Title: Remarkable long-term stability of nanoconfined metal–halide perovskite crystals against degradation and polymorph transitions
Metal–halide perovskites are promising candidates to advance optoelectronic devices but are known to suffer from rapid material degradation. Here we demonstrate that nanoconfinement is an effective strategy for the long-term stabilization of metal–halide perovskite MAPbI 3 crystals against humidity-induced degradation and temperature-induced polymorph transitions. Two-dimensional X-ray diffraction patterns of MAPbI 3 films reveal an unprecedented air-stability of up to 594 days in non-chemically modified, non-passivated MAPbI 3 films deposited on substrates imposing complete 2D confinement on the tens of nanometers length scale. Temperature-dependent X-ray diffraction analysis and optical spectroscopy further reveal the suppression of temperature-dependent phase transitions in nanoconfined MAPbI 3 crystals. Most notably, the high-temperature cubic phase of MAPbI 3 , typically stable at temperatures above 327 K, remains present until a temperature of 170 K when the perovskite crystals are nanoconfined within the 100 nm diameter pores of anodized aluminum oxide templates. Photoluminescence mapping confirms that nanoconfined MAPbI 3 crystals exhibit spatial uniformity on the tens of microns length scale, suggesting that nanoconfinement is an effective strategy for the formation of high-quality, stable MAPbI 3 crystals across large areas.  more » « less
Award ID(s):
1531237
PAR ID:
10080617
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
10
Issue:
17
ISSN:
2040-3364
Page Range / eLocation ID:
8320 to 8328
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Two-dimensional halide perovskites exhibit rich structural diversity and tunable optoelectronic properties, making them promising materials for energy, sensing, and photonic applications. We report the structural mapping of four distinct polymorphs, γ (P21/c), β (P4/mbm), α (P4/mmm), and δ (Cmcm) in the two-dimensional iodoplumbate, iodostannate, and iodogermanate perovskite so-called Dion–Jacobson series (3AMP)MI4 (M = Sn, Pb, Ge), where 3AMP is 3-(aminomethyl)piperidinium. The phases exhibit systematic evolution in octahedral distortion, lattice symmetry, and metal–halide geometry, enabling structural control over optoelectronic properties. Notably, the α-phase of (3AMP)SnI4 represents a rare, ambient-stable, high-symmetry structure for Sn-based perovskites, without a phase transition down to 100 K. Variable-temperature single-crystal diffraction, powder X-ray diffraction (PXRD), and calorimetry reveal metal- and temperature-dependent polymorph interconversions, including the emergence of long-range supercell reflections in Pb-rich compositions at low temperature. Optical spectroscopy and photoelectron yield spectroscopy confirm band gap tunability and band alignment trends, highlighting symmetry-dependent shifts and anomalous band gap bowing in mixed-metal systems, verified by electronic structure calculations. Calculations additionally indicate that the higher symmetry phases have reduced electron and hole effective masses compared to the lower symmetry phases. 
    more » « less
  2. Abstract Cesium methylammonium lead iodide (CsxMA1−xPbI3) nanocrystals were obtained with a wide range of A‐site Cs‐MA compositions by post‐synthetic, room temperature cation exchange between CsPbI3nanocrystals and MAPbI3nanocrystals. The alloyed CsxMA1−xPbI3nanocrystals retain their photoactive perovskite phase with incorporated Cs content,x, as high as 0.74 and the expected composition‐tunable photoluminescence (PL). Excess methylammonium oleate from the reaction mixture in the MAPbI3nanocrystal dispersions was necessary to obtain fast Cs‐MA cation exchange. The phase transformation and degradation kinetics of films of CsxMA1−xPbI3nanocrystals were measured and modeled using an Avrami expression. The transformation kinetics were significantly slower than those of the parent CsPbI3and MAPbI3nanocrystals, with Avrami rate constants,k, at least an order of magnitude smaller. These results affirm that A‐site cation alloying is a promising strategy for stabilizing iodide‐based perovskites. 
    more » « less
  3. Organic-inorganic halide perovskites are promising semiconductors for energy-conversion applications, but these materials face an inherent limitation due to poor intrinsic stability, particularly via decomposition upon exposure to water. The dimensionality and stability of perovskite materials are highly dependent on the organic cation in the perovskite. The incorporation of bulky organic ligands in the structure induces 2D layered perovskites where organic ligands are perpendicular to the inorganic layers and can enhance the perovskite moisture stability through the ligand hydrophobicity. Herein, the relative water stability of reportedly water-stable organic-inorganic halide perovskites were compared between microparticulate powders and compact thin films. In particular, the 3D perovskite DMASnBr3 (DMA = dimethylammonium) and 2D perovskite (PEA)2SnBr4 (PEA = phenylethylammonium) were synthesized in both forms and characterized for water stability. The microparticulate crystals of both materials exhibited significant stability in water while analogous thin films were highly unstable, which was attributed to the presence of a soluble intermixed phase. A new bulky organic ligand, 8-(2,5-bis(thiophen-2-yl)-1H-pyrrol-1-yl)-octylammonium (2TPO), with hydrophobic wing-like groups to help impede water ingress was synthesized and incorporated into a 2D perovskite structure. A thin film of (2TPO)2PbI4 exhibited strongly enhanced durability when fully immersed in water for several minutes or exposed to 85% relative humidity for several days. Material stability was characterized using techniques such as X-ray diffraction (XRD), UV-visible spectroscopy, and X-ray photoelectron spectroscopy (XPS). 
    more » « less
  4. Phase transitions in halide perovskites triggered by external stimuli generate significantly different material properties, providing a great opportunity for broad applications. Here, we demonstrate an In-based, charge-ordered (In+/In3+) inorganic halide perovskite with the composition of Cs2In(I)In(III)Cl6 in which a pressure-driven semiconductor-to-metal phase transition exists. The single crystals, synthesized via a solid-state reaction method, crystallize in a distorted perovskite structure with space group I4/m with a = 17.2604(12) Å, c = 11.0113(16) Å if both the strong reflections and superstructures are considered. The supercell was further confirmed by rotation electron diffraction measurement. The pressure-induced semiconductor-to-metal phase transition was demonstrated by high-pressure Raman and absorbance spectroscopies and was consistent with theoretical modeling. This type of charge-ordered inorganic halide perovskite with a pressure-induced semiconductor-to-metal phase transition may inspire a range of potential applications. 
    more » « less
  5. Photovoltaic cells based on metal‐halide perovskites have exceeded the performance of other thin film technologies and rival the performance of devices based on archetypical silicon. Attractively, the perovskite active layer can be processed via a variety of solution‐ and vapor‐based methods. Herein, emphasis is on the use of vapor transport codeposition (VTD) to process efficient n–i–p photovoltaic cells based on methylammonium lead iodide (MAPbI3). VTD utilizes a hot‐walled reactor operated under moderate vacuum in the range of 0.5–10 Torr. The organic and metal‐halide precursors are heated with the resulting vapor transported by a N2carrier gas to a cooled substrate where they condense and react to form a perovskite film. The efficiency of photovoltaic devices based on VTD‐processed MAPbI3is found to be highest in films with excess lead iodide content, with champion devices realizing exceeding 12%. 
    more » « less