skip to main content


Title: Light‐Ferroic Interaction in Hybrid Organic–Inorganic Perovskites
Abstract

Given the remarkable performance of hybrid organic–inorganic perovskites (HOIPs) in solar cells, light emitters, and photodetectors, the quest to advance the fundamental understanding of the photophysical properties in this class of materials remains highly relevant. Recently, the discovery of ferroic twin domains in HOIPs has renewed the debate of the ferroic effects on optoelectric processes. This work explores the interaction between light and ferroic twin domains in CH3NH3PbI3. Due to strain and chemical inhomogeneities, photogenerated electrons and holes show a preferential motion in the ferroelastic twin domains. Density functional theory (DFT) shows that electrons and holes result in lattice expansion in CH3NH3PbI3differently. Hence, light generates strain in the ferroelastic domains due to preferential photocarrier motion, leading to a screening of strain variation. X‐ray diffraction studies verify the DFT simulations and reveal that the photoinduced strain is light intensity dependent, and the photoexcitation is a prerequisite of inducing strain by light. This work extends the fundamental understanding of light‐ferroic interaction and offers guidance for developing functional devices.

 
more » « less
NSF-PAR ID:
10459729
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Optical Materials
Volume:
7
Issue:
23
ISSN:
2195-1071
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Hybrid organic–inorganic perovskite materials, such as CH 3 NH 3 PbI 3 , exhibit substantial potential in a variety of optoelectronic applications. Nevertheless, the interplay between the photoinduced excitations and iodine Frenkel defects which are abundant in CH 3 NH 3 PbI 3 films remains poorly understood. Here we study the light-triggered electronic and excitonic properties in the presence of iodine Frenkel defects in CH 3 NH 3 PbI 3 by using a combination of density functional theory (DFT) and time-dependent DFT approaches, the latter of which treats electron–hole and electron–nucleus interactions on the same footing. For isolated Frenkel defects, electrons are trapped close to the iodine vacancies and the electron–hole correlation brings the holes in close vicinity to the electrons, yielding tightly bound polaronic excitons. However, in the presence of multiple interactive Frenkel defects, the holes are pulled out from an electron–hole Coulomb well by the iodine interstitials, leading to spatially separated electron–hole pairs. The X-ray photoelectron spectra are then simulated, unravelling the light-triggered charge transfer induced by Frenkel defects at the atomistic level. We also find that the energy and spatial distributions of polaronic excitons at the Frenkel defects can be controlled by the dynamical rotation of organic cations. 
    more » « less
  2. Abstract

    With power conversion efficiencies now reaching 24.2%, the major factor limiting efficient electricity generation using perovskite solar cells (PSCs) is their long‐term stability. In particular, PSCs have demonstrated rapid degradation under illumination, the driving mechanism of which is yet to be understood. It is shown that elevated device temperature coupled with excess charge carriers due to constant illumination is the dominant force in the rapid degradation of encapsulated perovskite solar cells under illumination. Cooling the device to 20 °C and operating at the maximum power point improves the stability of CH3NH3PbI3solar cells over 100× compared to operation under open circuit conditions at 60 °C. Light‐induced strain originating from photothermal‐induced expansion is also observed in CH3NH3PbI3, which excludes other light‐induced‐strain mechanisms. However, strain and electric field do not appear to play any role in the initial rapid degradation of CH3NH3PbI3solar cells under illumination. It is revealed that the formation of additional recombination centers in PSCs facilitated by elevated temperature and excess charge carriers ultimately results in rapid light‐induced degradation. Guidance on the best methods for measuring the stability of PSCs is also given.

     
    more » « less
  3. