CsSnI(3) is an unusual perovskite that undergoes complex displacive and reconstructive phase transitions and exhibits near-infrared emission at room temperature. Experimental and theoretical studies of CsSnI(3) have been limited by the lack of detailed crystal structure characterization and chemical instability. Here we describe the synthesis of pure polymorphic crystals, the preparation of large crack-/bubble-free ingots, the refined single-crystal structures, and temperature-dependent charge transport and optical properties of CsSnI(3), coupled with ab initio first-principles density functional theory (DFT) calculations. In situ temperature-dependent single-crystal and synchrotron powder X-ray diffraction studies reveal the origin of polymorphous phase transitions of CsSnI(3). The black orthorhombic form of CsSnI(3) demonstrates one of the largest volumetric thermal expansion coefficients for inorganic solids. Electrical conductivity, Hall effect, and thermopower measurements on it show p-type metallic behavior with low carrier density, despite the optical band gap of 1.3 eV. Hall effect measurements of the black orthorhombic perovskite phase of CsSnI(3) indicate that it is a p-type direct band gap semiconductor with carrier concentration at room temperature of ∼ 10(17) cm(-3) and a hole mobility of ∼585 cm(2) V(-1) s(-1). The hole mobility is one of the highest observed among p-type semiconductors with comparable band gaps. Its powders exhibit a strong room-temperature near-IR emission spectrum at 950 nm. Remarkably, the values of the electrical conductivity and photoluminescence intensity increase with heat treatment. The DFT calculations show that the screened-exchange local density approximation-derived band gap agrees well with the experimentally measured band gap. Calculations of the formation energy of defects strongly suggest that the electrical and light emission properties possibly result from Sn defects in the crystal structure, which arise intrinsically. Thus, although stoichiometric CsSnI(3) is a semiconductor, the material is prone to intrinsic defects associated with Sn vacancies. This creates highly mobile holes which cause the materials to appear metallic.

Layered Ruddlesden-Popper (RP) hybrid perovskite semiconductors have recently emerged as promising materials for photovoltaics application. However, the strong quantum and dielectric confinement of RP perovskite compounds increases their optical bandgap and binding energy of exciton, which limit their application in solar cells. Herein, the doping of RP-based (BA) 2 (MA) 3 Pb 4 I 13 perovskite materials by means of Li + is reported for the first time, which can significantly help to reduce dielectric confinement and thus the exciton-binding energy via reducing the dielectric constant difference between organic spacer cation and inorganic framework. Furthermore, the Li + doping boosts the carrier mobility, reduces the trap density states, and thus allows to achieve power conversion efficiency of ≈15% via Li + -(BA) 2 (MA) 3 Pb 4 I 13 -based perovskite solar cell, which is the highest efficiency for layered perovskites (n = 4) so far. This work highlights the promising ionic doping engineering for further improvement of the layered perovskite materials.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) with tantalizing layer-dependent electronic and optical properties have emerged as a paradigm for integrated flat opto-electronic devices, but their widespread applications are hampered by challenges in deterministic fabrication with demanded shapes and thicknesses, as well as light field manipulation in such atomic-thick layers with negligible thicknesses compared to the wavelength. Here we demonstrate ultra-sensitive light field manipulation in full visible ranges based on MoS2 laser prints exfoliated with nanometric precisions. The nontrivial interfacial phase shifts stemming from the unique dispersion of MoS2 layers integrated on the metallic substrate empower an ultra-sensitive resonance manipulation up to 13.95 nm per MoS2 layer across the entire visible bands, which is up to one-order-of-magnitude larger than their counterparts. The interlayer van der Waals interactions and the anisotropic thermal conductivity of layered MoS2 films endow a laser exfoliation method for on-demand patterning MoS2 with atomic thickness precision and subwavelength feature sizes. With this, nanometric flat color prints and further amplitude-modulated diffractive components for binocular stereoscopic images can be realized in a facile and lithography-free fashion. Our results with demonstrated practicality unlock the potentials of, and pave the way for, widespread applications of emerging 2D flat optics.

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