How Bromine Stabilizes CsPbI$_{3}$: Atomistic Insights from Reactive Molecular Dynamics Simulations DOI Creative Commons
Mike Pols, Adri C. T. van Duin, Sofı́a Calero

et al.

arXiv (Cornell University), Journal Year: 2023, Volume and Issue: unknown

Published: Jan. 1, 2023

All-inorganic halide perovskites have received a lot of attention as attractive alternatives to overcome the stability issues hybrid that are commonly associated with organic cations. To find compromise between optoelectronic properties CsPbI$_{3}$ and CsPbBr$_{3}$, CsPb(Br$_{\rm{x}}$I$_{\rm{1-x}}$)$_{3}$ mixed compositions used. An additional benefit is that, without sacrificing for applications such solar cells or LEDs, small amounts Br in can prevent inorganic perovskite from degrading photoinactive nonperovskite yellow phase. Despite indications strain lattice plays role stabilization material, full understanding lacking. Here we develop reactive force field (ReaxFF) starting our previous work CsPbI$_{3}$, extend this CsPbBr$_{3}$ compounds. This used large-scale molecular dynamics simulations study phase transitions internal ion transitions. We an increase content lowers temperature at which reaches cubic structure. Specifically, by substituting I, smaller ionic radius induces changes octahedra. Importantly, effect propagates through ranging up distances 2 nm, explaining why concentrations (x $\leq$ 1/4) significant impact on perovskites.

Language: Английский

Phase Transitions and Dynamics in Mixed Three- and Low-Dimensional Lead Halide Perovskites DOI Creative Commons
Mantas Šimėnas, Anna Gągor, J. Banys

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(5), P. 2281 - 2326

Published: Feb. 29, 2024

Lead halide perovskites are extensively investigated as efficient solution-processable materials for photovoltaic applications. The greatest stability and performance of these compounds achieved by mixing different ions at all three sites the APbX

Language: Английский

Citations

38
Structure Prediction of Ionic Epitaxial Interfaces with Ogre Demonstrated for Colloidal Heterostructures of Lead Halide Perovskites DOI Creative Commons
Stefano Toso,

Derek Dardzinski,

Liberato Manna

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Colloidal epitaxial heterostructures are nanoparticles composed of two different materials connected at an interface, which can exhibit properties from those their individual components. Combining dissimilar offers exciting opportunities to create a wide variety functional heterostructures. However, assessing structural compatibility─the main prerequisite for growth─is challenging when pairing complex with lattice parameters and crystal structures. This complicates both the selection target synthesis assignment interface models new obtained. Here, we demonstrate Ogre as powerful tool accelerate design characterization colloidal To this end, implemented developments tailored high-efficiency prediction interfaces between ionic/polar materials, encompass most semiconductors. These include use pre-screening candidate based on charge balance classical potential fast energy evaluations, automatically calculated input bulk validated perovskite-based CsPbBr3/Pb4S3Br2 heterostructures, where produces in excellent agreement density theory experiments. Furthermore, rationalize templating effect CsPbCl3 growth lead sulfochlorides, perovskite seeds induce formation Pb4S3Cl2 rather than Pb3S2Cl2 due better compatibility. Finally, combining simulations experimental data enables us unravel structure composition hitherto unsolved CsPbBr3/BixPbySz assign several other reported metal halide- oxide-based interfaces. The package is available GitHub or via OgreInterface desktop application, Windows, Linux, Mac.

Language: Английский

Citations

2
Octahedral units in halide perovskites DOI
Yong Wang, Yu Wang, Tiarnan A. S. Doherty

et al.

Nature Reviews Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Language: Английский

Citations

1
Structural Dynamics Descriptors for Metal Halide Perovskites DOI Creative Commons

Xia Liang,

Johan Klarbring, William J. Baldwin

et al.

The Journal of Physical Chemistry C, Journal Year: 2023, Volume and Issue: 127(38), P. 19141 - 19151

Published: Aug. 30, 2023

Metal halide perovskites have shown extraordinary performance in solar energy conversion technologies. They been classified as "soft semiconductors" due to their flexible corner-sharing octahedral networks and polymorphous nature. Understanding the local average structures continues be challenging for both modeling experiments. Here, we report quantitative analysis of structural dynamics time space from molecular simulations perovskite crystals. The compact descriptors provided cover a wide variety properties, including tilting distortion, lattice parameters, orientations, well spatial correlation. To validate our methods, trained machine learning force field (MLFF) methylammonium lead bromide (CH3NH3PbBr3) using an on-the-fly training approach with Gaussian process regression. known stable phases are reproduced, find additional symmetry-breaking effect cubic tetragonal close phase-transition temperature. test implementation large trajectories, also apply it 69,120 atom CsPbI3 based on MLFF developed atomic cluster expansion formalism. Python toolkit general readily transferable more complex compositions.

