Superfluorescence from Electron-Hole Plasma at Moderate Temperatures of 175 K.

Superfluorescence, a cooperative coherent spontaneous emission, is of great importance to the understanding of many-body correlation in optical processes. Even though superfluorescence has been demonstrated in many diverse systems, it is hard to observe in electron-hole plasma (EHP) due to its rapid dephasing and hence needs strong magnetic fields or complex microcavities. Herein, we report the first experimental observation of superfluorescence from EHP up to a moderate temperature of 175 K without external stimuli in a coupled metal halide perovskite quantum dots film. The EHP exhibits macroscopic quantum coherence through spontaneous synchronization. The coherence of the excited state decays by superfluorescence, which is redshifted 40 meV from the spontaneous emission with a ∼1700 times faster decay rate and exhibits quadratic fluence dependence. Notably, the excited state population's delayed growth and abrupt decay, which are strongly influenced by the pump fluence and the Burnham-Chiao ringing, are the characteristics of the superfluorescence. Our findings will open up a new frontier for cooperative emission and light beam-based technologies.

Effect of film morphology on circular dichroism of low-dimensional chiral hybrid perovskites.

Chiral hybrid lead halide perovskites show interesting chiral optoelectronic properties. The extent of chirality is often estimated by their circular dichroism (CD) response. Here, we show that the CD data depend strongly on film morphology. Four of the six chiral hybrid lead halide films prepared, 2D (R- and S-MBA)2PbI4 and 1D (R- and S-MBA)PbI3 (MBA: methylbenzylammonium), form homogenous non-textured films and show an isotropic CD signal. In contrast, the other two samples, 1D (R- and S-MBA)PbBr3, form textured films, showing uncorrelated CD signals from different parts of the film. Therefore, the role of film morphology needs to be verified before designing and comparing the chiroptic and chiral optoelectronic properties of hybrid perovskites.

Emissive Dark Excitons in Monoclinic Two-Dimensional Hybrid Lead Iodide Perovskites.

Typically, bright excitons (XB) emit light in two-dimensional (2D) layered hybrid perovskites. There are also dark excitons (XD), for which radiative recombination is spin-forbidden. Application of a magnetic field can somewhat relax the spin-rule, yielding XD emission. Can we obtain XD light emission in the absence of a magnetic field? Indeed, we observe unusually intense XD emission at ∼7 K for (Rac-MBA)2PbI4, (Rac-4-Br-MBA)2PbI4, and (R-4-Br-MBA)2PbI4 (Rac-MBA: racemic methylbenzylammonium), which crystallize in a lower symmetry monoclinic phase. For comparison, orthorhombic (R-MBA)2PbI4 does not exhibit XD emission. XD has a lower energy than XB, with energy difference ΔE. In monoclinic samples, ΔE ∼ 20 meV is large enough to suppress the thermal excitation of XD to XB, at temperatures <30 K. Consequently, XD recombines by emitting light with a long lifetime (∼205 ns). At higher temperatures, the emission switches to the spin-allowed XB (lifetime < 1 ns).

Broad Dual Emission by Codoping Cr3+ (d→d) and Bi3+ (s→p) in Cs2 Ag0.6 Na0.4 InCl6 Double Perovskite.

A phosphor emitting both white light and broad near-infrared (NIR) radiation can simultaneously provide visual inspection and early signs of rotting of food products. The broad NIR emission is absorbed by the vibrational overtones of water molecules present in food items, providing the non-invasive image contrast to assess the food freshness. Here we design a phosphor, namely, Cr3+ -Bi3+ -codoped Cs2 Ag0.6 Na0.4 InCl6 , that simultaneously emit warm white light and broad NIR (1000 nm) radiation with quantum yield 27 %. This dual emitter is designed by combining the features of s2 -electron (Bi3+ ) and d3 -electron (Cr3+ ) doping in a weak crystal field of the halide perovskite host. 6 s 2 → 6 s 1 6 p 1 ${6{s}^{2}\to 6{s}^{1}6{p}^{1}}$ excitation of Bi3+ , using a commercial 370 nm ultraviolet light-emitting-diodes (UV-LED), yields both the emissions. A fraction of the excited Bi3+ dopants emit the warm white light, and the other fraction transfers its energy non-radiatively to Cr3+ . Then the Cr3+ de-excites emitting broad NIR emission. Temperature dependent (6.4-300 K) photoluminescence in combination with Tanabe-Sugano diagram show that the Cr3+ experiences a weak crystal field ( D q / B ${{D}_{q}/B}$ =2.2), yielding the 4 T 2 → 4 A 2 ${{{\rm \ }}^{4}{{\rm T}}_{2}\to {{\rm \ }}^{4}{{\rm A}}_{2}}$ NIR emission. As a proof of concept, we fabricated a panel containing 122 phosphor-converted LEDs, demonstrating its capability to inspect food products.

