Exposure to environmental factors is generally expected to cause degradation in perovskite films and solar cells. Herein, we show that films with certain defect profiles can display the opposite effect, healing upon exposure to oxygen under illumination. We tune the iodine content of methylammonium lead triiodide perovskite from understoichiometric to overstoichiometric and expose them to oxygen and light prior to the addition of the top layers of the device, thereby examining the defect dependence of their photooxidative response in the absence of storage-related chemical processes. The contrast between the photovoltaic properties of the cells with different defects is stark. Understoichiometric samples indeed degrade, demonstrating performance at 33% of their untreated counterparts, while stoichiometric samples maintain their performance levels. Surprisingly, overstoichiometric samples, which show low current density and strong reverse hysteresis when untreated, heal to maximum performance levels (the same as untreated, stoichiometric samples) upon the photooxidative treatment. A similar, albeit smaller-scale, effect is observed for triple cation and methylammonium-free compositions, demonstrating the general application of this treatment to state-of-the-art compositions. We examine the reasons behind this response by a suite of characterization techniques, finding that the performance changes coincide with microstructural decay at the crystal surface, reorientation of the bulk crystal structure for the understoichiometric cells, and a decrease in the iodine-to-lead ratio of all films. These results indicate that defect engineering is a powerful tool to manipulate the stability of perovskite solar cells.

Defects in metal halide perovskites (MHP) are photosensitive, making the observer effect unavoidable when laser spectroscopy methods are applied. Photoluminescence (PL) bleaching and enhancement under light soaking and recovery in dark are examples of the transient phenomena that are consequent to the creation and healing of defects. Depending on the initial sample composition, environment, and other factors, the defect nature and evolution can strongly vary, making spectroscopic data analysis prone to misinterpretations. Herein, the use of an automatically acquired dependence of PL quantum yield (PLQY) on the laser pulse repetition rate and pulse fluence as a unique fingerprint of both charge carrier dynamics and defect evolution is demonstrated. A simple visual comparison of such fingerprints allows for assessment of similarities and differences between MHP samples. The study illustrates this by examining methylammonium lead triiodide (MAPbI 3 ) films with altered stoichiometry that just after preparation showed very pronounced defect dynamics at time scale from milliseconds to seconds, clearly distorting the PLQY fingerprint. Upon weeks of storage, the sample fingerprints evolve toward the standard stoichiometric MAPbI 3 in terms of both charge carrier dynamics and defect stability. Automatic PLQY mapping can be used as a universal method for assessment of perovskite sample quality.

The interface between wurtzite and zinc blende InP has been identified as type-II, where electrons gather on the zinc blende side and holes on the wurtzite side of the interface. The photoluminescence resulting from recombination across the interface is expected to be long-lived and to exhibit non-exponential decay of emission intensity after pulsed excitation. We verify this prediction using time-resolved photoluminescence spectroscopy on nanowires containing a single heterostructure between a single segment of wurtzite and zinc blende. We find that a significant intensity of type-II emission remains even more than 30 ns after excitation. The decay of the emission intensity is also non-exponential and considerably longer than the exponential decay of the wurtzite InP segment (260 ps). Our results are consistent with the expected photoluminescence characteristics of a type-II interface between the two polytypes. We also find that the lifetime becomes shorter if we create an electron gas at the interface by n-type doping the entire wurtzite segment of the nanowire. This is expected since there are many electrons that a given hole can recombine with, in contrast to the undoped case.

The ancient technology of colouring by mechanical rubbing of a dry pigment onto surfaces can be applied to metal halide perovskites, enabling the fabrication of highly luminescent templated micro and nano arrays.

Metal halide perovskites are an important class of emerging semiconductors. Their charge carrier dynamics is poorly understood due to limited knowledge of defect physics and charge carrier recombination mechanisms. Nevertheless, classical ABC and Shockley-Read-Hall (SRH) models are ubiquitously applied to perovskites without considering their validity. Herein, an advanced technique mapping photoluminescence quantum yield (PLQY) as a function of both the excitation pulse energy and repetition frequency is developed and employed to examine the validity of these models. While ABC and SRH fail to explain the charge dynamics in a broad range of conditions, the addition of Auger recombination and trapping to the SRH model enables a quantitative fitting of PLQY maps and low-power PL decay kinetics, and extracting trap concentrations and efficacies. However, PL kinetics at high power are too fast and cannot be explained. The proposed PLQY mapping technique is ideal for a comprehensive testing of theories and applicable to any semiconductor. Charge dynamics in perovskite is not well-understood, limited by the knowledge of defect physics and charge recombination mechanism, yet the ABC and SRH models are widely used. Here, the authors introduce advanced PLQY mapping as function of excitation pulse energy and repetition frequency to examine the validity of these models.

Low-dimensional hybrid organic-inorganic metal halides have received increased attention because of their outstanding optical and electronic properties. However, the most studied hybrid compounds contain lead and have long-term stability issues, which must be addressed for their use in practical applications. Here, we report a new zero-dimensional hybrid organic-inorganic halide, RInBr4, featuring photoemissive trimethyl(4-stilbenyl)methylammonium (R+) cations and nonemissive InBr4- tetrahedral anions. The crystal structure of RInBr4 is composed of alternating layers of inorganic anions and organic cations along the crystallographic a axis. The resultant hybrid demonstrates bright-blue emission with Commission Internationale de l'Eclairage color coordinates of (0.19, 0.20) and a high photoluminescence quantum yield (PLQY) of 16.36% at room temperature, a 2-fold increase compared to the PLQY of 8.15% measured for the precursor organic salt RBr. On the basis of our optical spectroscopy and computational work, the organic component is responsible for the observed blue emission of the hybrid material. In addition to the enhanced light emission efficiency, the novel hybrid indium bromide demonstrates significantly improved environmental stability. These findings may pave the way for the consideration of hybrid organic In(III) halides for light emission applications.

