Optical and scintillation properties of hybrid manganese(II) bromides with formamidinium and acetamidinium cations.

In recent years, hybrid manganese(II) halides (HMHs) have attracted wide attention due to their impressive optical properties, low toxicity, and facile synthetic processibility. Being effective reabsorption-free phosphors, these compounds demonstrate the potential to be used as low-cost solution-processable scintillators. However, most of the HMHs studied to date contain bulk organic cations and, as a result, are characterized by low density and low X-ray stopping power. For this reason, we studied manganese(II) bromides with compact organic cations such as formamidinium (FA+) and acetamidinium (AcA+). In particular, we synthesized four new phases, two of which are characterized by octahedral coordination of manganese ions ((FA)MnBr3 and (AcA)MnBr3) and red emission, whereas the other two have tetrahedrally coordinated Mn2+ ions ((FA)3MnBr5 and (AcA)2MnBr4) and green emission. Photoluminescence (PL) and radioluminescence measurements demonstrated high PL quantum yields and reasonable scintillation light yields of acetamidinium-based compounds. In addition, unlike most known HMH-based scintillators, the discovered materials have a relatively high density due to the small fraction of the volume occupied by organic cations, so their X-ray attenuation coefficients are comparable to the well-known oxide scintillators.

Exceptional structural diversity of hybrid halocuprates(I) with methylammonium and formamidinium cations.

Hybrid halocuprates(I) are nowadays the subject of intensive studies as promising materials for various optoelectronic applications. This class of materials is characterized by wide structural diversity enabled by a great variety in the size and shape of organic cations. Therefore, the study of composition-structure-property relationships is a key step for the rational design of new halocuprate materials with desired properties. In this paper, we comprehensively studied MABr/CuBr and FABr/CuBr systems (MA+ = methylammonium and FA+ = formamidinium) and established the existence of five novel phases (namely, MACu2Br3, FA2[Cu4Br6], MACuBr2, FACuBr2, and FA3CuBr4) related to four different structural types and three distinct A+ : Cu+ stoichiometries (A+ = MA+/FA+). The optical properties of the discovered phases are studied by absorption and low-temperature photoluminescence spectroscopy. Based on a crystal-chemical analysis, we explained a unique structural diversity of the MA- and FA-based bromocuprates, as well as revealed new structure-property relationships.

Crystallization Pathways of FABr-PbBr2-DMF and FABr-PbBr2-DMSO Systems: The Comprehensive Picture of Formamidinium-Based Low-Dimensional Perovskite-Related Phases and Intermediate Solvates.

In this study, we systematically investigated the phase diversity and crystallization pathways of the FABr excessive regions of two ternary systems of FABr-PbBr2-DMF and FABr-PbBr2-DMSO (where FA+-formamidinium cations, DMF-dimethylformamide and DMSO-dimethyl sulfoxide solvents). In these systems, a new FA3PbBr5 phase with a structure containing chains of vertex-connected PbBr6 octahedra is discovered, and its crystal structure is refined. We experimentally assess fundamental information on differences in the mechanisms of crystallization process in FABr-PbBr2-DMF and FABr-PbBr2-DMSO systems and determine possible pathways of crystallization of hybrid perovskites. We show that intermediate solvate phases are not observed in the system with DMF solvent, while a number of crystalline solvates tend to form in the system with DMSO at various amounts of FABr excess.

Butanediammonium Salt Additives for Increasing Functional and Operando Stability of Light-Harvesting Materials in Perovskite Solar Cells.

Organic diammonium cations are a promising component of both layered (2D) and conventional (3D) hybrid halide perovskites in terms of increasing the stability of perovskite solar cells (PSCs). We investigated the crystallization ability of phase-pure 2D perovskites based on 1,4-butanediammonium iodide (BDAI2) with the layer thicknesses n = 1, 2, 3 and, for the first time, revealed the presence of a persistent barrier to obtain BDA-based layered compounds with n > 1. Secondly, we introduced BDAI2 salt into 3D lead−iodide perovskites with different cation compositions and discovered a threshold-like nonmonotonic dependence of the perovskite microstructure, optoelectronic properties, and device performance on the amount of diammonium additive. The value of the threshold amount of BDAI2 was found to be ≤1%, below which bulk passivation plays the positive effect on charge carrier lifetimes, fraction of radiative recombination, and PSCs power conversion efficiencies (PCE). In contrast, the presence of any amount of diammonium salt leads to the sufficient enhancement of the photothermal stability of perovskite materials and devices, compared to the reference samples. The performance of all the passivated devices remained within the range of 50 to 80% of the initial PCE after 400 h of continuous 1 sun irradiation with a stabilized temperature of 65 °C, while the performance of the control devices deteriorated after 170 h of the experiment.

Iodine Solution Treatment in Nonpolar Solvents as a Facile Approach to Improve the Morphology and Photostability of Perovskite Films.

We propose a new, simple, and easily implemented approach to improve the morphology of thin films of lead halide perovskites. A key feature of the approach is the controllable size increase of perovskite grains facilitated by polyiodides formed on the surface of the perovskite upon its treatment with iodine solutions in nonpolar solvents with the best results obtained for iodine solution in toluene saturated with MAI. Such a treatment demonstrated an increase in the average grain size of the films of up to 3.5 times in approximately 2 min followed by significantly enhanced photostability.

Nonmonotonic Photostability of BA2MAn-1PbnI3n+1 Homologous Layered Perovskites.

Layered lead halide perovskites (2D LHPs) are attracting considerable attention as a promising material for a new generation of solar cell devices. LHPs have been presented as a more stable alternative to the more widespread 3D bulk perovskite materials; however, a critical analysis of their photostability is still lacking. In this work, we perform a comparative study between BA2MAn-1PbnI3n+1 (BA─butylammonium and MA─methylammonium) 2D LHPs with different dimensionalities (n = 1-3) and MAPbI3 3D perovskites. We compare different stability testing protocols including photometrical determination of iodine-containing products in nonpolar solvents, X-ray diffraction, and photoluminescence (PL) spectroscopy. The resulting trends of the photostability in an inert atmosphere based on PL spectroscopy measurements demonstrate a nonmonotonic dependence of the degradation rate on the perovskite layer thickness n with a "stability island" at n ≥ 3, which is caused by a combination of antibate factors of electronic structures and chemical compositions in the family of 2D perovskites. We also identify a critical oxygen concentration in the surrounding environment that affects the mechanism and strongly enhances the rate of layered perovskite photodegradation.

Solubility of Hybrid Halide Perovskites in DMF and DMSO.

Solution methods remain the most popular means for the fabrication of hybrid halide perovskites. However, the solubility of hybrid perovskites has not yet been quantitively investigated. In this study, we present accurate solubility data for MAPbI3, FAPbI3, MAPbBr3 and FAPbBr3 in the two most widely used solvents, DMF and DMSO, and demonstrate huge differences in the solubility behavior depending on the solution compositions. By analyzing the donor numbers of the solvents and halide anions, we rationalize the differences in the solubility behavior of hybrid perovskites with various compositions, in order to take a step forward in the search for better processing conditions of hybrid perovskites for solar cells and optoelectronics.

Structural Disorder in Layered Hybrid Halide Perovskites: Types of Stacking Faults, Influence on Optical Properties and Their Suppression by Crystallization Engineering.

Layered hybrid halide perovskites (LHHPs) are an emerging type of semiconductor with a set of unique optoelectronic properties. However, the solution processing of high-quality LHHPs films with desired optical properties and phase composition is a challenging task, possibly due to the structural disorder in the LHHP phase. Nevertheless, there is still a lack of experimental evidence and understanding of the nature of the structural disorder in LHHPs and its influence on the optical properties of the material. In the current work, using 2D perovskites (C4H9NH3)2(CH3NH3)n-1PbnI3n+1 (further BA2MAn-1PbnI3n+1) with n = 1-4 as a model system, we demonstrate that deviations in LHHPs optical properties and X-ray diffraction occur due to the presence of continuous defects-Stacking Faults (SFs). Upon analyzing the experimental data and modeled XRD patterns of a possible set of stacking faults (SFs) in the BA2MAPb2I7 phase, we uncover the most plausible type of SFs, featured by the thickness variation within one perovskite slab. We also demonstrate the successful suppression of SFs formation by simple addition of BAI excess into BA2MAn-1PbnI3n+1 solutions.

Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative.

Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I3)2⋅2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2⋅I2 and new (DMPDA)2(BiI6)(I3)⋅2H2O, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic-inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋅⋅⋅I and (N)H⋅⋅⋅O hydrogen bonds as well as I⋅⋅⋅I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.

Crystal structure of new formamidinium triiodide jointly refined by single-crystal XRD, Raman scattering spectroscopy and DFT assessment of hydrogen-bond network features.

A novel triiodide phase of the formamidinium cation, CH5N2 +·I3 -, crystallizes in the triclinic space group P at a temperature of 110 K. The structure consists of two independent isolated triiodide ions located on inversion centers. The centrosymmetric character of I3 - was additionally confirmed by the observed pronounced peaks of symmetrical oscillations of I3 - at 115-116 cm-1 in Raman scattering spectra. An additional structural feature is that each terminal iodine atom is connected with three neighboring planar formamidinium cations by N-H⋯I hydrogen bonding with the N-H⋯I bond length varying from 2.81 to 3.08 Å, forming a deformed two-dimensional framework of hydrogen bonds. A Mulliken population analysis showed that the calculated charges of hydrogen atoms correlate well with hydrogen-bond lengths. The crystal studied was refined as a three-component twin with domain ratios of 0.631 (1):0.211 (1):0.158 (1).

New Methylamine-Iodine-Mediated Solvent-Free Approach of Hybrid Perovskite Synthesis via the Redox Conversion of Metallic Lead Films.

The fast progress of lab-scale perovskite solar cells makes the problem of upscaling of perovskite thin-film deposition more and more acute; therefore, the development of new methods for perovskite deposition is highly desired. In this work, we proposed a new solution-free preparation approach for hybrid perovskite films based on the in situ generation of methylammonium iodide from methylamine and iodine vapors in the presence of an organic reducing agent conjugated with a redox process of metallic lead conversion with iodine vapor. At first, we demonstrated that either metallic lead or lead iodide powders can readily react with the solution of methylamine and iodine in the presence of isopropyl alcohol acting as a reducing agent, resulting in a phase-pure polycrystalline CH3NH3PbI3 perovskite. A possible mechanism of underlying chemical processes has been proposed. In order to convert the predeposited thin films of metallic lead to CH3NH3PbI3 perovskite, a protocol of sequential treatment by iodine and methylamine vapors was proposed. Finally, we revealed the optimal conditions of processing, which were proven to be facile and robust for the sake of the better control of perovskite grain morphology.

Methylammonium Polyiodides in Perovskite Photovoltaics: From Fundamentals to Applications.

Discovered in 2017, methylammonium polyiodides were proposed as a facile precursor for synthesis of hybrid perovskites by means of their interaction with metallic lead, which initiated further active exploration of their potential applications. Investigation of their unusual properties such as liquid state, unprecedented phase diversity and high reactivity revealed that methylammonium polyiodides are the first representatives of a new class of compounds-reactive polyhalide melts (RPM). In this review, we summarize the reported data on the unique properties of these compounds, discuss their potential for fabrication of hybrid perovskite films and describe the role of polyhalides in degradation of perovskite solar cells.

New Acidic Precursor and Acetone-Based Solvent for Fast Perovskite Processing via Proton-Exchange Reaction with Methylamine.

A new solvent system for PbI2 based on HI solution in acetone with a low boiling point is proposed. High solubility of PbI2 is caused by the formation of iodoplumbate complexes, and reaches a concentration of 1.6 M. Upon its crystallization metastable solvate phases PbI2∙HI∙n{(CH3)2CO} are formed. The latter allows for their easy deposition on substrates in a form of smooth and uniform thin films by spin-coating. Through a fast acid-base reaction with a gaseous amine, the films of the intermediate phase can be completely converted to single-phase perovskite films. The developed method allows one to form smooth perovskite films with high crystallinity with a thickness up to 1 µm. Due to easy and fast processing, the developed method can be promising for perovskite technology upscaling.

From Metallic Lead Films to Perovskite Solar Cells through Lead Conversion with Polyhalide Solutions.

Solutions of methylammonium and formamidinium polyhalides (AX1+n, A = MA, FA, X = I, Br) in isopropanol are introduced as novel versatile precursors for the fabrication of APbX3 hybrid perovskite thin films via oxidation of metallic Pb. The polyhalide solution with adjustable reactivity is distributed over a metallic Pb layer followed by iodine vapor postprocessing to tune the morphology and composition of the film using only the elements inherently present in the perovskite. This method is easily reproducible in any materials science laboratory with equipment commonly used for perovskite solar cell fabrication and resulted in power conversion efficiencies of 16.2 and 17.2% for planar solar cells using MAPbI3 and MA0.25FA0.75PbI2.75Br0.25 perovskites, respectively, as a proof of concept. Implementation of metallic lead thin films as the single Pb-containing precursors reduces a number of in-lab handling hazards compared to classical PbI2 powder and solutions and provides a variety of scalable deposition options.

New Features of Photochemical Decomposition of Hybrid Lead Halide Perovskites by Laser Irradiation.