Combining π-Conjugation and Cation-π Interaction for Water-Stable and Photoconductive One-Dimensional Hybrid Lead Bromide.

Hybrid lead halide perovskites and their derivatives are important optoelectronic materials but suffer from water instability. Combining both the optoelectronics and the water stability of such systems is a major challenge in material design today. To address this issue, we employ the well-known π-conjugation and cation-π interaction concepts in designing a hybrid lead halide perovskite derivative system. (4,4'-VDP)Pb2Br6 (VDP = vinylenedipyridinium) single crystals are prepared. They have a one-dimensional (1D) arrangement of inorganic Pb-Br sublattices connected via the 4,4'-VDP organic sublattice. The π-conjugation in the 4,4'-VDP sublattice allows electronic communication between the 1D Pb-Br units, reducing the band gap and improving the photoconductivity. Importantly, N+ of one 4,4'-VDP molecular ion interacts with the π-electron cloud of the adjacent one. This intermolecular cation-π interaction extends throughout the organic sublattice, making the hybrid crystal stable when stored under water for more than a year without requiring any encapsulations.

Rational Design of Non-Centrosymmetric Hybrid Halide Perovskites.

Structural non-centrosymmetry in semiconducting organic-inorganic hybrid halide perovskites can introduce functionalities like anomalous photovoltaics and nonlinear optical properties. Here we introduce a design principle to prepare Pb- and Bi-based two- and one-dimensional hybrid perovskites with polar non-centrosymmetric space groups. The design principle relies on creating dissimilar hydrogen and halogen bonding non-covalent interactions at the organic-inorganic interface. For example, in organic cations like I-(CH2)3-NH2(CH3)+ (MIPA), -CH3 is substituted by -CH2I at one end, and -NH3+ is substituted by -NH2(CH3)+ at the other end. These substitutions of two -H atoms by -I and -CH3 reduce the rotational symmetry of MIPA at both ends, compared to an unsubstituted cation, for example, H3C-(CH2)3-NH3+. Consequently, the dissimilar hydrogen-iodine and iodine-iodine interactions at the organic-inorganic interface of (MIPA)2PbI4 2D perovskites break the local inversion symmetries of Pb-I octahedra. Owing to this non-centrosymmetry, (MIPA)2PbI4 displays visible to infrared tunable nonlinear optical properties with second and third harmonic generation susceptibility values of 5.73 pm V-1 and 3.45 × 10-18 m2 V-2, respectively. Also, the single crystal shows photocurrent on shining visible light at no external bias, exhibiting anomalous photovoltaic effect arising from the structural asymmetry. The design strategy was extended to synthesize four new non-centrosymmetric hybrid perovskite compounds. Among them, one-dimensional (H3N-(CH2)3-NH(CH3)2)BiI5 shows a second harmonic generation susceptibility of 7.3 pm V-1 and a high anomalous photovoltaic open-circuit voltage of 22.6 V.

Magnetoplasmonics beyond Metals: Ultrahigh Sensing Performance in Transparent Conductive Oxide Nanocrystals.

