitive to early-time, shorter-range (tens of nm length scale) mobilities. Mobilities of 8 and 45 cm2 (V s)–1 in the case of the PEA2PbI4 and FA0.9Cs0.1PbI3, respectively, are obtained. This previously unreported concurrence between the long-range and short-range mobility in a 2D material indicates that the polycrystalline thin films already have single-crystal-like qualities. Hence, their fundamental charge carrier transport properties should aid device performance

Exciton formation dynamics and band-like free charge-carrier transport in 2D metal halide perovskite semiconductors

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

Ultra-narrow room-temperature emission from single CsPbBr₃ perovskite quantum dots

Semiconductor quantum dots have long been considered artificial atoms, but despite the overarching analogies in the strong energy-level quantization and the single-photon emission capability, their emission spectrum is far broader than typical atomic emission lines. Here, by using ab-initio molecular dynamics for simulating exciton-surface-phonon interactions in structurally dynamic CsPbBr(3) quantum dots, followed by single quantum dot optical spectroscopy, we demonstrate that emission line-broadening in these quantum dots is primarily governed by the coupling of excitons to low-energy surface phonons. Mild adjustments of the surface chemical composition allow for attaining much smaller emission linewidths of 35−65 meV (vs. initial values of 70–120 meV), which are on par with the best values known for structurally rigid, colloidal II-VI quantum dots (20−60 meV). Ultra-narrow emission at room-temperature is desired for conventional light-emitting devices and paramount for emerging quantum light sources

Ultra-narrow room-temperature emission from single CsPbBr3 perovskite quantum dots

Semiconductor quantum dots have long been considered artificial atoms, but despite the overarching analogies in the strong energy-level quantization and the single-photon emission capability, their emission spectrum is far broader than typical atomic emission lines. Here, by using ab-initio molecular dynamics for simulating exciton-surface-phonon interactions in structurally dynamic CsPbBr3 quantum dots, followed by single quantum dot optical spectroscopy, we demonstrate that emission line-broadening in these quantum dots is primarily governed by the coupling of excitons to low-energy surface phonons. Mild adjustments of the surface chemical composition allow for attaining much smaller emission linewidths of 35−65 meV (vs. initial values of 70–120 meV), which are on par with the best values known for structurally rigid, colloidal II-VI quantum dots (20−60 meV). Ultra-narrow emission at room-temperature is desired for conventional light-emitting devices and paramount for emerging quantum light sources

Long-range charge carrier mobility in metal halide perovskite thin-films and single crystals via transient photo-conductivity

Charge carrier mobility is a fundamental property of semiconductors. The authors of this study demonstrate a novel way to estimate long-range mobilities of perovskite thin-films and single crystals by taking early-time carrier dynamics into account

Hydrogen Bond-Assisted Dual Passivation for Blue Perovskite Light-Emitting Diodes

Althoughsignificantprogresshas been madein the developmentof green,red,and near-infraredperovskitelight-emittingdiodes(PeLEDs),blue PeLEDsexhibitinferiorperformance,owingto variousdefectsand poorcarrierinjectionin solution-processedperovskitefilms.Thus,this studyincorporatesdual-passivationadditivediphenylphosphina-mide(DPPA)into perovskitefilms,and throughdensityfunctionaltheorycalculationsandexperimentalcharacterizations,DPPAhas beenprovento be an effectivepassivator.Itsphosphineoxidegroupcoordinateswith unsaturatedlead ions, passivatingperovskitedefects,whilethe aminogroupformshydrogenbondswith adjacenthalideions, suppressingtheirmigrationand furtherstrengtheningthe passivationeffect.Bluequasi-two-dimensionalPeLEDsbasedon DPPA-modifiedperovskitefilms achievedan externalquantumefficiencyof12.31%with an emissionpeak at 486 nm. Moreover,the deviceoperationallifetimewasextendedby 32% with morestablespectraowingto the decreaseddefectdensityand suppressedion migrationin theperovskitefil