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Recent advances in stabilizing simple FAPbI3 perovskite composition have challenged the use of complex multiple cation/anion compositions for fabrication of highly efficient and stable perovskite solar cells.

We use the free radical polymerization initiator 4,40-azobis(cyanovaleric acid) coordinated to the open metal sites of metal-organic frameworks (MOFs) to give rise to highly uniform MOF/polymer hybrids.We demonstrate this strategy on two robust zirconium MOFs (NU-1000 and MOF- 808), which are the most effective catalysts for degradation of chemical warfare nerve agents. The resulting hybrid materials maintain their hydrolytic catalytic activity and have substantially improved adhesion to polypropylene and activated carbon textile fibers, yielding highly robust MOF/polymer/textile hybrid systems. These composites are suitable for the green production of active protective clothing and filters capable of detoxifying organophosphorus warfare agents., National Science Center (NCN) of Poland 2020/37/N/ST5/01107 UMO-2014/14/E/ST5/00652, Polish NAWA Agency under the Ulam Fellowship program PPN/ULM/2020/1/00218, University of Warwick, MCIN/AEI PID2020-113608RB-I00, UK Research & Innovation (UKRI), Biotechnology and Biological Sciences Research Council (BBSRC) EP/T015063/1, Engineering & Physical Sciences Research Council (EPSRC), European Commission, Birmingham Science City Advanced Materials Project 1 - Advantage West Midlands (AWM) Birmingham Science City Advanced Materials Project 2 - Advantage West Midlands (AWM)

Advanced materials 35(5), 2208061 (2023). doi:10.1002/adma.202208061, Incorporating large organic cations to form 2D and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. However, due to their low electron mobility, aligning the organic sheets to ensure unimpeded charge transport is critical to rival the high performances of pure 3D systems. While additives such as methylammonium chloride (MACl) can enable this preferential orientation, so far, no complete description exists explaining how they influence the nucleation process to grow highly aligned crystals. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3-fluorobenzylammonium in quasi-2D perovskite solar cells. Upon assisting the crystallization with MACl, films with a degree of preferential orientation of 94%, capable of withstanding moisture levels of 97% relative humidity for 10 h without significant changes in the crystal structure are achieved. Finally, by combining macroscopic, microscopic, and spectroscopic studies, the nucleation process leading to highly oriented perovskite films is elucidated. Understanding this mechanism will aid in the rational design of future additives to achieve more defect tolerant and stable perovskite optoelectronics., Published by Wiley-VCH, Weinheim

CsPbI3 is a promising material for optoelectronics owing to its thermal robustness and favorable bandgap. However, its fabrication is challenging because its photoactive phase is thermodynamically unstable at room temperature. Adding dimethylammonium (DMA) alleviates this instability and is currently understood to result in the formation of DMA(x)Cs(1-x)PbI(3) perovskite solid solutions. Here, we use NMR of the Cs-133 and C-13 local structural probes to show that these solid solutions are not thermodynamically stable, and their synthesis under thermodynamic control leads to a segregated mixture of yellow one-dimensional DMAPbI(3) phase and delta-CsPbI3. We show that mixed-cation DMA(x)Cs(1-x)PbI(3) perovskite phases only form when they are kinetically trapped by rapid antisolvent-induced crystallization. We explore the energetics of DMA incorporation into CsPbI3 using first-principles calculations and molecular dynamics simulations and find that this process is energetically unfavorable. Our results provide a complete atomic-level picture of the mechanism of DMA-induced stabilization of the black perovskite phase of CsPbI3 and shed new light on this deceptively simple material.

