We assess the performance of recent density functionals for the exchange-correlation energy of a nonmolecular solid, by applying accurate calculations with the GAUSSIAN, BAND, and VASP codes to a test set of 24 solid metals and nonmetals. The functionals tested are the modified Perdew-Burke-Ernzerhof generalized gradient approximation PBEsol GGA, the second-order GGA SOGGA, and the Armiento-Mattsson 2005 AM05 GGA. For completeness, we also test more standard functionals: the local density approximation, the original PBE GGA, and the Tao-Perdew-Staroverov-Scuseria meta-GGA. We find that the recent density functionals for solids reach a high accuracy for bulk properties lattice constant and bulk modulus. For the cohesive energy, PBE is better than PBEsol overall, as expected, but PBEsol is actually better for the alkali metals and alkali halides. For fair comparison of calculated and experimental results, we consider the zeropoint phonon and finite-temperature effects ignored by many workers. We show how GAUSSIAN basis sets and inaccurate experimental reference data may affect the rating of the quality of the functionals. The results show that PBEsol and AM05 perform somewhat differently from each other for alkali metal, alkaline-earth metal, and alkali halide crystals where the maximum value of the reduced density gradient is about 2, but perform very similarly for most of the other solids where it is often about 1. Our explanation for this is consistent with the importance of exchange-correlation nonlocality in regions of core-valence overlap.

https://dspace.mit.edu/openaccess-disseminate/1721.1/51869

Assessing the performance of recent density functionals for bulk solids

Quasi-2D perovskites have long been considered to have favorable "energy funnel/cascade" structures and excellent optical properties compared with their 3D counterparts. However, most quasi-2D perovskite light-emitting diodes (PeLEDs) exhibit high external quantum efficiency (EQE) but unsatisfactory operating stability due to Auger recombination induced by high current density. Herein, a synergetic dual-additive strategy is adopted to prepare perovskite films with low defect density and high environmental stability by using 18-crown-6 and poly(ethylene glycol) methyl ether acrylate (MPEG-MAA) as the additives. The dual additives containing COC bonds can not only effectively reduce the perovskite defects but also destroy the self-aggregation of organic ligands, inducing the formation of perovskite nanocrystals with quasi-core/shell structure. After thermal annealing, the MPEG-MAA with its CC bond can be polymerized to obtain a comb-like polymer, further protecting the passivated perovskite nanocrystals against water and oxygen. Finally, state-of-the-art green PeLEDs with a normal EQE of 25.2% and a maximum EQE of 28.1% are achieved, and the operating lifetime (T50 ) of the device in air environment is over ten times increased, providing a novel and effective strategy to make high efficiency and long operating lifetime PeLEDs.

Perovskite Light-Emitting Diodes with EQE Exceeding 28% through a Synergetic Dual-Additive Strategy for Defect Passivation and Nanostructure Regulation.

Quasi-two-dimensional (quasi-2D) Ruddlesden–Popper (RP) perovskites such as BA2Csn–1PbnBr3n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A−1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far. Owing to large exciton binding energy, quasi-2D perovskite is promising for light-emitting application, yet inhomogeneous phases distribution limits the potential. Here, the authors improve the performance by using MeS additive to regulate the phase distribution and to reduce defect density in the films.

/pdf/smoothing-the-energy-transfer-pathway-in-quasi-2d-perovskite-i2nia41mip.pdf

Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices.

Inorganic Halide Perovskite Solar Cells: Progress and Challenges

Surface reaction for efficient and stable inverted perovskite solar cells

In halide perovskite solar cells the formation of secondary-phase excess lead iodide (PbI2) has some positive effects on power conversion efficiency (PCE) but can be detrimental to device stability and lead to large hysteresis effects in voltage sweeps. We converted PbI2 into an inactive (PbI2)2RbCl compound by RbCl doping, which effectively stabilizes the perovskite phase. We obtained a certified PCE of 25.6% for FAPbI3 (FA, formamidinium) perovskite solar cells on the basis of this strategy. Devices retained 96% of their original PCE values after 1000 hours of shelf storage and 80% after 500 hours of thermal stability testing at 85°C. Description Managing excess lead iodide In hybrid perovskite solar cells, the formation of lead iodide (PbI2) can provide some passivation effects but can lead to device instability and hysteresis in current–density changes with voltage. Zhao et al. show that doping with rubidium chloride (RbCl) can create a passive inactive (PbI2)2RbCl phase that stabilizes the perovskite phase and lowers its bandgap. Devices exhibited 25.6% certified power efficiency and maintained 80% of that efficiency after 500 hours of operation at 85°C. —PDS Converting PbI2 into inactive (PbI2)2RbCl by RbCl doping can stabilize the perovskite phase and increase efficiency.

