skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Entropy-driven stabilization of the cubic phase of MaPbI 3 at room temperature
Methylammonium lead iodide (MAPbI 3 ) is an important light-harvesting semiconducting material for solar-cell devices. We investigate the effect of long thermal annealing in an inert atmosphere of compacted MAPbI 3 perovskite powders. The microstructure morphology of the MAPbI 3 annealed samples reveals a well-defined grain boundary morphology. The voids and neck-connecting grains are observed throughout the samples, indicating a well-sintered process due to mass diffusion transfer through the grain boundary. The long 40 h thermal annealing at T = 522 K ( k B T = 45 meV) causes a significant shift in the structural phase transition, stabilizing the low-electrical conductivity and high-efficiency cubic structure at room temperature. The complete disordered orientation of MA cations maximizes the entropy of the system, which, in turn, increases the Pb–I–Pb angle close to 180°. The MA rotation barrier and entropy analysis determined through DFT calculations suggest that the configurational entropy is a function of the annealing time. The disordered organic molecules are quenched and become kinetically trapped in the cubic phase down to room temperature. We propose a new phase diagram for this important system combining different structural phases as a function of temperature with annealing time for MAPbI 3 . The absence of the coexistence of different structural phases, leading to thermal hysteresis, can significantly improve the electrical properties of the solar cell devices. Through an entropy-driven stabilization phenomenon, we offer an alternative path for improving the maintenance, toughness, and efficiency of the optoelectronic devices by removing the microstructural stress brought by the structural phase transformation within the solar cell working temperature range.  more » « less
Award ID(s):
1652994
PAR ID:
10211425
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry A
Volume:
9
Issue:
2
ISSN:
2050-7488
Page Range / eLocation ID:
1089 to 1099
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, MRS Advances)
    ABSTRACT Hybrid perovskite solar cells (PSCs) under normal operation will reach a temperature above ∼ 60 °C, across the tetragonal-cubic structural phase transition of methylammonium lead iodide (MAPbI 3 ). Whether the structural phase transition could result in dramatic changes of ionic, electrical and optical properties that may further impact the PSC performances should be studied. Herein, we report a structural phase transition temperature of MAPbI 3 thin film at ∼ 55 °C, but a striking contrast occurred at ∼ 45 °C in the ionic and electrical properties of MAPbI 3 due to a change of the ion activation energy from 0.7 eV to 0.5 eV. The optical properties exhibited no sharp transition except for the steady increase of the bandgap with temperature. It was also observed that the activation energy for ionic migration steadily increased with increased grain sizes, and reduction of the grain boundary density reduced the ionic migration. 
    more » « less
  2. ; ; ; (, Advanced Materials Interfaces)
    Abstract Nanostructuring to reduce thermal conductivity is among the most promising strategies for designing next‐generation, high‐performance thermoelectric materials. In practice, electrical grain boundary resistance can overwhelm the thermal conductivity reduction induced by nanostructuring, which results in worse overall performance. Since a large body of work has characterized the transport of both polycrystalline ceramics and single crystals of SrTiO3, it is an ideal material system for conducting a case study of electrical grain boundary resistance. An effective mass model is used to characterize the transport signatures of electrical grain boundary resistance and evaluate thermodynamic design principles for controlling that resistance. Treating the grain boundary as a secondary phase to the bulk crystallites explains the transport phenomena. Considering that the interface can be engineered by controlling oxygen partial pressure, temperature, and the addition of extrinsic elements into the grain boundary phase, the outlook for SrTiO3as a nanostructured thermoelectric is promising, and thezTcould be greater than 0.5 at room temperature. 
    more » « less
  3. ; ; ; ; ; ; (, Advanced Science)
    Abstract The vast high entropy alloy (HEA) composition space is promising for discovery of new material phases with unique properties. This study explores the potential to achieve rare‐earth‐free high magnetic anisotropy materials in single‐phase HEA thin films. Thin films of FeCoNiMnCu sputtered on thermally oxidized Si/SiO2substrates at room temperature are magnetically soft, with a coercivity on the order of 10 Oe. After post‐deposition rapid thermal annealing (RTA), the films exhibit a single face‐centered‐cubic phase, with an almost 40‐fold increase in coercivity. Inclusion of 50 at.% Pt in the film leads to ordering of a singleL10high entropy intermetallic phase after RTA, along with high magnetic anisotropy and 3 orders of magnitude coercivity increase. These results demonstrate a promising HEA approach to achieve high magnetic anisotropy materials using RTA. 
    more » « less
  4. ; ; ; ; ; ; (, Journal of Applied Physics)
    In this study, phase transitions (structural and magnetic) and associated magnetocaloric properties of stoichiometric MnCoGe have been investigated as a function of annealing pressure. Metastable phases were generated by annealing at 800 °C followed by rapid cooling under pressures up to 6.0 GPa. The x-ray diffraction results reveal that the crystal cell volume of the metastable phases continuously decreases with increasing thermal processing pressure, leading to a decrease in the structural transition temperature. The magnetic and structural transitions merge and form a first-order magnetostructural transition between the ferromagnetic orthorhombic and paramagnetic hexagonal phases over a broad temperature range (>80 K) spanning room temperature, yielding considerable magnetic entropy changes. These findings demonstrate the utility of thermal processing under high pressure, i.e., high-pressure annealing, to control the magnetostructural transitions and associated magnetocaloric properties of MnCoGe without altering its chemical composition. 
    more » « less
  5. ; ; ; ; ; (, Angewandte Chemie International Edition)
    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
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email