Understanding defects is of paramount importance for the development of stable halide perovskite solar cells (PSCs). However, isolating their distinctive effects on device efficiency and stability is currently a challenge. We report that adding the organic molecule 3-phosphonopropionic acid (H3pp) to the halide perovskite results in unchanged overall optoelectronic performance while having a tremendous effect on device stability. We obtained PSCs with ∼21% efficiency that retain ∼100% of the initial efficiency after 1,000 h at the maximum power point under simulated AM1.5G illumination. The strong interaction between the perovskite and the H3pp molecule through two types of hydrogen bonds (HI and OH) leads to shallow point defect passivation that has a significant effect on device stability but not on the non-radiative recombination and device efficiency. We expect that our work will have important implications for the current understanding and advancement of operational PSCs., We thank the Spanish MINECO through the Severo Ochoa Centers of Excellence Program under grant no. SEV-2017-0706 for the postdoctoral contract to H.X. We thank the King Abdulaziz City for Science and Technology (KACST) for the financial support to M.G. and S.M.Z. A.H. is thankful for the financial support from the European Union H2020, ESPResSo project grant agreement 764047, and Swiss National Science Foundation project IZLCZ2_170177. Z.W. and S.F. are thankful for the “China Scholarship Council” fellowship (CSC). H.-S.K., M.G., and S.M.Z. are thankful for the financial support from the GRAPHENE Flagship Core 2 project supported by the European Commission H2020 Programme under contract 785219. P.T. and J.A. acknowledge funding from Generalitat de Catalunya 2017 SGR 327 and the Spanish MINECO project ANAPHASE (ENE2017-85087-C3). D.J.K. and L.E. acknowledge support from the Swiss National Science Foundation grant no. 200021_160112. S.T. acknowledges funding from the Computational Sciences for Energy Research tenure track programme of Shell, NWO, and FOM (project no. 15CST04-2), the Netherlands. S.D.S. and M.A. acknowledge funding from the Marie Skłodowska-Curie actions (grant agreement no. 841386) under the European Union’s Horizon 2020 research and innovation programme. S.D.S acknowledges support from the Royal Society and Tata Group (UF150033) and EPSRC (EP/R023980/1). X.S. and F.F. acknowledge the funding from the Swiss Federal Office of Energy (SFOE)-BFE (project no. SI/501805-01). K.G. appreciates support from the Polish Ministry of Science and Higher Education within the Mobilnosc Plus program (grant no. 1603/MOB/V/2017/0). K.J.T. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 804349 (ERC StG Cuhl) and RyC fellowship no. RYC-2017-22330. We give thanks to the Spanish State Research Agency for the grant Self-Power (PID2019-104272RB-C54 / AEI / 10.13039/501100011033) and the OrgEnergy Excelence Network (CTQ2016-81911-REDT), and to the Agència de Gestiód'Ajuts Universitaris i de Recerca (AGAUR) for the support to the consolidated Catalonia research group 2017 SGR 329 and the Xarxa d’R+D+I Energy for Society (XRE4S). Part of this work is under Materials Science Ph.D. Degree for A.M. and P.T. and the Chemistry Ph.D. programme for C.P. of the Universitat Autonoma de Barcelona (UAB, Spain). We thank CONACYT for the scholarship to C.P. We acknowledge Libertad Sole and also the Clean-Room from IMB-CNM for FIB process. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (grant no. SEV-2017-0706) and is funded by the CERCA Programme/Generalitat de Catalunya.

Layered hybrid halide perovskites are known to be more environmentally stable than their 3D analogues. The enhanced stability is particularly relevant for Dion–Jacobson-type layered perovskites due...

All-inorganic double perovskites (elpasolites) are a promising potential alternatives to lead halide perovskites in optoelectronic applications. Although halide mixing is a well-established strateg...

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 leads to substitution of up to 7% of the Bi(III) ions by equal quantities of Sn(II) and Sn(IV). The nature of the substitutional defects was studied by X-ray diffraction, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(II) and Sn(IV) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(II) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(II) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure–property relationships of lead-free vacancy-ordered perovskite structures.

Cesium-lead-bromide (CsPbBr3) is the simplest all inorganic halide perovskite. It serves as a reference material for understanding the exceptional solar cell properties of the organic-inorganic hybrid halide perovskites and is itself discussed as an alternative absorber material. Broadband dielectric spectroscopy has proven to yield an in depth understanding of charge screening mechanisms in the halide solar cell absorbers based on methylammonium and modifications hereof. For a deeper understanding of charge carrier screening, we have investigated CsPbBr(3)across wide temperature (120 K-450 K) and frequency ranges. Besides the two known phase transitions at 403 K and 361 K, the dielectric data show another anomaly around 220 K, which can be interpreted as another phase transition. XRD and EPR studies confirm the presence of this anomaly, but Raman scattering spectra do not show any lattice anomalies in the vicinity of 220 K. This additional anomaly is of first order character (different transition temperatures upon cooling and heating) but hardly influences the lattice dynamics. Our broadband dielectric investigations of CsPbBr(3)display the same microwave limit permittivity as for MAPbX(3)(epsilon(r)approximate to 30, X = Cl, Br, I, MA = CH3NH3+) but do not afford a second permittivity relaxation up to this frequency. Our prior assignment of the second contribution in the methylammonium compounds being due to the relaxation dynamics of the methylammonium ion as a dipole is herewith proven. Nevertheless, CsPbBr(3)shows large charge carrier screening up to very high frequencies which can still play a vital role in charge carrier dynamics and exciton behaviour in this material as well.

Summary Interfacial modification is crucial to fully develop the potential of semiconductor devices, including the revolutionary halide perovskite-based optoelectronics, such as photovoltaics, light-emitting diodes, and photodetectors. The all-inorganic halide perovskites, which are potential long-term stable photovoltaic materials, are suffering from poor interfacial contact with metal oxide charge-selective layer, severely limiting the power conversion efficiency and stability of inorganic perovskite solar cells. Here, we propose an intermediate-phase engineering strategy to improve the inorganic perovskite/metal oxide interface by utilizing volatile salts. The introduction of organic cations (such as methylammonium and formamidinium), which can be doped into the perovskite lattice, leads to the formation of an organic-inorganic hybrid perovskite intermediate phase, promoting a robust interfacial contact through hydrogen bonding. A champion CsPb(I0.75Br0.25)3-based device with a power conversion efficiency of 17.0% and an open-circuit voltage of 1.34 V was realized, implying that a record of over 65% of the Shockley-Queisser efficiency limit is achieved.

