Two-dimensional (2D) hybrid perovskites are stoichiometric compounds consisting of alternating inorganic metal-halide sheets and organoammonium cationic layers. This materials class is widely tailorable in composition, structure, and dimensionality and is providing an intriguing playground for the solid-state chemistry and physics communities to uncover structure-property relationships. In this Perspective, we describe semiconducting 2D perovskites containing lead and tin halide inorganic frameworks. In these 2D perovskites, charges are typically confined to the inorganic framework because of strong quantum and dielectric confinement effects, and exciton binding energies are many times greater than kT at room temperature. We describe the role of the heavy atoms in the inorganic framework; the geometry and chemistry of organic cations; and the "softness" of the organic-inorganic lattice on the electronic structure and dynamics of electrons, excitons, and phonons that govern the physical properties of these materials.

Quantum and dielectric confinement effects in 2D hybrid perovskites create excitons with a binding energy exceeding 150 meV. We exploit the large exciton binding energy to study exciton and carrier dynamics as well as electron-phonon coupling in hybrid perovskites using absorption and photoluminescence (PL) spectroscopies. At temperatures below 75 K, we resolve splitting of the excitonic absorption and PL into multiple regularly-spaced resonances every 40-46 meV, consistent with electron-phonon coupling to phonons located on the organic cation. We also resolve resonances with a 14 meV spacing, in accord with coupling to phonons with mixed organic and inorganic character, and these assignments are supported by density-functional theory calculations. Hot exciton PL and time-resolved PL measurements show that vibrational relaxation occurs on a picosecond timescale competitive with that for PL. At temperatures above 75 K, excitonic absorption and PL exhibit homogeneous broadening. While absorption remains homogeneous, PL becomes inhomogeneous below 75K, which we speculate is caused by the formation and subsequent dynamics of a polaronic exciton.

We use solid-state methods to synthesize single crystals of perovskite-phase cesium lead iodide (γ-CsPbI3) that are kinetically stable at room temperature. Single crystal X-ray diffraction characterization shows that the compound is orthorhombic with the GdFeO3 structure at room temperature. Unlike conventional semiconductors, the optical absorption and the joint density-ofstates of bulk γ-CsPbI3 is greatest near the band edge and decreases beyond Eg for at least 1.9 eV.Bulk γ-CsPbI3 does not show an excitonic resonance and has an optical band gap of 1.63(3) eV, ~90 meV smaller than has been reported in thin films; these and other differences indicate that previously-measured thin film γ-CsPbI3 shows signatures of quantum confinement. By flowing gases over γ-CsPbI3 during in situ powder X-ray diffraction measurements, we confirm that γ-CsPbI3 is stable to oxygen but rapidly and catalytically converts to non-perovskite δ-CsPbI3 in the presence of moisture. Our results on bulk γ-CsPbI3 provide vital parameters for theoretical and experimental investigations into perovskite-phase CsPbI3 that will the guide the design and synthesis of atmospherically stable inorganic halide perovskites.

We synthesize and characterize derivatives of the two-dimensional hybrid perovskite (2DHP) phenethylammonium lead iodide ((PEA)2PbI4) in which the para H on the cation is replaced with F, Cl, CH3, or Br. These substitutions increase the length of the cation but leave the cross-sectional area unchanged, resulting in structurally similar PbI4 2– frameworks with increasing interlayer spacing. Longer cations result in broader, blue-shifted excitonic absorption spectra with reduced or eliminated structure, indicating greater energetic disorder. Photoluminescence spectra are largely invariant and insensitive to cation length, suggesting polaron formation stabilizes a structural and electronic minimum. Temperature-dependent line width analysis reveals excitons couple to a vibration on the organic framework that is weakly sensitive to these cation substitutions, and Raman spectra and electronic structure calculations support the presence of such a cationic mode. Despite carriers being confined to the inorganic framework, the length of the organic cation alters the optical and electronic properties of 2DHPs.

Despite the tremendous interest in halide perovskite solar cells, the structural reasons that cause the all‐inorganic perovskite CsPbI3 to be unstable at room temperature remain mysterious, especially since many tolerance‐factor‐based approaches predict CsPbI3 should be stable as a perovskite. Here single‐crystal X‐ray diffraction and X‐ray pair distribution function (PDF) measurements characterize bulk perovskite CsPbI3 from 100 to 295 K to elucidate its thermodynamic instability. While Cs occupies a single site from 100 to 150 K, it splits between two sites from 175 to 295 K with the second site having a lower effective coordination number, which, along with other structural parameters, suggests that Cs rattles in its coordination polyhedron. PDF measurements reveal that on the length scale of the unit cell, the PbI octahedra concurrently become greatly distorted, with one of the IPbI angles approaching 82° compared to the ideal 90°. The rattling of Cs, low number of CsI contacts, and high degree of octahedral distortion cause the instability of perovskite‐phase CsPbI3. These results reveal the limitations of tolerance factors in predicting perovskite stability and provide detailed structural information that suggests methods to engineer stable CsPbI3‐based solar cells.