Active modulation of the plasmonic response is at the forefront of today's research in nano-optics. For a fast and reversible modulation, external magnetic fields are among the most promising approaches. However, fundamental limitations of metals hamper the applicability of magnetoplasmonics in real-life active devices. While improved magnetic modulation is achievable using ferromagnetic or ferromagnetic-noble metal hybrid nanostructures, these suffer from severely broadened plasmonic response, ultimately decreasing their performance. Here we propose a paradigm shift in the choice of materials, demonstrating for the first time the outstanding magnetoplasmonic performance of transparent conductive oxide nanocrystals with plasmon resonance in the near-infrared. We report the highest magneto-optical response for a nonmagnetic plasmonic material employing F- and In-codoped CdO nanocrystals, due to the low carrier effective mass and the reduced plasmon line width. The performance of state-of-the-art ferromagnetic nanostructures in magnetoplasmonic refractometric sensing experiments are exceeded, challenging current best-in-class localized plasmon-based approaches.

Effect of chirality on the optical properties of layered hybrid perovskite R- and S-α-methylbenzylammonium lead iodide.

The introduction of chirality in layered hybrid perovskites breaks the symmetry of their inorganic sub-lattices. Consequently, they show intriguing linear and non-linear optical properties. Here we explore the effect of chirality on the excitonic photoluminescence of chiral (R- and S-α-MBA)2PbI4 (MBA: methylbenzylammonium) at cryogenic temperatures. The induced chirality splits the excitonic emissions below 150 K. Additionally, (R- and S-α-MBA)2PbI4 show wavelength-tunable second harmonic generation (SHG) that depends strongly on the polarization angle of the incident light.

Sb3+ -Er3+ -Codoped Cs2 NaInCl6 for Emitting Blue and Short-Wave Infrared Radiation.

Cs2 NaInCl6 double perovskite is stable, environmentally benign and easy to prepare. But it has a wide band gap (5.1 eV), and therefore, does not show optical and optoelectronic properties in the visible and short-wave infrared (SWIR) region. Here we introduce such functionalities in Cs2 NaInCl6 by codoping Sb3+ (s-electron doping) and Er3+ (f-electron doping) ions. Sb3+ doping introduces optically allowed 5s2 → 5s1 5p1 electronic absorption at the sub-band gap level, which then emits blue photoluminescence with ≈93 % quantum yield. But f-f electronic absorption of Er3+ is parity forbidden. Codoping Sb3+ -Er3+ , leads to transfer of excitation energy from Sb3+ to Er3+ , yielding SWIR emission at 1540 nm. Temperature (6 to 300 K) dependent photoluminescence measurements elucidate the excitation and emission mechanism. A phosphor converted light emitting diode (pc-LED) fabricated by using the codoped sample emits stable blue and SWIR radiation over prolonged (84 hours) operation at 5.1 V.

Origin of Luminescence in Sb3+- and Bi3+-Doped Cs2SnCl6 Perovskites: Excited State Relaxation and Spin-Orbit Coupling.

Sb3+- and Bi3+-doped Cs2SnCl6 zero-dimensional perovskites are emerging as stable and nontoxic phosphors for light emitting diodes. The outermost s-electrons (ns2) of the dopants are responsible for both light absorption (ns2 to ns1np1) and emission (ns1np1 to ns2). At cryogenic temperatures, the Sb3+ dopant shows two emission peaks, but Bi3+ shows only one emission peak. Why? Here we address such questions, revealing the origin of luminescence in Sb3+- and Bi3+-doped Cs2SnCl6. We find that the emitting excited state ns1np1 is a triplet state 3T1u*. The notation "*" implies spin-orbit coupling between the 3T1u and 1T1u states. After light absorption, 3T1u* is occupied with one electron, which then undergoes Jahn-Teller distortion yielding a relaxed excited state (RES). For the Sb3+ dopant, the combination of Jahn-Teller distortion and spin-orbit coupling gives rise to two minima in RES 3T1u*, resulting in two emission peaks, whereas for the Bi3+ dopant, the spin-orbit coupling significantly dominates over the Jahn-Teller splitting yielding a single minimum in RES 3T1u* and, therefore, a single emission peak.

Temperature-Dependent Photoluminescence of Hexafluorobenzene-Intercalated Phenethylammonium Tin Iodide 2D Perovskite.

