Gamma-ray detection and spectroscopy is the quantitative determination of their energy spectra, and is of critical value and critically important in diverse technological and scientific fields. Here we report an improved melt growth method for cesium lead bromide and a special detector design with asymmetrical metal electrode configuration that leads to a high performance at room temperature. As-grown centimeter-sized crystals possess extremely low impurity levels (below 10 p.p.m. for total 69 elements) and detectors achieve 3.9% energy resolution for 122 keV 57Co gamma-ray and 3.8% for 662 keV 137Cs gamma-ray. Cesium lead bromide is unique among all gamma-ray detection materials in that its hole transport properties are responsible for the high performance. The superior mobility-lifetime product for holes (1.34 × 10−3 cm2 V−1) derives mainly from the record long hole carrier lifetime (over 25 μs). The easily scalable crystal growth and high-energy resolution, highlight cesium lead bromide as an exceptional next generation material for room temperature radiation detection.

High-performance and good-stability hollow Sn-based perovskite solar cells using ethylenediammonium and formamidinium cations.

The unique hybrid nature of 2D Ruddlesden–Popper (R–P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R–P perovskites, by utilizing pentylamine (PA)2(MA) n−1Pb n I3n+1 (n = 1–5, PA = CH3(CH2)4NH3 +, C5) and hexylamine (HA)2(MA) n−1Pb n I3n+1 (n = 1–4, HA = CH3(CH2)5NH3 +, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R–P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20–80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

Tin-based perovskites have very comparable electronic properties to lead-based perovskites and are regarded as possible lower toxicity alternates for solar cell applications. However, the efficiency of tin-based perovskite solar cells is still low and they exhibit poor air stability. Here, we report lead-free tin-based solar cells with greatly enhanced performance and stability using so-called "hollow" ethylenediammonium and methylammonium tin iodide ({en}MASnI) perovskite as absorbers. Our results show that en can improve the film morphology and most importantly can serve as a new cation to be incorporated into the 3D MASnI lattice. When the cation of en becomes part of the 3D structure, a high density of SnI vacancies is created resulting in larger band gap, larger unit cell volume, lower trap-state density, and much longer carrier lifetime compared to classical MASnI. The best-performing {en}MASnI solar cell has achieved a high efficiency of 6.63% with an open circuit voltage of 428.67 mV, a short-circuit current density of 24.28 mA cm, and a fill factor of 63.72%. Moreover, the {en}MASnI device shows much better air stability than the neat MASnI device. Comparable performance is also achieved for cesium tin iodide solar cells with en loading, demonstrating the broad scope of this approach.

Singlet fission (SF) is a spin-allowed process that involves absorption of a photon by two electronically interacting chromophores to produce a singlet exciton state, (SS), followed by rapid formation of two triplet excitons if the singlet exciton energy is about twice that of the triplet exciton. The initial formation of the multiexciton correlated triplet pair state, (TT), is thought to involve the agency of charge transfer (CT) states. The dynamics of these electronic states were studied in a covalent slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer in which the conformation of two TDI molecules is determined by a xanthene spacer (XanTDI). Femtosecond mid-infrared (fsIR) spectroscopy shows that the multiexciton (TT) state has absorptions characteristic of the T state in the carbonyl stretch region of the IR spectrum, in addition to IR absorptions specific to the CT state in the C═C stretch region. The simultaneous presence of CT and triplet state features in both high dielectric constant CHCl and low dielectric constant 1,4-dioxane throughout the multiexciton state lifetime suggests that this state has both CT and triplet character.

Low-dimensional halide perovskites have recently attracted intense interest as alternatives to the three-dimensional (3D) perovskites because of their greater tunability and higher environmental stability. Herein, we present the new homologous 2D series (NHC HNH)(CHNH) PbI ( m = 4-9; n = 1-4), where m represents the carbon-chain number and n equals layer-thickness number. Multilayer ( n > 1) 2D perovskites incorporating diammonium cations were successfully synthesized by the solid-state grinding method for m = 4 and 6 and by the solution method for m = 7-9. Structural characterization by single-crystal X-ray diffraction for the m = 8 and m = 9 series ( n = 1-4) reveals that these compounds adopt the Cc space group for even n members and Pc for odd n members. The optical bandgaps are 2.15 eV for two-layer ( n = 2), 2.01 eV for three-layer ( n = 3), and 1.90 eV for four-layer ( n = 4). The materials exhibit excellent solution processability, and casting thin-films of the n = 3 members was successfully accomplished. The films show a clear tendency for the higher- m members to have preferred orientation on the glass substrate, with m = 8 exhibiting almost perfect vertical layer orientation and m = 9 displaying both vertical and parallel layer orientation, as confirmed by grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The vertical layer orientation for the (NHCHNH)(CHNH)PbI member results in the best thermal, light, and air stability within this series, thus showing excellent potential for solar cell applications.

Hybrid halide perovskite solar cells with mixed cations demonstrate superior optical and electrical properties, especially for lead-based perovskite devices. Here, we report leadfree tin-based perovskite solar cells with diammonium cations, which can significantly improve the device performance. Formamidinium tin iodide (FASnI 3 ) perovskite can incorporate propylenediammonium (PN) and trimethylenediammonium (TN) and retain its three-dimensional structure while at the same time providing better film morphology and optoelectronic properties. As a result, solar cell devices using FASnI 3 absorbers mixed with 10% PN and 10% TN achieve higher power conversion efficiencies of 5.85% and 5.53%, respectively, compared to 2.53% of the pristine FASnI 3 solar cell. This difference in device performance can be mainly attributed to the reduced leakage current, lower trap-state density, and reduced recombination, as evidenced by our dark current−voltage, space-charge-limited current, and impedance measurements. The results suggest that perovskite absorbers with mixed diammonium cations are beneficial in achieving high-performance perovskite solar cells.

Singlet fission (SF) is a photophysical process in which one of two adjacent organic molecules absorbs a single photon, resulting in rapid formation of a correlated triplet pair (T1T1) state whose spin dynamics influence the successful generation of uncorrelated triplets (T1). Femtosecond transient visible and near-infrared absorption spectroscopy of a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI2), in which the two TDI molecules are directly linked at one of their imide positions, reveals ultrafast formation of the (T1T1) state. The spin dynamics of the (T1T1) state and the processes leading to uncoupled triplets (T1) were studied at room temperature for TDI2aligned in 4-cyano-4′-pentylbiphenyl (5CB), a nematic liquid crystal. Time-resolved electron paramagnetic resonance spectroscopy shows that the (T1T1) state has mixed5(T1T1) and3(T1T1) character at room temperature. This mixing is magnetic field dependent, resulting in a maximum triplet yield at ∼200 mT. The accessibility of the3(T1T1) state opens a pathway for triplet–triplet annihilation that produces a single uncorrelated T1state. The presence of the5(T1T1) state at room temperature and its relationship with the1(T1T1) and3(T1T1) states emphasize that understanding the relationship among different (T1T1) spin states is critical for ensuring high-yield T1formation from singlet fission.