Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH3NH3PbCl3 and CH3NH3PbI3 or (C4H9NH3)2(CH3NH3) n-1Pb nI3 n+1 Mixtures.

Lead halide perovskites present a versatile class of solution-processable semiconductors with highly tunable bandgaps that span ultraviolet, visible, and near-infrared portions of the spectrum. We explore phase-separated chloride and iodide lead perovskite mixtures as candidate materials for intermediate band applications in future photovoltaics. X-ray diffraction and scanning electron microscopy reveal that deposition of precursor solutions across the MAPbCl3/MAPbI3 composition space affords quasi-epitaxial cocrystallized films, in which the two perovskites do not alloy but instead remain phase-segregated. First-principle calculations further support the formation of an epitaxial interface and predict energy offsets in the valence band and conduction band edges that could result in intermediate energy absorption. The charge dynamics of variable mixtures of the relatively narrow bandgap (1.57 eV) MAPbI3 perovskite and wide bandgap (3.02 eV) MAPbCl3 are probed to map charge and energy flow direction and kinetics. Time-resolved photoluminescence and transient absorption measurements reveal charge transfer of photoexcited carriers in MAPbCl3 to MAPbI3 in tens of picoseconds. The rate of quenching can be further tuned by replacing MAPbI3 with two-dimensional Ruddlesden-Popper (BA)2(MA) n-1Pb nI3 n+1 ( n = 3, 2, and 1) perovskites, which also remain phase-separated.

Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices.

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH3NH3PbI3) are game-changing semiconductors for solar cells and light-emitting devices owing to their defect tolerance and exceptionally long carrier lifetimes and diffusion lengths. Determining whether the dynamically disordered organic cations with large dipole moment benefit the optoelectronic properties of CH3NH3PbI3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the inorganic sublattice. The resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that the induced atomic motions of the organic cations do not alter the absorption or the photoluminescence response of CH3NH3PbI3, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH3NH3PbI3 mainly derive from the inorganic lead-halide framework.

Structural and thermodynamic limits of layer thickness in 2D halide perovskites.

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A')2(A) n-1M n X3n+1 [where A = Cs+, CH3NH3+, HC(NH2)2+; A' = ammonium cation acting as spacer; M = Ge2+, Sn2+, Pb2+; and X = Cl-, Br-, I-] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure-function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH3(CH2)2NH3)2(CH3NH3)5Pb6I19 (n = 6) and (CH3(CH2)2NH3)2(CH3NH3)6Pb7I22 (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for "(CH3(CH2)2NH3)2(CH3NH3)8Pb9I28" ("n = 9"). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔHf), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9-12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.

Interconversion between Free Charges and Bound Excitons in 2D Hybrid Lead Halide Perovskites.

The optoelectronic properties of hybrid perovskites can be easily tailored by varying their components. Specifically, mixing the common short organic cation (methylammonium (MA)) with a larger one (e.g., butyl ammonium (BA)) results in 2-dimensional perovskites with varying thicknesses of inorganic layers separated by the large organic cation. In both of these applications, a detailed understanding of the dissociation and recombination of electron-hole pairs is of prime importance. In this work, we give a clear experimental demonstration of the interconversion between bound excitons and free charges as a function of temperature by combining microwave conductivity techniques with photoluminescence measurements. We demonstrate that the exciton binding energy varies strongly (between 80 and 370 meV) with the thickness of the inorganic layers. Additionally, we show that the mobility of charges increases with the layer thickness, in agreement with calculated effective masses from electronic structure calculations.

Importance of Reducing Vapor Atmosphere in the Fabrication of Tin-Based Perovskite Solar Cells.

Tin-based halide perovskite materials have been successfully employed in lead-free perovskite solar cells, but the tendency of these materials to form leakage pathways from p-type defect states, mainly Sn4+ and Sn vacancies, causes poor device reproducibility and limits the overall power conversion efficiencies (PCEs). Here, we present an effective process that involves a reducing vapor atmosphere during the preparation of Sn-based halide perovskite solar cells to solve this problem, using MASnI3, CsSnI3, and CsSnBr3 as the representative absorbers. This process enables the fabrication of remarkably improved solar cells with PCEs of 3.89%, 1.83%, and 3.04% for MASnI3, CsSnI3, and CsSnBr3, respectively. The reducing vapor atmosphere process results in more than 20% reduction of Sn4+/Sn2+ ratios, which leads to greatly suppressed carrier recombination, to a level comparable to their lead-based counterparts. These results mark an important step toward a deeper understanding of the intrinsic Sn-based halide perovskite materials, paving the way to the realization of low-cost and lead-free Sn-based halide perovskite solar cells.