Zero – dimensional (0D) hybrid organic – inorganic lead halides are receiving global attention because of their outstanding photophysical properties, tunable light emission properties, and relatively high photoluminescence quantum yields (PLQY). Despite these advances, the innate toxicity of lead and poor stability are obstacles for their large-scale commercialization. Here, we report a new, lead-free hybrid organic inorganic compound (C18H22N)InBr4. In this study, the organic precursor salt (C18H22NBr) was studied and compared to the hybrid compound (C18H22N)InBr4. We see a two-fold increase in the PLQY, and improved stability in the hybrid compound compared to the organic salt on its own.

The efficiency of bulk heterojunction (BHJ) based organic solar cells is highly dependent on the morphology of the blend film, which is a result of a fine interplay between donor, acceptor, and solvent during the film drying. In this work, a versatile set-up of in situ spectroscopies is used to follow the morphology evolution during blade coating of three iconic BHJ systems, including polymer:fullerene, polymer:nonfullerene small molecule, and polymer:polymer. the drying and photoluminescence quenching dynamics are systematically study during the film formation of both pristine and BHJ films, which indicate that the component with higher molecular weight dominates the blend film formation and the final morphology. Furthermore, Time-resolved photoluminescence, which is employed for the first time as an in situ method for such drying studies, allows to quantitatively determine the extent of dynamic and static quenching, as well as the relative change of quantum yield during film formation. This work contributes to a fundamental understanding of microstructure formation during the processing of different blend films. The presented setup is considered to be an important tool for the future development of blend inks for solution-cast organic or hybrid electronics.

A novel iodobismuthate semiconductor (MA)4Bi6I22 (measured bandgap of 1.9 eV) was prepared using solution methods in the presence of HgI2 additive.

All-inorganic metal halides such as Cs4PbX6 and CsPbX3 (X = Cl, Br, and I) are attracting global attention owing to their promise in optoelectronic applications. However, the presence of the toxic heavy metal lead (Pb) in these materials is a major concern. Here, a family of nontoxic high-efficiency blue-emitting all-inorganic halides Rb2CuX3 (X = Br and Cl) is reported; the compounds exhibit 1D crystal structures featuring anionic infinity 1[CuX3](2-) ribbons separated by Rb+ cations. The measured record high photoluminescence quantum yield values range from 64% to 100% for Rb2CuBr3 and Rb2CuCl3, respectively. Furthermore, the measured emission linewidths are quite narrow with full width at half maximum values of 54 and 52 nm for Rb2CuBr3 and Rb2CuCl3, respectively. Single crystals of Rb2CuCl3 demonstrate an anti-Stokes photoluminescence signal, shown for the first time for Pb-free metal halides. The discovery of highly efficient narrow blue emitters based on a nontoxic and inexpensive metal copper paves a way for the consideration of low-cost and environmentally friendly copper halides for practical applications.

In article number 1901338, Bayrammurad Saparov and co-workers introduce a family of nontoxic all-inorganic halides Rb2CuX3 (X = Br, Cl), prepared by using high temperature and solution techniques. The materials exhibit one-dimensional crystal structures and show high photoluminescence quantum yield blue emission up to unity attributed to self-trapped excitons. Single crystals of Rb2CuCl3 have also been shown to demonstrate an up-conversion photoluminescence, the first example of such behavior for a Pb-free metal halide.

Perovskite solar cells have recently enabled power conversion efficiency comparable to established technologies such as silicon and cadmium telluride. Ongoing efforts to improve the stability of halide perovskites in ambient air has yielded promising results. However, the presence of toxic heavy element lead (Pb) remains a major concern requiring further attention. Herein, we report three new Pb-free hybrid organic-inorganic perovskite-type halides based on gold (Au), (CH3 NH3 )AuBr4 ⋅H2 O (1), (CH3 NH3 )AuCl4 ⋅H2 O (2), and (CH3 NH3 )AuCl4 (3). Hydrated compounds 1 and 2 crystallize in a brand-new structure type featuring perovskite-derived 2D layers and 1D chains based on pseudo-octahedral AuX6 building blocks. In contrast, the novel crystal structure of the solvent-free compound 3 shows an exotic non-perovskite quasi-2D layered structure containing edge- and corner-shared AuCl6 octahedra. The use of Au metal instead of Pb results in unprecedented low band gaps below 2.5 eV for single-layered metal chlorides and bromides. Moreover, at room temperature the three compounds show a weak blue emission due to the electronic transition between Au-6s and Au-5d, in agreement with the density function theory (DFT) calculation results. These findings are discussed in the context of viability of Au-based halides as alternatives for Pb-based halides for optoelectronic applications.

We present a new example of a mononuclear iron(ii) complex exhibiting a correlated spin-crossover (SCO) transition and strong fluorescence, whose coordination sphere is saturated, for the first time, by six phosphorescent ligands. The interplay between SCO and light emission properties in the thermal region of the spin transition was investigated by means of magnetic, fluorescence, optical absorption and optical microscopy measurements on a single crystal. Overall, the results show an excellent correlation between fluorescence and magnetic data of the present gradual transition, indicating an extreme sensitivity of the optical activity of the ligand to the spin state of the active iron(ii) ions. These results open the way for conceiving new prototypes of pressure and temperature sensors based on this synergy between SCO and luminescence properties. In particular, the fact that cooperative SCO material is not a prerequisite for obtaining such synergetic effects, is useful for the design of thin films or nanoparticles, in which the cooperativity is reduced, for appropriate implementation in nanosized devices to enhance the sensing properties at the nanoscale.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.