Search

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.

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.

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.

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

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.

Organic–inorganic lead halide perovskites are a promising family of light absorbers for a new generation of solar cells, with reported efficiencies currently exceeding 22%. A common problem of solar cells fabricated using these materials is that their efficiency depends on their cycling history, an effect known as current–voltage (J–V) hysteresis. Potassium doping has recently emerged as a universal way to overcome this adverse phenomenon. While the atomistic origins of J–V hysteresis are still not fully understood, it is essential to rationalize the atomic-level effect of protocols that lead to its suppression. Here, using 39K MAS NMR at 21.1 T we provide for the first time atomic-level characterization of the potassium-containing phases that are formed upon KI doping of multication and multianion lead halide perovskites. We find no evidence of potassium incorporation into 3D perovskite lattices of the recently reported materials. Instead, we observe formation of a mixture of potassium-rich phases and un...

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.

The efficiency of perovskite solar cells (PSCs) is currently limited by non-radiative recombination losses. One potential loss channel consists of electrons recombining at the interface with the hole transport layer (HTL). We synthesized adamantylammonium halides (ADAHX, X = Cl-, Br-, I-) and demonstrated that ADAHI interacts with the perovskite surface using solid-state NMR spectroscopy. As a result, ADAHI reduces non-radiative recombination when added to the HTL, raising the PSC photovoltage to an average value of 1.185 V, the power conversion efficiency (PCE) to almost 22%, and the maximum external electroluminescence quantum yield to 2.5% at an injection current that is equal to the photocurrent under solar illumination. The lowest value measured for the loss in potential is only 365 mV with respect to the band gap, surpassing the highest-efficiency silicon solar cells. Devices with ADAHI-modified HTL show excellent operational stability for 500 hours. We show the general validity of our new approach for a variety of perovskite formulations and hole conductors.

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.

The high conversion efficiency has made metal halide perovskite solar cells a real breakthrough in thin film photovoltaic technology in recent years. Here, we introduce a straightforward strategy to reduce the level of electronic defects present at the interface between the perovskite film and the hole transport layer by treating the perovskite surface with different types of ammonium salts, namely ethylammonium, imidazolium and guanidinium iodide. We use a triple cation perovskite formulation containing primarily formamidinium and small amounts of cesium and methylammonium. We find that this treatment boosts the power conversion efficiency from 20.5% for the control to 22.3%, 22.1%, and 21.0% for the devices treated with ethylammonium, imidazolium and guanidinium iodide, respectively. Best performing devices showed a loss in efficiency of only 5% under full sunlight intensity with maximum power tracking for 550 h. We apply 2D- solid-state NMR to unravel the atomic-level mechanism of this passivation effect., Various approaches have been developed to push higher the efficiency of halide perovskite solar cells. Here Alharbi et al. show that ammonium salts treatment can reduce the defect density at the perovskite surface and understand the passivation mechanism with 2D-solid state NMR.

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.

Engineering the chemical composition of inorganic-organic hybrid perovskite materials is an effective strategy to boost the performance and operational stability of perovskite solar cells (PSCs). Among the diverse family of ABX(3) perovskites, methylammonium-free mixed A-site cation Cs(x)FA(1-x)PbI(3) perovskites appear as attractive light-absorber materials because of their optimum band gap, superior optoelectronic property, and good thermal stability. Here, we develop a simple and very effective one-step solution method for the preparation of high-quality (Cs)(x)(FA)(1-x)PbI3 perovskite films upon the addition of excess CsCl to the FAPbI(3) precursor solution. It is found that the addition of CsCl as a source of Cs cation instead of relevant addition of CsI to the parent perovskite solution increases effectively the grain size and film quality leading to improved charge mobility, reduced carrier recombination, and long carrier lifetime. The resultant mesoscopic perovskite devices exhibit a maximum efficiency of 20.60% with a stabilized power conversion efficiency of 19.85% and lower hysteresis compared to the reference device. This performance is among the highest reported for PSC devices incorporating mixed cation (Cs)(x)(FA)(1-x)PbI3 perovskites.

Perovskite solar cells present one of the most prominent photovoltaic technologies, yet their stability, scalability, and engineering at the molecular level remain challenging. We demonstrate a concept of multifunctional molecular modulation of scalable and operationally stable perovskite solar cells that exhibit exceptional solar-to-electric power conversion efficiencies. The judiciously designed bifunctional molecular modulator SN links the mercapto-tetrazolium (S) and phenylammonium (N) moieties, which passivate the surface defects, while displaying a structure-directing function through interaction with the perovskite that induces the formation of large grain crystals of high electronic quality of the most thermally stable formamidinium cesium mixed lead iodide perovskite formulation. As a result, we achieve greatly enhanced solar cell performance with efficiencies exceeding 20% for active device areas above 1 cm2 without the use of antisolvents, accompanied by outstanding operational stability under ambient conditions., Engineering hybrid perovskites at the molecular level to solve the stability problem remains a challenge. Here Grätzel et al. design a multifunctional molecular modulator that interacts with the perovskite via modes elucidated by solid state NMR spectroscopy and show high efficiency and operational stability.

Hybrid (organic-inorganic) multi-cation 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 understan...

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.

Methylammonium (MA)- and formamidinium (FA)-based organic-inorganic lead halide perovskites provide outstanding performance as photovoltaic materials, due to their versatility of fabrication and their power conversion efficiencies reaching over 22%. The proposition of guanidinium (GUA)-doped perovskite materials generated considerable interest due to their potential to increase carrier lifetimes and open circuit voltages as compared to pure MAPbI3. However, simple size considerations based on the Goldshmidt tolerance factor suggest that guanidinium is too big to replace methylammonium as an A cation in the APbI3 perovskite lattice, and its effect was thus ascribed to passivation of surface trap states at grain boundaries. As guanidinium was not thought to incorporate into the MAPbI3 lattice, interest waned since it appeared unlikely that it could be used to modify the intrinsic perovskite properties. Here, using solid-state NMR, we show that not only is GUA directly incorporated into the MAPbI3 and FAPbI3 lattices, forming pure GUAxMA1-xPbI3 or GUAxFA1-xPbI3 phases, but we also find that it reorients on the picosecond timescale within the perovskite lattice, which explains its superior charge carrier stabilisation capacity. Our findings establish a fundamental link between charge carrier lifetimes observed in photovoltaic perovskites and the A cation structure in ABX3 type metal halide perovskites.

Formamidinium (FA) lead iodide perovskite materials feature promising photovoltaic performances and superior thermal stabilities. However, conversion of the perovskite α-FAPbI3 phase to the thermodynamically stable yet photovoltaically inactive δ-FAPbI3 phase compromises the photovoltaic performance. A strategy is presented to address this challenge by using low-dimensional hybrid perovskite materials comprising guaninium (G) organic spacer layers that act as stabilizers of the three-dimensional α-FAPbI3 phase. The underlying mode of interaction at the atomic level is unraveled by means of solid-state nuclear magnetic resonance spectroscopy, X-ray crystallography, transmission electron microscopy, molecular dynamics simulations, and DFT calculations. Low-dimensional-phase-containing hybrid FAPbI3 perovskite solar cells are obtained with improved performance and enhanced long-term stability.

All-inorganic metal halide perovskites are showing promising development towards efficient long-term stable materials and solar cells. Element doping, especially on the lead site, has been proved to be a useful strategy to obtain the desired film quality and material phase for high efficient and stable inorganic perovskite solar cells. Here we demonstrate a function by adding barium in CsPbI2Br. We find that barium is not incorporated into the perovskite lattice but induces phase segregation, resulting in a change in the iodide/bromide ratio compared with the precursor stoichiometry and consequently a reduction in the band gap energy of the perovskite phase. The device with 20 mol% barium shows a high power conversion efficiency of 14.0% and a great suppression of non-radiative recombination within the inorganic perovskite, yielding a high open-circuit voltage of 1.33 V and an external quantum efficiency of electroluminescence of 10−4., Element doping has been proven a useful strategy to tune the properties of halide perovskites. Here Xiang et al. show that barium unexpectedly does not incorporate in perovskite lattice but induces phase segregation and bandgap reduction and inhibits non-radiative recombination.

There is an ongoing surge of interest in the use of formamidinium (FA) lead iodide perovskites in photovoltaics due to their exceptional optoelectronic properties. However, thermodynamic instability of the desired cubic perovskite (α-FAPbI3) phase at ambient conditions leads to the formation of a yellow non-perovskite (δ-FAPbI3) phase that compromises its utility. A stable α-FAPbI3 perovskite phase is achieved by employing benzylammonium iodide (BzI) and the microscopic structure is elucidated by using solid-state NMR spectroscopy and X-ray scattering measurements. Perovskite solar cells based on the FAPbI3(BzI)0.25 composition achieve power conversion efficiencies exceeding 20%, which is accompanied by enhanced shelf-life and operational stability, maintaining 80% of the performance after one year at ambient conditions.