Chemical doping of inorganic-organic hybrid perovskites is an effective way of improving the performance and operational stability of perovskite solar cells (PSCs). Here we use 5-ammonium valeric acid iodide (AVAI) to chemically stabilize the structure of α-FAPbI3. Using solid-state MAS NMR, we demonstrate the atomic-level interaction between the molecular modulator and the perovskite lattice and propose a structural model of the stabilized three-dimensional structure, further aided by density functional theory (DFT) calculations. We find that one-step deposition of the perovskite in the presence of AVAI produces highly crystalline films with large, micrometer-sized grains and enhanced charge-carrier lifetimes, as probed by transient absorption spectroscopy. As a result, we achieve greatly enhanced solar cell performance for the optimized AVA-based devices with a maximum power conversion efficiency (PCE) of 18.94%. The devices retain 90% of the initial efficiency after 300 h under continuous white light illumination and maximum-power point-tracking measurement.

Gadolinium(III) complexes have recently been demonstrated to have potential as polarizing agents for high-field dynamic nuclear polarization (DNP) NMR spectroscopy. By tailoring the ligand design to reduce the zero-field splitting (ZFS), we demonstrate a quadratic improvement in DNP through the investigation of a stable, water-soluble, narrow-line Gd(III) complex, [Gd-(tpatcn)], doubling the magic-angle-spinning DNP enhancement of the previous state-of-the-art [Gd(dota)-(H2O)](-) at 9.4 T and 100 K.

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 leads to substitution of up to 7% of the Bi(III) ions by equal quantities of Sn(II) and Sn(IV). The nature of the substitutional defects was studied by X-ray diffraction, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(II) and Sn(IV) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(II) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(II) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure-property relationships of lead-free vacancy-ordered perovskite structures.

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 leads to substitution of up to 7% of the Bi(iii) ions by equal quantities of Sn(ii) and Sn(iv). The nature of the substitutional defects was studied by X-ray diffraction, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(ii) and Sn(iv) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(ii) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(ii) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure–property relationships of lead-free vacancy-ordered perovskite structures., Mixed valence Sn doping of Cs3Bi2Br9 leads to broad visible light absorption.

Hybrid-perovskite-based optoelectronic devices are demonstrating unprecedented growth in performance, and defect passivation approaches are highly promising routes to further improve properties. Here, the effect of the molecular ion BF4 - , introduced via methylammonium tetrafluoroborate (MABF4 ) in a surface treatment for MAPbI3 perovskite, is reported. Optical spectroscopy characterization shows that the introduction of tetrafluoroborate leads to reduced non-radiative charge-carrier recombination with a reduction in first-order recombination rate from 6.5 × 106 to 2.5 × 105 s-1 in BF4 - -treated samples, and a consequent increase in photoluminescence quantum yield by an order of magnitude (from 0.5 to 10.4%). 19 F, 11 B, and 14 N solid-state NMR is used to elucidate the atomic-level mechanism of the BF4 - additive-induced improvements, revealing that the BF4 - acts as a scavenger of excess MAI by forming MAI-MABF4 cocrystals. This shifts the equilibrium of iodide concentration in the perovskite phase, thereby reducing the concentration of interstitial iodide defects that act as deep traps and non-radiative recombination centers. These collective results allow us to elucidate the microscopic mechanism of action of BF4 - .

In this reply, we address the concerns that were raised about our paper on CsPbBr3 single crystals. M. Szafranski criticized the dielectric and DSC data in our original paper claiming that they were a ´ ffected by the experimental artefacts or poor quality of the investigated single crystals, as his DSC and dielectric data did not show any low temperature anomalies in CsPbBr3. We argue in this reply that our main conclusions were not made based on the DSC and dielectric experiments. Here, we emphasize the importance of other experiments like EPR and XRD that were performed to understand if there are any structural transformations of CsPbBr3 at low temperatures. We believe that M. Szafranski did not take ´ into account all the discussion that was presented in our original paper. We hope to clear the doubts in this reply. published

International audience; Metal halide perovskites (MHPs) are promising light harvesting and emitting materials that have enabled solar energy conversion efficiencies of over 25% in solution-processed single-junction cells, and found applications in flexible electronics, detectors and other display technologies. Research on MHPs has achieved significant fundamental and technological advancements over the last decade, in large part due to improvements in characterization approaches to understand these materials. It has become clear that engineering the interfaces between device layers, and within the MHP layer itself, is crucially important to develop stable and efficient optoelectronic devices. Interfaces in MHP-based devices exhibit varying degrees of order, which manifest heterogeneities in compositions, structures and optoelectronic properties. This review assesses the overall prospects for a range of solid-state (ss)NMR spectroscopy techniques to facilitate structure-based understanding of complex interfaces in MHPs and contact layers. The role of ssNMR in elucidating local compositions and structures, intermolecular connectivity, phase transitions, degradation products and molecular passivation at MHP interfaces is discussed. In addition, an overview of different dynamic processes in MHPs probed by ssNMR is provided. Finally, we discuss perspectives on the development of ssNMR spectroscopy for investigating interfaces in MHPs for various optoelectronics.