We found that laser irradiation, being widely used in perovskite photovoltaics for both laser scribing and materials characterization, inevitably causes a cascade of complex photo- and thermochemical conjugated reactions, material melting, and ablation with deep morphological and composition changes of perovskite thin films over a much larger area compared to the initial laser spot. A crucial issue in the advancing or suppression of these degradation processes is related to the origin of the surrounding atmosphere. In particular, an effective approach utilizing an inert gas flow directed onto the exposed area is suggested for the first time to eliminate the negative consequences of perovskite laser scribing. This finding is naturally related to experimental observations of spreading the volatile decomposition products, including elemental iodine, over the pristine perovskite material, regardless of its composition, followed by laser-induced formation of liquid polyiodides. Suppression of decomposition product amount by proper selection of the gas atmosphere and power regime of the laser treatment is of interest to enhance the scribing procedure.

Methylammonium Polyiodides: Remarkable Phase Diversity of the Simplest and Low-Melting Alkylammonium Polyiodide System.

Newly discovered methylammonium polyiodides (MAIx) are unique precursors for innovative solvent-free technologies in perovskite photovoltaics because MAIx are liquids at room temperature and demonstrate high chemical reactivity. We investigated the features of an MAI-I2 system and built up a first phase diagram in wide temperature and composition ranges using data from differential scanning calorimetry, single-crystal X-ray diffraction, and visual thermal analysis. The phase diagram has been found to differ drastically from that of any related systems owing to the unique propensity of methylammonium toward forming a diversity of polyiodides with complicated crystal structures, namely, MAI2, MAI2.67, MAI4, and MAI5.5, found in this system for the first time. The performed density functional theory calculations revealed the crucial role of entropy contributing to the formation of higher methylammonium polyiodides, in good agreement with experimental data.

Patterned films of a hybrid lead halide perovskite grown using space-confined conversion of metallic lead by reactive polyiodide melts.

A unique technique for preparation of thin patterned perovskite films is suggested based on an interaction of reactive polyiodide melts with metallic lead coatings using a patterned die with a given relief. The growth of perovskite in confined space results in pin-hole free textured films.

Strategic advantages of reactive polyiodide melts for scalable perovskite photovoltaics.

Despite tremendous progress in efficiency and stability, perovskite solar cells are still facing the challenge of upscaling. Here we present unique advantages of reactive polyiodide melts for solvent- and adduct-free reactionary fabrication of perovskite films exhibiting excellent quality over large areas. Our method employs a nanoscale layer of metallic Pb coated with stoichiometric amounts of CH3NH3I (MAI) or mixed CsI/MAI/NH2CHNH2I (FAI), subsequently exposed to iodine vapour. The instantly formed MAI3(L) or Cs(MA,FA)I3(L) polyiodide liquid converts the Pb layer into a pure perovskite film without byproducts or unreacted components at nearly room temperature. We demonstrate highly uniform and relatively large area MAPbI3 perovskite films, such as 100 cm2 on glass/fluorine-doped tin oxide (FTO) and 600 cm2 on flexible polyethylene terephthalate (PET)/indium tin oxide (ITO) substrates. As a proof-of-concept, we demonstrate solar cells with reverse scan power conversion efficiencies of 16.12% (planar MAPbI3), 17.18% (mesoscopic MAPbI3) and 16.89% (planar Cs0.05MA0.2FA0.75PbI3) in the standard FTO/c(m)-TiO2/perovskite/spiro-OMeTAD/Au architecture.

Formamidinium iodide: crystal structure and phase transitions.

At a temperature of 100 K, CH5N2+·I- (I), crystallizes in the monoclinic space group P21/c. The formamidinium cation adopts a planar symmetrical structure [the r.m.s. deviation is 0.002 Å, and the C-N bond lengths are 1.301 (7) and 1.309 (8) Å]. The iodide anion does not lie within the cation plane, but deviates from it by 0.643 (10) Å. The cation and anion of I form a tight ionic pair by a strong N-H⋯I hydrogen bond. In the crystal of I, the tight ionic pairs form hydrogen-bonded zigzag-like chains propagating toward [20-1] via strong N-H⋯I hydrogen bonds. The hydrogen-bonded chains are further packed in stacks along [100]. The thermal behaviour of I was studied by different physicochemical methods (thermogravimetry, differential scanning calorimetry and powder diffraction). Differential scanning calorimetry revealed three narrow endothermic peaks at 346, 387 and 525 K, and one broad endothermic peak at ∼605 K. The first and second peaks are related to solid-solid phase transitions, while the third and fourth peaks are attributed to the melting and decomposition of I. The enthalpies of the phase transitions at 346 and 387 K are estimated as 2.60 and 2.75 kJ mol-1, respectively. The X-ray powder diffraction data collected at different temperatures indicate the existence of I as the monoclinic (100-346 K), ortho-rhom-bic (346-387 K) and cubic (387-525 K) polymorphic modifications.