Tin halide perovskites are potential alternatives of lead halide perovskites. However, the easy oxidation of Sn2+ to Sn4+ brings in a challenge. Recently, layered two-dimensional hybrid tin halide perovskites have been shown to partially resist the oxidation process because of the presence of hydrophobic organic molecules. Consequently, such layered hybrid perovskites are being explored for optoelectronic applications. The optical properties of layered tin halide perovskites depend on the interlayer separation and the dielectric mismatch between the organic and inorganic layers. Intercalation (insertion) of a molecular species between the layers modifies the interlayer interactions affecting the optical properties of layered hybrid perovskites. We investigated the effect of hexafluorobenzene (HFB) intercalation in phenethylammonium tin iodide [(PEA)2 SnI4 ] using temperature-dependent (6 K to 300 K) photoluminescence (PL). HFB intercalation increases the bandgap. A strong PL quenching is observed in pristine (PEA)2 SnI4 below 150 K, probably because of the presence of non-emissive states. HFB intercalation suppresses the influence of such non-emissive states resulting in an increase in PL intensity at the cryogenic temperatures. Our results highlight that a simple molecular intercalation (non-covalent interaction) into layered hybrid perovskites can significantly tailor the electronic and optical properties.

Introducing Intermolecular Cation-π Interactions for Water-Stable Low Dimensional Hybrid Lead Halide Perovskites.

Optoelectronically active hybrid lead halide perovskites dissociate in water. To prevent this dissociation, here, we introduce long-range intermolecular cation-π interactions between A-site cations of hybrid perovskites. An aromatic diamine like 4,4'-trimethylenedipyridine, if protonated, can show a long-range cation-π stacking, and therefore, serves as our A-site cation. Consequently, 4,4'-trimethylenedipyridinium lead bromide [(4,4'-TMDP)Pb2 Br6 ], a one-dimensional hybrid perovskite, remains completely stable after continuous water treatment for six months. Mechanistic insights about the cation-π interactions are obtained by single-crystal X-ray diffraction and nuclear magnetic resonance spectroscopy. The concept of long-range cation-π interaction is further extended to another A-site cation 4,4'-ethylenedipyridinium ion (4,4'-EDP), forming water-stable (4,4'-EDP)Pb2 Br6 perovskite. These water-stable perovskites are then used to fabricate white light-emitting diode and for light up-conversion through tunable third-harmonic generation. Note that the achieved water stability is the intrinsic stability of perovskite composition, unlike the prior approach of encapsulating the unstable perovskite material (or device) by water-resistant materials. The introduced cation-π interactions can be a breakthrough strategy in designing many more compositions of water-stable low-dimensional hybrid perovskites.

State of the Art and Prospects for Halide Perovskite Nanocrystals.

Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

Colloidal BaZrS3 chalcogenide perovskite nanocrystals for thin film device fabrication.

The theoretical optoelectronic properties of chalcogenide perovskites (e.g., BaZrS3) are as good as those of halide perovskites (e.g., CH3NH3PbI3). But the fabrication of optoelectronic devices is rarely reported, mainly because researchers still do not know how to prepare good quality thin films of chalcogenide perovskites. Here, we report colloidal BaZrS3 nanocrystals (NCs, 40-60 nm) and their solution processed thin film transistors. BaZrS3 NCs are first prepared using a solid-state synthesis route, and the subsequent surface modifications lead to a colloidal dispersion of NCs in both polar N-methyl-2-pyrrolidinone and non-polar chloroform solvents. The NCs exhibit good thermal (15-673 K) and aqueous stability. Colloidal BaZrS3 NCs in chloroform are then used to make field effect transistors showing ambipolar properties with a hole mobility of 0.059 cm2 V-1 s-1 and an electron mobility of 0.017 cm2 V-1 s-1. This report of solution processed chalcogenide perovskite thin films with reasonable carrier mobility and optical absorption and emission is expected to pave the way for future optoelectronic devices of chalcogenide perovskites.

Dielectric confinement for designing compositions and optoelectronic properties of 2D layered hybrid perovskites.

Two dimensional (2D) layered hybrid lead halide perovskites are a fascinating class of semiconductors displaying a plethora of interesting optoelectronic properties with potential for application in solar cells, light emitting diodes, etc. Most of these properties can be linked to their repeating quantum well-like structures providing 2D excitons. In this perspective, we discuss how dielectric confinement of excitons originates in these layered hybrid perovskites, and then, how it can be used to tune the excitonic properties. In particular, we discuss the recent theoretical and experimental advances correlating dielectric confinement with chemical composition, excitonic binding energy, and optoelectronic property. The freedom from the restrictions of the Goldsmith tolerance factor allows the synthesis of hundreds of compositions of 2D layered hybrid perovskites by independently varying the organic and inorganic layers. We envisage that the combination of this compositional flexibility with the concepts of dielectric confinement discussed in this perspective would be a path forward for designing novel optoelectronic materials.