Solid-state magic-angle spinning NMR spectroscopy is a powerful technique to probe atomic-level microstructure and structural dynamics in metal halide perovskites. It can be used to measure dopant incorporation, phase segregation, halide mixing, decomposition pathways, passivation mechanisms, short-range and long-range dynamics, and other local properties. This Review describes practical aspects of recording solid-state NMR data on halide perovskites and how these afford unique insights into new compositions, dopants and passivation agents. We discuss the applicability, feasibility and limitations of 1H, 13C, 15N, 14N, 133Cs, 87Rb, 39K, 207Pb, 119Sn, 113Cd, 209Bi, 115In, 19F and 2H NMR in typical experimental scenarios. We highlight the pivotal complementary role of solid-state mechanosynthesis, which enables highly sensitive NMR studies by providing large quantities of high-purity materials of arbitrary complexity and of chemical shifts calculated using density functional theory. We examine the broader impact of solid-state NMR on materials research and how its evolution over seven decades has benefitted structural studies of contemporary materials such as halide perovskites. Finally, we summarize some of the open questions in perovskite optoelectronics that could be addressed using solid-state NMR. We, thereby, hope to stimulate wider use of this technique in materials and optoelectronics research. Solid-state NMR is useful to study the local structure, dynamics and dopant speciation in metal halide perovskites. This Perspective describes the practical aspects of the method that make it broadly applicable to optoelectronic materials.

Optoelectronic devices based on lead halide perovskites are processed in facile ways, yet are remarkably efficient. There are extensive research efforts investigating lead-free perovskite and perovskite-related compounds, yet there are challenges to synthesize these materials in forms that can be directly integrated into thin film devices rather than as bulk powders. Here, we report on the colloidal synthesis and characterization of lead-free, antifluorite Cs2ZrX6 (X = Cl, Br) nanocrystals that are readily processed into thin films. We use transmission electron microscopy and powder X-ray diffraction measurements to determine their size and structural properties, and solid-state nuclear magnetic resonance measurements reveal the presence of oleate ligand, together with a disordered distribution of Cs surface sites. Density functional theory calculations reveal the band structure and fundamental band gaps of 5.06 and 3.91 eV for Cs2ZrCl6 and Cs2ZrBr6, respectively, consistent with experimental values. Finally, we demonstrate that the Cs2ZrCl6 and Cs2ZrBr6 nanocrystal thin films exhibit tunable, broad white photoluminescence with quantum yields of 45% for the latter, with respective peaks in the blue and green spectral regions and mixed systems exhibiting properties between them. Our work represents a critical step toward the application of lead-free Cs2ZrX6 nanocrystal thin films into next-generation light-emitting applications.

International audience; Identifying and characterizing systems that generate well-defined states with large electron spin polarization is of high interest for applications in molecular spintronics, high-energy physics, and magnetic resonance spectroscopy. The generation of electron spin polarization on free-radical substituents tethered to pentacene derivatives has recently gained a great deal of interest for its applications in molecular electronics. After photoexcitation of the chromophore, pentacene−radical derivatives can rapidly form spinpolarized triplet excited states through enhanced intersystem crossing. Under the right conditions, the triplet spin polarization, arising from m S-selective intersystem crossing rates, can be transferred to the tethered stable radical. The efficiency of this spin polarization transfer depends on many factors: local magnetic and electric fields, excitedstate energetics, molecular geometry, and spin-spin coupling. Here, we present transient electron paramagnetic resonance (EPR) measurements on three pentacene derivatives tethered to Finland trityl, BDPA, or TEMPO radicals to explore the influence of the nature of the radical on the spin polarization transfer. We observe efficient polarization transfer between the pentacene excited triplet and the trityl radical but do not observe the same for the BDPA and TEMPO derivatives. The polarization transfer behavior in the pentacene−trityl system is also investigated in different glassy matrices and is found to depend markedly on the solvent used. The EPR results are rationalized with the help of femtosecond and nanosecond transient absorption measurements, yielding complementary information on the excited-state dynamics of the three pentacene derivatives. Notably, we observe a 2 orders of magnitude difference in the time scale of triplet formation between the pentacene−trityl system and the pentacene systems tethered with the BDPA and TEMPO radicals.

The development of magic-angle spinning dynamic nuclear polarization (MAS DNP) has allowed atomic-level characterization of materials for which conventional solid-state NMR is impractical due to the lack of sensitivity. The rapid progress of MAS DNP has been largely enabled through the understanding of rational design concepts for more efficient polarizing agents (PAs). Here, we identify a new design principle which has so far been overlooked. We find that the local geometry around the unpaired electron can change the DNP enhancement by an order of magnitude for two otherwise identical conformers. We present a set of 13 new stable mono- and dinitroxide PAs for MAS DNP NMR where this principle is demonstrated. The radicals are divided into two groups of isomers, named open (O-) and closed (C-), based on the ring conformations in the vicinity of the N-O bond. In all cases, the open conformers exhibit dramatically improved DNP performance as compared to the closed counterparts. In particular, a new urea-based biradical named HydrOPol and a mononitroxide O-MbPyTol yield enhancements of 330 ± 60 and 119 ± 25, respectively, at 9.4 T and 100 K, which are the highest enhancements reported so far in the aqueous solvents used here. We find that while the conformational changes do not significantly affect electron spin-spin distances, they do affect the distribution of the exchange couplings in these biradicals. Electron spin echo envelope modulation (ESEEM) experiments suggest that the improved performance of the open conformers is correlated with higher solvent accessibility.

