spectrum featuring a marked excitonic resonance, the majority optical excitation in prototypical HP materials for photovoltaics are not bound excitons, but unbound charge carriers. Therefore, electrons and holes excited by solar light can be directed to the electrodes at a negligible energy cost, without the need to split tightly bound excitons as in organics. Taking advantage of the flexibility of the materials class, layered 2D HPs are obtained by inserting bulky organic cations into the formulation, leading to materials inherently more stable than their 3D counterparts against degradation. [8][9][10] However, in 2D HPs the exciton binding energy can be as large as 400 meV, [8] so that it is commonly assumed that their excited states are mostly excitons.A second peculiar characteristic of the excited states in perovskites is the formation of large polarons, that is, charge carriers coupled to lattice deformations and delocalized over many crystal lattice sites. [11][12][13][14][15][16][17][18][19][20] Unlike small polarons in organics, localized in a single molecule, large polarons are compatible with band transport, but are also able to screen the excited states from scattering with defects and reduce non-radiative recombination through trap states, resulting in large mobilities and long lifetimes. Large polarons are also believed to reduce scattering with phonons and have been proposed as an explanation for hot carriers persisting for several nanoseconds at temperatures significantly higher than the lattice one. [12,16,17,[21][22][23][24][25][26] Large polarons may therefore be the enabling microscopic mechanism for efficient solar cells, including innovative architectures that exploit photoconversion with hot carriers. [27,28] Theoretical estimations forecast that the energy associated with polaron formation is comparable with the binding energy gained by forming an exciton, maybe even larger in some materials. [12,14,24,[29][30][31][32] When do polarons form and whether excitons or polarons are the lowest-energy optical excitations is still an open question. The issue is particularly relevant for layered 2D HPs, where polaronic effects have been demonstrated, although it is not clear if small or large polarons are formed. [33][34][35][36][37] In spite of the large exciton binding energy, unbound charge carriers have been reported, so that it is not clear yet how much energy needs to be spent in solar cells to split bound excitons.

Lead‐free Cs2AgInCl6 and Cs2AgInBr6 double perovskites are studied by a combination of advanced ab‐initio calculations and photoluminescence experiments. We show that they are insulators with direct band gaps of 2.53 and 1.17 eV, respectively; most importantly, they are characterized by unusually low absorption rates in a ~1 eV wide energy region above the band gap, caused by rather peculiar electronic properties. Consequently, this low absorption conveys very long recombination lifetimes, up to milliseconds at low temperature. Our theoretical analysis suggests that such materials can achieve a good compromise between photoconversion efficiency (above 10%) and visible transmittance (above 30%), which makes them potentially suited for lead‐free semitransparent solar cell applications.

Highly performing mixed Sn/Pb-metal halide perovskite solar cells (PSCs) are among the most promising options to reduce Pb content in perovskite devices and enable, owing to their reduced bandgap, the fabrication of all-perovskite tandem solar cells. Whereas pure-Pb perovskite devices exhibit efficiency up to 25.5%, alongside a high open-circuit voltage (≈1.2 V), Sn-Pb PSCs still show lower performances (22.2%) due to higher open-circuit voltage losses. Here, we introduced 2,3,4,5,6-pentafluorophenethylammonium cations in a perovskite active layer of composition (FASnI3)0.5(MAPbI3)0.5 to obtain highly oriented films with improved thermal stability. The treated films exhibit merged grains with no evidence of 2D structures, which could help to reduce the trap state density at the surface and grain boundaries. Solar cells fabricated with the fluorinated cation added to the active layer displayed reduced trap-assisted recombination losses and lower background carrier density, which leads to enhanced open-circuit voltages with respect to the reference samples and the active layers incorporating unfluorinated phenethylammonium cations. The best device reached an efficiency of 19.13%, with an open-circuit voltage of 0.84 V, which is substantially improved with respect to the reference sample showing 17.47% efficiency and 0.77 V open-circuit voltage. More importantly, the fluorinated cations' addition is instrumental to improve the device's thermal stability; 90.3% of the solar cell initial efficiency is maintained after 90 min of thermal stress at 85 °C in a nitrogen atmosphere.

Hybrid metal halide perovskite materials are produced with facile routes, but their morphology is sensitive to water, oxygen, temperature, and exposure to light. While phase separation and self-assembly of perovskite nanostructures have been demonstrated, the realization of controlled perovskite–perovskite heterostructures has been limited up to now. We demonstrate here the growth of stable CH3NH3PbI3–xBrx nanocrystals in a CH3NH3PbBr3 matrix. Optical emission from the nanocrystals can be reversibly activated upon illumination through a photobrightening process. Optical microscopy images show that nanocrystals are stable in time, through several illumination cycles. Ultrafast photoluminescence measurements imply that optical excitations are funneled from the matrix into the lower bandgap nanocrystals. Because the nanocrystals represent <2% of the materials volume, the local carrier concentration is higher in the nanocrystals than in the matrix, leading to an increase in the photoluminescence quantum yield, highlighting the promise of such self-assembled heterostructures for efficient light-emitting device

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Layered 2D perovskites are making inroads as materials for photovoltaics and light emitting diodes, but their photophysics is still lively debated. Although their large exciton binding energies should hinder charge separation, significant evidence has been uncovered for an abundance of free carriers among optical excitations. Several explanations have been proposed, like exciton dissociation at grain boundaries or polaron formation, without clarifying yet if excitons form and then dissociate, or if the formation is prevented by competing relaxation processes. Here we address exciton stability in layered Ruddlesden-Popper PEA2PbI4 (PEA stands for phenethylammonium) both in form of thin film and single crystal, by resonant injection of cold excitons, whose dissociation is then probed with femtosecond differential transmission. We show the intrinsic nature of exciton dissociation in 2D layered perovskites, demonstrating that both 2D and 3D perovskites are free carrier semiconductors and their photophysics is described by a unique and universal framework.

The rate of light emission per unit carrier concentration, or radiative rate, is a fundamental semiconductor parameter that determines the limit photoconversion efficiency of solar cells. In hybrid perovskites, a...

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