Lead-Free Double Perovskite Cs2 AgInCl6.

Lead-free halide perovskites have drawn wide attention as alternatives to their toxic and poorly stable lead-based counterparts. Among them, double perovskites with Cs2 AgInCl6 composition, often doped with various elements, have been in the spotlight owing to their intriguing optical properties, namely, self-trapped exciton (STEs) emission and dopant-induced photoluminescence. This interest has sparked different synthesis approaches towards both crystals and nanocrystals, and the exploration of many alloy compositions with mono- and trivalent cations other than Ag+ and In3+ . In this Minireview we describe the recent developments on Cs2 AgInCl6 bulk crystals and nanocrystals, their synthesis strategies, intrinsic optical properties, and tunable photoluminescence originating from different alloying and doping effects. We also discuss progress on computational studies aimed at understanding the thermodynamic stability, the role of defects, and the origin of photoluminescence in relation to the STEs and the direct band gap character.

Don't Let the Lead Out: New Material Chemistry Approaches for Sustainable Lead Halide Perovskite Solar Cells.

Lead halide perovskites are seriously considered for next generation photovoltaic technology. They have a unique combination of easy synthesis, high efficiency, and cost-effective techniques. Still, the major concern is the toxicity of lead used in perovskite devices. The research community is still debating whether the amount of lead used in a solar cell really poses a danger or not. However, it is pretty clear that mitigating the lead leakage from the lead halide perovskite device is of utmost importance. In this review, we discuss new material chemistry approaches that can be applied to reduce the lead leakage/wastage from damaged lead halide perovskite solar cells. ECR (encapsulate, capture, and recycle) approaches have the potential to significantly reduce the environmental and health hazard risks of lead halide perovskite devices. Encapsulation by a self-healing material and rigid glass can help the perovskite survive the extreme conditions and avoid exposure of the perovskite layer to the external environment. Capturing of lead can also be done by an encapsulant layer that can very quickly and efficiently bind to lead, in the case that it leaks from the damaged perovskite device. Moreover, the recycling of damaged or decommissioned devices helps to avoid the lead wastage and contamination in the environment. Finally, we also discuss the potential of lead-free perovskite for optoelectronic applications.

Molecular Intercalation and Electronic Two Dimensionality in Layered Hybrid Perovskites.

In layered hybrid perovskites, such as (BA)2 PbI4 (BA=C4 H9 NH3 ), electrons and holes are considered to be confined in atomically thin two dimensional (2D) Pb-I inorganic layers. These inorganic layers are electronically isolated from each other in the third dimension by the insulating organic layers. Herein we report our experimental findings that suggest the presence of electronic interaction between the inorganic layers in some parts of the single crystals. The extent of this interaction is reversibly tuned by intercalation of organic and inorganic molecules in the layered perovskite single crystals. Consequently, optical absorption and emission properties switch reversibly with intercalation. Furthermore, increasing the distance between inorganic layers by increasing the length of the organic spacer cations systematically decreases these electronic interactions. This finding that the parts of the layered hybrid perovskites are not strictly electronically 2D is critical for understanding the electronic, optical, and optoelectronic properties of these technologically important materials.

Bi3+ -Er3+ and Bi3+ -Yb3+ Codoped Cs2 AgInCl6 Double Perovskite Near-Infrared Emitters.

Bi3+ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi3+ and lanthanide ions. Codoping of Bi3+ and Ln3+ (Ln=Er and Yb) in Cs2 AgInCl6 double perovskite is presented. Bi3+ -Er3+ codoped Cs2 AgInCl6 shows Er3+ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi3+ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi3+ -Er3+ codoped Cs2 AgInCl6 shows ca. 45 times higher emission intensity compared to the Er3+ doped Cs2 AgInCl6 . Similar results are also observed in Bi3+ -Yb3+ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.