Lead halide perovskites belong to a broad class of compounds with appealing optoelectronic and photovoltaic properties. Doping with transition metal ions such as Mn2+ and Co2+ has recently been reported to substantially enhance luminescence and stability of these materials. However, so far atomic-level evidence for incorporation of the dopants into perovskite phases has been missing. Here, we introduce a general and straightforward method for confirming the substitutional doping of bulk perovskite phases with paramagnetic dopants. Using 133Cs and 1H solid-state MAS NMR relaxation measurements we provide for the first time direct evidence that, consistent with current understanding, Mn2+ is incorporated into the perovskite lattice of CsPbCl3 and CsPbBr3 and does not form clusters. We also show that, contrary to current conviction, Co2+ is not incorporated into the perovskite lattice of MAPbI3.

Summary All-inorganic perovskite films hold promise for improving the stability of perovskite solar cells (PSCs). However, the 3D α phase of narrow-bandgap inorganic perovskites is thermodynamically unstable at room temperature, limiting the development of high-performance inorganic PSCs. Here, we show that europium doping of CsPbI2Br stabilizes the α phase of this inorganic perovskite at room temperature. We rationalize it by using solid-state nuclear magnetic resonance and high-angle annular dark-field scanning transmission electron microscopy, which show that europium is incorporated into the perovskite lattice. We demonstrate a maximum power-conversion efficiency of 13.71% for an inorganic PSC with the CsPb0.95Eu0.05I2Br perovskite and a stable power output of 13.34%. Using electroluminescence we show that incorporation of europium reduces non-radiative recombination, resulting in high open-circuit voltage of 1.27 V. The devices retain 93% of the initial efficiency after 370 hr under 100 mW cm−2 continuous white light illumination under maximum-power point-tracking measurement.

Submitted version after revision; International audience; Organic−inorganic tin(II) halide perovskites have emerged as promising alternatives to lead halide perovskites in optoelectronic applications. While they suffer from considerably poorer performance and stability in comparison to their lead analogues, their performance improvements have so far largely been driven by trial and error efforts due to a critical lack of methods to probe their atomic-level microstructure. Here, we identify the challenges and devise a 119 Sn solid-state NMR protocol for the determination of the local structure of mixed-cation and mixed-halide tin(II) halide perovskites as well as their degradation products and related phases. We establish that the longitudinal relaxation of 119 Sn can span 6 orders of magnitude in this class of compounds, which makes judicious choice of experimental NMR parameters essential for the reliable detection of various phases. We show that Cl/Br and I/Br mixed-halide perovskites form solid alloys in any ratio, while only limited mixing is possible for I/Cl compositions. We elucidate the degradation pathways of Cs-, MA-, and FA-based tin(II) halides and show that degradation leads to highly disordered, qualitatively similar products, regardless of the A-site cation and halide. We detect the presence of metallic tin among the degradation products, which we suggest could contribute to the previously reported high conductivities in tin(II) halide perovskites. 119 Sn NMR chemical shifts are a sensitive probe of the halide coordination environment as well as of the A-site cation composition. Finally, we use variable-temperature multifield relaxation measurements to quantify ion dynamics in MASnBr 3 and establish activation energies for motion and show that this motion leads to spontaneous halide homogenization at room temperature whenever two different pure-halide perovskites are put in physical contact. ■ INTRODUCTION Organic−inorganic halide perovskites (OIHPs) have emerged as a new class of materials for solar cells and light emission applications owing to the ease of solution processing, immunity to most defects, and long charge carrier lifetimes, which can be tuned by compositional engineering. 1,2 Following the first report of perovskite-based solar cells (PSC) a decade ago, 3 the field of perovskite-based photovoltaics has been developing at a very fast pace, now reaching power conversion efficiencies of over 25%. 1,4,5 OIHPs are represented by the generic ABX 3 formula, in which A is typically a small cation such as methylammonium (CH 3 NH 3 + , MA), formamidinium (CH 3 (NH 2) 2 + , FA), and/or cesium ions. The inorganic sublattice is composed of [BX 6 ] 4− octahedra, where B is a divalent metal such as Pb 2+ , Sn 2+ , and Ge 2+ or a mixture of monovalent and trivalent metals (e.g., Ag + and In 3+) and X is a halide: I − , Br − , or Cl −. Lead halide

Organic–inorganic tin(II) halide perovskites have emerged as promising alternatives to lead halide perovskites in optoelectronic applications. While they suffer from considerably poorer performance and stability in comparison to their lead analogues, their performance improvements have so far largely been driven by trial and error efforts due to a critical lack of methods to probe their atomic-level microstructure. Here, we identify the challenges and devise a 119Sn solid-state NMR protocol for the determination of the local structure of mixed-cation and mixed-halide tin(II) halide perovskites as well as their degradation products and related phases. We establish that the longitudinal relaxation of 119Sn can span 6 orders of magnitude in this class of compounds, which makes judicious choice of experimental NMR parameters essential for the reliable detection of various phases. We show that Cl/Br and I/Br mixed-halide perovskites form solid alloys in any ratio, while only limited mixing is possible for I/Cl compositions. We elucidate the degradation pathways of Cs-, MA-, and FA-based tin(II) halides and show that degradation leads to highly disordered, qualitatively similar products, regardless of the A-site cation and halide. We detect the presence of metallic tin among the degradation products, which we suggest could contribute to the previously reported high conductivities in tin(II) halide perovskites. 119Sn NMR chemical shifts are a sensitive probe of the halide coordination environment as well as of the A-site cation composition. Finally, we use variable-temperature multifield relaxation measurements to quantify ion dynamics in MASnBr3 and establish activation energies for motion and show that this motion leads to spontaneous halide homogenization at room temperature whenever two different pure-halide perovskites are put in physical contact.