Language: Английский

Citations

14
Disentangling the effects of structure and lone-pair electrons in the lattice dynamics of halide perovskites DOI Creative Commons
Sebastián Caicedo‐Dávila, Adi Cohen, Silvia G. Motti

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 17, 2024

Halide perovskites show great optoelectronic performance, but their favorable properties are paired with unusually strong anharmonicity. It was proposed that this combination derives from the ns2 electron configuration of octahedral cations and associated pseudo-Jahn-Teller effect. We such not a prerequisite for anharmonicity low-energy lattice dynamics encountered in these materials. combine X-ray diffraction, infrared Raman spectroscopies, molecular to contrast CsSrBr3 those CsPbBr3, two compounds structurally similar former lacking propensity form lone pairs. exploit low-frequency diffusive scattering, nominally symmetry-forbidden cubic phase, as fingerprint reveal tilting occurs irrespective cation configuration. This highlights role structure perovskite dynamics, providing design rules emerging class soft semiconductors.

Language: Английский

Citations

6
Revealing the Free Energy Landscape of Halide Perovskites: Metastability and Transition Characters in CsPbBr3 and MAPbI3 DOI Creative Commons
Erik Fransson, J. Magnus Rahm, Julia Wiktor

et al.

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(19), P. 8229 - 8238

Published: Sept. 28, 2023

Halide perovskites have emerged as a promising class of materials for photovoltaic applications. A challenge these applications is preventing the crystal structure from degrading to photovoltaically inactive phases, which requires an understanding free energy landscape materials. Here, we uncover two prototypical halide perovskites, CsPbBr3 and MAPbI3, via atomic-scale simulations using umbrella sampling machine-learned potentials. For CsPbBr3, find very small differences barriers close transition temperatures both tetragonal-to-cubic orthorhombic-to-tetragonal transitions. however, situation more intricate. In particular, exhibits large barrier, there are several competing tetragonal phases. Using large-scale molecular dynamics simulations, explore character transitions observe latent heat discrete change in structural parameters phase indicating first-order We that orthorhombic has extended metastability range, identify second metastable phase. Finally, compile diagram MAPbI3 includes potential

Language: Английский

Citations

12
Mixing I and Br in Inorganic Perovskites: Atomistic Insights from Reactive Molecular Dynamics Simulations DOI Creative Commons
Mike Pols, Adri C. T. van Duin, Sofı́a Calero

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(9), P. 4111 - 4118

Published: Feb. 23, 2024

All-inorganic halide perovskites have received a great deal of attention as attractive alternatives to overcome the stability issues hybrid that are commonly associated with organic cations. To find compromise between optoelectronic properties CsPbI

Language: Английский

Citations

4
Nanoscale size effects in α-FAPbI3 evinced by large-scale ab initio simulations DOI Creative Commons
Ursula Röthlisberger, Virginia Carnevali,

Lorenzo Agosta

et al.

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract Formamidinium-lead-iodide (FAPbI3) has established itself as the state of art for high solar-energy conversion efficiency in perovskite-based solar cells. FAPbI3 a rich phase diagram, and it been noted that long-range correlation between organic lattice dipoles can influence transitions and, consequently, optoelectronic properties. In this regard, system size effects play crucial role an appropriate theoretical description FAPbI3. context, we perform systematic study on structural electronic properties photoactive (α-FAPbI3) function size. Utilizing ab initio molecular dynamics at 300 K first-principles calculations, demonstrate selection computational system/setup must satisfy three criteria concurrently to ensure accurate description: (correct) value band gap, extent (or absence of) distortions, zeroing out total dipole moment. We net moment vanishes increases due PbI6 octahedra distortions rather than FA+ rotations. Additionally, show thermal gap fluctuations are predominantly correlated with octahedral tilting. The optimal agreement simulation results experimental is only achieved by sizes approaching nanoscale.

Language: Английский

Citations

0
Effect of Overdamped Phonons on the Fundamental Band Gap of Perovskites DOI
Xiangzhou Zhu, David A. Egger

Physical Review Letters, Journal Year: 2025, Volume and Issue: 134(1)

Published: Jan. 10, 2025

Anharmonic atomic motions can strongly influence the optoelectronic properties of materials but how these effects are connected to underlying phonon band structure is not understood well. We investigate electronic gap influenced by overdamped phonons, which occur in an intriguing regime phonon-phonon interactions where vibrational lifetimes fall below one oscillation period. contrast anharmonic halide perovskite CsPbBr_{3}, known exhibit phonons its cubic phase, with oxide SrTiO_{3} underdamped at sufficiently high temperatures. Our results show that impact and cause slow dynamic fluctuations levels have been implicated unique perovskites. This finding enabled developing augmented stochastic Monte Carlo methods accounting for renormalization imaginary modes typically neglected. work provides guidelines capturing theoretical calculations materials.

Language: Английский

Citations

0
First-principles calculation on electronic structures, phonon dispersions, electronic and thermal conductivity and molecular dynamics of CsYbCl3 perovskite crystal DOI
Atsushi Suzuki, Takeo Oku

Computational Condensed Matter, Journal Year: 2025, Volume and Issue: unknown, P. e01008 - e01008

Published: Jan. 1, 2025

Language: Английский

Citations

0