Liquid Water- and Heat-Resistant Hybrid Perovskite Photovoltaics via an Inverted ALD Oxide Electron Extraction Layer Design.

Despite rapid advances in conversion efficiency (>22%), the environmental stability of perovskite solar cells remains a substantial barrier to commercialization. Here, we show a significant improvement in the stability of inverted perovskite solar cells against liquid water and high operating temperature (100 °C) by integrating an ultrathin amorphous oxide electron extraction layer via atomic layer deposition (ALD). These unencapsulated inverted devices exhibit a stable operation over at least 10 h when subjected to high thermal stress (100 °C) in ambient environments, as well as upon direct contact with a droplet of water without further encapsulation.

Amorphous TiO2 Compact Layers via ALD for Planar Halide Perovskite Photovoltaics.

A low-temperature (<120 °C) route to pinhole-free amorphous TiO2 compact layers may pave the way to more efficient, flexible, and stable inverted perovskite halide device designs. Toward this end, we utilize low-temperature thermal atomic layer deposition (ALD) to synthesize ultrathin (12 nm) compact TiO2 underlayers for planar halide perovskite PV. Although device performance with as-deposited TiO2 films is poor, we identify room-temperature UV-O3 treatment as a route to device efficiency comparable to crystalline TiO2 thin films synthesized by higher temperature methods. We further explore the chemical, physical, and interfacial properties that might explain the improved performance through X-ray diffraction, spectroscopic ellipsometry, Raman spectroscopy, and X-ray photoelectron spectroscopy. These findings challenge our intuition about effective electron selective layers as well as point the way to a greater selection of flexible substrates and more stable inverted device designs.

Overcoming Short-Circuit in Lead-Free CH3NH3SnI3 Perovskite Solar Cells via Kinetically Controlled Gas-Solid Reaction Film Fabrication Process.

The development of Sn-based perovskite solar cells has been challenging because devices often show short-circuit behavior due to poor morphologies and undesired electrical properties of the thin films. A low-temperature vapor-assisted solution process (LT-VASP) has been employed as a novel kinetically controlled gas-solid reaction film fabrication method to prepare lead-free CH3NH3SnI3 thin films. We show that the solid SnI2 substrate temperature is the key parameter in achieving perovskite films with high surface coverage and excellent uniformity. The resulting high-quality CH3NH3SnI3 films allow the successful fabrication of solar cells with drastically improved reproducibility, reaching an efficiency of 1.86%. Furthermore, our Kelvin probe studies show the VASP films have a doping level lower than that of films prepared from the conventional one-step method, effectively lowering the film conductivity. Above all, with (LT)-VASP, the short-circuit behavior often obtained from the conventional one-step-fabricated Sn-based perovskite devices has been overcome. This study facilitates the path to more successful Sn-perovskite photovoltaic research.

2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications.

We report on the fabrication and properties of the semiconducting 2D (CH3(CH2)3NH3)2(CH3NH3)(n-1)Pb(n)I(3n+1) (n = 1, 2, 3, and 4) perovskite thin films. The band gaps of the series decrease with increasing n values, from 2.24 eV (CH3(CH2)3NH3)2PbI4 (n = 1) to 1.52 eV CH3NH3PbI3 (n = ∞). The compounds exhibit strong light absorption in the visible region, accompanied by strong photoluminescence at room temperature, rendering them promising light absorbers for photovoltaic applications. Moreover, we find that thin films of the semi-2D perovskites display an ultrahigh surface coverage as a result of the unusual film self-assembly that orients the [Pb(n)I(3n+1)](-) layers perpendicular to the substrates. We have successfully implemented this 2D perovskite family in solid-state solar cells, and obtained an initial power conversion efficiency of 4.02%, featuring an open-circuit voltage (V(oc)) of 929 mV and a short-circuit current density (J(sc)) of 9.42 mA/cm(2) from the n = 3 compound. This result is even more encouraging considering that the device retains its performance after long exposure to a high-humidity environment. Overall, the homologous 2D halide perovskites define a promising class of stable and efficient light-absorbing materials for solid-state photovoltaics and other applications.