All-inorganic double perovskites (elpasolites) are a promising potential alternatives to lead halide perovskites in optoelectronic applications. Although halide mixing is a well-established strategy for band gap tuning, little is known about halide mixing and phase segregation phenomena in double perovskites. Here, we synthesize a wide range of single- and mixed-halide Cs2AgBiX6 (X = Cl, Br, and I) double perovskites using mechanosynthesis and probe their atomic-level microstructure using 133Cs solid-state MAS NMR. We show that mixed Cl/Br materials form pure phases for any Cl/Br ratio while Cl/I and Br/I mixing is only possible within a narrow range of halide ratios (

State-of-the-art cesium-containing multiple-cation perovskites are generally synthesized from stock solutions of perovskite precursors and CsI in DMSO and DMF. However, compositional diversity of multi-component perovskites is significantly hampered due to the poor solubility of other cesium halides in these solvents. Here, we show how insoluble CsCl, as a new source of cesium cation, can be integrated into a multiple-cation perovskite material by a one-step method involving grinding of the precursors. The resulting polycrystalline powder is fully soluble in a DMSO/DMF mixture and allows formation of perovskite thin films. 133Cs solid-state MAS NMR data indicate that the cesium cation is almost fully (90%) incorporated into the 3D perovskite lattice, while the remaining 10% forms a cesium-rich mixed-halide secondary phase. The planar heterojunction device fabricated using this original mechanoperovskite yielded a power conversion efficiency of 19.12% and an open circuit voltage of 1.16 V. Moreover, we show that the introduction of CsCl improves both interfacial and bulk photovoltaic metrics. Our one-step approach provides an efficient general method for incorporating poorly soluble salts into multi-component perovskite crystal lattices.

A commercial design, bench scale microfluidic processor, Microfluidics M110-P, was used to study the deagglomeration of clusters of nanosized silica particles. Breakup kinetics, mechanisms and the smallest attainable size were determined over a range of particle concentrations of up to 17% wt. in water and liquid viscosities of up to 0.09 Pa s at 1% wt. particle concentration. The device was found to be effective in achieving complete breakup of agglomerates into submicron size aggregates of around 150 nm over the range covered. A single pass was sufficient to achieve this at a low particle concentration and liquid viscosity. As the particle concentration or continuous phase viscosity was increased, either a higher number of passes or a higher power input (for the same number of passes) was required to obtain a dispersion with a size distribution in the submicron range. Breakup took place through erosion resulting in a dispersion of a given mean diameter range regardless of the operating condition. This is in line with results obtained using rotor-stators. Breakup kinetics compared on the basis of energy density indicated that whilst Microfluidizer M110-P and an in-line rotor-stator equipped with the emulsor screen are of similar performance at a viscosity of 0.01 Pa s, fines volume fraction achieved with the Microfluidizer was much higher at a viscosity of 0.09 Pa s.

Dion-Jacobson (DJ) iodoplumbates based on 1,4-phenylenedimethanammonium (PDMA) have recently emerged as promising light absorbers for perovskite solar cells. While PDMA is one of the simplest aromatic spacers potentially capable of forming a DJ structure based on (PDMA)An-1 Pbn I3n+1 composition, the crystallographic proof has not been reported so far. Single crystal structure of a DJ phase based on PDMA is presented and high-field solid-state NMR spectroscopy is used to characterize the structure of PDMA-based iodoplumbates prepared as thin films and bulk microcrystalline powders. It is shown that their atomic-level structure does not depend on the method of synthesis and that it is ordered and similar for all iodoplumbate homologues. Moreover, the presence of lower (n) homologues in thin films is identified through UV-Vis spectroscopy, photoluminescence spectroscopy, and X-ray diffraction measurements, complemented by cathodoluminescence mapping. A closer look using cathodoluminescence shows that the micron-scale microstructure corresponds to a mixture of different layered homologues that are well distributed throughout the film and the presence of layer edge states which dominate the emission. This work therefore determines the formation of DJ phases based on PDMA as the spacer cation and reveals their properties on a multi-length scale, which is relevant for their application in optoelectronics.

Mixed-cation organic lead halide perovskites attract unfaltering attention owing to their excellent photovoltaic properties. Currently, the best performing perovskite materials contain multiple cations and provide power conversion efficiencies up to around 22%. Here, we report the first quantitative, cation-specific data on cation reorientation dynamics in hybrid mixed-cation formamidinium (FA)/methylammonium (MA) lead halide perovskites. We use 14N, 2H, 13C, and 1H solid-state MAS NMR to elucidate cation reorientation dynamics, microscopic phase composition, and the MA/FA ratio, in (MA)x(FA)1–xPbI3 between 100 and 330 K. The reorientation rates correlate in a striking manner with the carrier lifetimes previously reported for these materials and provide evidence of the polaronic nature of charge carriers in PV perovskites.