Inactive (PbI2)2RbCl stabilizes perovskite films for efficient solar cells

Perovskite light-emitting diodes (PeLEDs) have showed significant progress in recent years; the external quantum efficiency (EQE) of electroluminescence in green and red regions has exceeded 20%, but the efficiency in blue lags far behind. Here, a large cation CH3CH2NH2+ is added in PEA2(CsPbBr3)2PbBr4 perovskite to decrease the Pb–Br orbit coupling and increase the bandgap for blue emission. X-ray diffraction and nuclear magnetic resonance results confirmed that the EA has successfully replaced Cs+ cations to form PEA2(Cs1-xEAxPbBr3)2PbBr4. This method modulates the photoluminescence from the green region (508 nm) into blue (466 nm), and over 70% photoluminescence quantum yield in blue is obtained. In addition, the emission spectra is stable under light and thermal stress. With configuration of PeLEDs with 60% EABr, as high as 12.1% EQE of sky-blue electroluminescence located at 488 nm has been demonstrated, which will pave the way for the full color display for the PeLEDs. Blue light-emitting diodes (LEDs) are critical for displays. Employing a large organic cation into a quasi-two dimensional perovskite with green emission, Chu et al. achieve LEDs exhibiting a high external quantum efficiency of 12.1% and stable spectra in the sky-blue region.

/pdf/large-cation-ethylammonium-incorporated-perovskite-for-2jrapbjdj1.pdf

Large cation ethylammonium incorporated perovskite for efficient and spectra stable blue light-emitting diodes

Perovskite light-emitting diodes (PeLEDs) are considered as particularly attractive candidates for high-quality lighting and displays, due to possessing the features of wide gamut and real color expression However, most PeLEDs are made from polycrystalline perovskite films that contain a high concentration of defects, including point and extended imperfections Reducing and mitigating non-radiative recombination defects in perovskite materials are still crucial prerequisites for achieving high performance in light-emitting applications Here, ethoxylated trimethylolpropane triacrylate (ETPTA) is introduced as a functional additive dissolved in antisolvent to passivate surface and bulk defects during the spinning process The ETPTA can effectively decrease the charge trapping states by passivation and/or suppression of defects Eventually, the perovskite films that are sufficiently passivated by ETPTA make the devices achieve a maximum external quantum efficiency (EQE) of 2249% To our knowledge, these are the most efficient green PeLEDs up to now In addition, a threefold increase in the T50 operational time of the devices was observed, compared to control samples These findings provide a simple and effective strategy to make highly efficient perovskite polycrystalline films and their optoelectronics devices

Perovskite Light-Emitting Diodes with External Quantum Efficiency Exceeding 22% via Small-Molecule Passivation.

Cesium-based inorganic perovskite solar cells (PSCs) are promising due to their potential for improving device stability. However, the power conversion efficiency of the inorganic PSCs is still low compared with the hybrid PSCs due to the large open-circuit voltage (VOC ) loss possibly caused by charge recombination. The use of an insulated shunt-blocking layer lithium fluoride on electron transport layer SnO2 for better energy level alignment with the conduction band minimum of the CsPbI3-x Brx and also for interface defect passivation is reported. In addition, by incorporating lead chloride in CsPbI3-x Brx precursor, the perovskite film crystallinity is significantly enhanced and the charge recombination in perovksite is suppressed. As a result, optimized CsPbI3-x Brx PSCs with a band gap of 1.77 eV exhibit excellent performance with the best VOC as high as 1.25 V and an efficiency of 18.64%. Meanwhile, a high photostability with a less than 6% efficiency drop is achieved for CsPbI3-x Brx PSCs under continuous 1 sun equivalent illumination over 1000 h.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/adma.202100344

Fei Ma

Papers

Inactive (PbI2)2RbCl stabilizes perovskite films for efficient solar cells

Large cation ethylammonium incorporated perovskite for efficient and spectra stable blue light-emitting diodes

Perovskite Light-Emitting Diodes with External Quantum Efficiency Exceeding 22% via Small-Molecule Passivation.

Cesium Lead Inorganic Solar Cell with Efficiency beyond 18% via Reduced Charge Recombination.

Nickel oxide for inverted structure perovskite solar cells