Mixed cation perovskites, [HC(NH2)2]xCs(1-x)PbI3, (FAxCs(1-x)PbI3) with x=0.8 achieve high solar cell power conversion efficiencies (PCEs) while exhibiting long-term stability under ambient conditions. In this work, we perform density functional theory (DFT) calculations, first-principles molecular dynamics (MD) simulations, solid-state nuclear magnetic resonance (NMR) and X-ray powder diffraction (XRD) measurements aimed at investigating the possible phase stability of Cs+-rich FAxCs(1-x)PbI3, (0≤x≤0.5) mixed-cation materials as potential candidates for tandem solar cell applications. Estimations of the free energy of the mixtures with respect to the pure compounds together with calculations of the relative phase stability at 0 K and at finite temperature show that although the mixtures can form, the δ phase remains the thermodynamically most stable phase at room temperature. This is fully corroborated by solid-state NMR and XRD measurements and is in contrast to FA+-rich Cs/FA mixtures where small additions of Cs+ are sufficient to stabilize the perovskite phase at ambient conditions. The atomistic origin for this contrasting behavior arises from an energetic destabilization of the perovskite phase on the one hand caused by the incorporation of a large cation (FA+) into the relatively small host lattice of γ-CsPbI3 and on the other hand is induced by the lower degree of distortion of the host lattice. These observations allow us to propose a new design principle for the preferential stabilization of the perovskite phase over the competing δ phase.

There has been an ongoing effort to overcome the limitations associated with the stability of hybrid organic–inorganic perovskite solar cells by using different organic agents as additives to the perovskite formulations. The functionality of organic additives has been predominantly limited to exploiting hydrogen-bonding interactions, while the relevant atomic-level binding modes remain elusive. Herein, we introduce a bifunctional supramolecular modulator, 1,2,4,5-tetrafluoro-3,6-diiodobenzene, which interacts with the surface of the triple-cation double-halide perovskite material via halogen bonding. We elucidate its binding mode using two-dimensional solid-state 19F NMR spectroscopy in conjunction with density functional theory calculations. As a result, we demonstrate a stability enhancement of the perovskite solar cells upon supramolecular modulation, without compromising the photovoltaic performances.

Hybrid organic–inorganic perovskites have become one of the leading thin-film semiconductors for optoelectronics. Their broad application will greatly depend on overcoming the key obstacles associated with poor stability and limited scalability. There has been an ongoing effort to diminish some of these limitations by using organic additives. However, considering the lack of understanding of the underlying structure–property relationships, this progress was greatly based on trial and error as molecular-level design remains challenging. Our approach for enhancing the stability of hybrid perovskites without compromising their efficiency is based on judicious molecular design of multifunctional molecular modulators through fine-tuning of noncovalent interactions and exploiting their structural adaptability. The design principles were scrutinized by solid-state NMR spectroscopy to unravel a new path for stable and scalable perovskite solar cells, which we review in this article.

In-line rotor-stators are used for a wide range of power intensive dispersion applications, including the breakup of immiscible liquid droplets or agglomerates. This study, performed within the DOMINO project at BHR Group, aimed at studying the performance of three different rotor-stator head designs for deagglomeration processes. A given test system, nanoscale silica particles-in-water, was used to identify the mechanism and kinetics of break-up and determine the smallest attainable size. Three rotor-stator head designs used were the GPDH-SQHS and EMSC screens from Silverson and Ytron Z-Lab from Ytron. These in-line rotor-stators were used in the recirculation loop of a stirred tank with a total dispersion volume of 100 l. Power input and residence time were varied by changing the rotor speed and dispersion flow rate. Breakup was found to occur through erosion regardless of the operating conditions or rotor-stator design. The smalleachieves a higher fraction of finesst fragments obtained were aggregates, rather than primary particles, and these were of a mean diameter of 150–200 nm; also independent of the operating conditions or rotor-stator head design. With a given rotor-stator operated at a given flow rate, increasing the rotor speed and hence the power input increased the break up kinetics. For a given design at a given specific power input, whilst the break up rate per tank turnover decreased when the flow rate was increased, the total processing time could be reduced. There were differences in the volume of the mixer head and chamber volumes; in addition, a smaller flow rate range could be covered with the Ytron design. Comparison of the different designs was therefore not straightforward. It could however be shown that the rotor-stator designs with a high number and small size of holes and/or gaps have a faster break up rate.

Hybrid (organic–inorganic) multication lead halide perovskites hold promise for a new generation of easily processable solar cells. Best performing compositions to date are multiple-cation solid alloys of formamidinium (FA), methylammonium (MA), cesium, and rubidium lead halides which provide power conversion efficiencies up to around 22%. Here, we elucidate the atomic-level nature of Cs and Rb incorporation into the perovskite lattice of FA-based materials. We use 133Cs, 87Rb, 39K, 13C, and 14N solid-state MAS NMR to probe microscopic composition of Cs-, Rb-, K-, MA-, and FA-containing phases in double-, triple-, and quadruple-cation lead halides in bulk and in a thin film. Contrary to previous reports, we have found no proof of Rb or K incorporation into the 3D perovskite lattice in these systems. We also show that the structure of bulk mechanochemical perovskites bears close resemblance to that of thin films, making them a good benchmark for structural studies. These findings provide fundamental understanding of previously reported excellent photovoltaic parameters in these systems and their superior stability.

We thank Claire Sauvee and Dr. Gilles Casano (Universite Aix-Marseille) for synthesizing the biradicals used here. We thank Bruker France and Drs. Alain Belguise and Fabien Aussenac for providing initial access to the DNP spectrometer.; International audience; There is currently great interest in understanding the limits on NMR signal enhancements provided by dynamic nuclear polarization (DNP), and in particular if the theoretical maximum enhancements can be achieved. We show that over a 2-fold improvement in cross-effect DNP enhancements can be achieved in MAS experiments on frozen solutions by simply incorporating solid particles into the sample. At 9.4 T and similar to 105 K, enhancements up to epsilon(H) = 515 are obtained in this way, corresponding to 78% of the theoretical maximum. We also underline that degassing of the sample is important to achieve highest enhancements. We link the amplification effect to the dielectric properties of the solid material, which probably gives rise to scattering, diffraction, and amplification of the microwave field in the sample. This is substantiated by simulations of microwave propagation. A reduction in sample heating at a given microwave power also likely occurs due to reduced dielectric loss. Simulations indicate that the microwave field (and thus the DNP enhancement) is inhomogeneous in the sample, and we deduce that in these experiments between 5 and 10% of the solution actually yields the theoretical maximum signal enhancement of 658. The effect is demonstrated for a variety of particles added to both aqueous and organic biradical solutions.

In-line rotor-stators are used in a wide range of industrial applications—primarily for dispersion processes such as emulsification, deagglomeration. Three rotor-stator heads have been used to investigate their performance in breaking up of nanoparticle clusters within a large project. This article reports the findings of a part of this study aimed at investigating the flow and power characteristics in single phase to highlight the differences of three different mixer heads. Power characteristics are determined using the calorimetry allowing the characteristic power numbers for these devices to be obtained. These are also compared with CFD calculations. Flow characteristics are studied through numerical simulations.

A series of 37 dinitroxide biradicals have been prepared and their performance studied as polarizing agents in cross-effect DNP NMR experiments at 9.4 T and 100 K in 1,1,2,2-tetrachloroethane (TCE). We observe that in this regime the DNP performance is strongly correlated with the substituents on the polarizing agents, and electron and nuclear spin relaxation times, with longer relaxation times leading to better enhancements. We also observe that deuteration of the radicals generally leads to better DNP enhancement but with longer build-up time. One of the new radicals introduced here provides the best performance obtained so far under these conditions. ISSN:2041-6520 ISSN:2041-6539

A series of novel complexes [Ni(η(5)-C5H4R)(L)(NHC)](+)A(-)2a-2j and [Ni(η(5)-C5H5)(A)(NHC)] 3a-3c has been obtained by anion metathesis from the corresponding chlorides 1a-1d, depending on the anion binding properties and reaction conditions. Solid-state structures of two cationic complexes (2c, 2j) and two complexes with a coordinated anion (3a, 3c) have been determined by X-ray diffraction revealing a trigonal planar geometry in all cases. Unexpectedly, 3c displayed unprecedented for this type of compounds temperature-dependent NMR spectra that were interpreted in terms of spin equilibrium. The cationic complexes 2 were less efficient in styrene polymerization than the parent chlorides 1. However, the activity of 2 and 3 in Suzuki cross-coupling did not depend considerably on the counterion.

Quantum-confined CsPbBr3 nanoplatelets (NPLs) are extremely promising for use in low-cost blue light-emitting diodes, but their tendency to coalesce in both solution and film form, particularly under operating device conditions with injected charge-carriers, is hindering their adoption. We show that employing a short hexyl-phosphonate ligand (C6H15O3P) in a heat-up colloidal approach for pure, blue-emitting quantum-confined CsPbBr3 NPLs significantly suppresses these coalescence phenomena compared to particles capped with the typical oleyammonium ligands. The phosphonate-passivated NPL thin films exhibit photoluminescence quantum yields of ∼40% at 450 nm with exceptional ambient and thermal stability. The color purity is preserved even under continuous photoexcitation of carriers equivalent to LED current densities of ∼3.5 A/cm2. 13C, 133Cs, and 31P solid-state MAS NMR reveal the presence of phosphonate on the surface. Density functional theory calculations suggest that the enhanced stability is due to the stronger binding affinity of the phosphonate ligand compared to the ammonium ligand.

The use of layered perovskites is an important strategy to improve the stability of hybrid perovskite materials and their optoelectronic devices. However, tailoring their properties requires accurate structure determination at the atomic scale, which is a challenge for conventional diffraction-based techniques. We demonstrate the use of nuclear magnetic resonance (NMR) crystallography in determining the structure of layered hybrid perovskites for a mixed-spacer model composed of 2-phenylethylammonium (PEA+) and 2-(perfluorophenyl)ethylammonium (FEA+) moieties, revealing nanoscale phase segregation. Moreover, we illustrate the application of this structure in perovskite solar cells with power conversion efficiencies that exceed 21%, accompanied by enhanced operational stability.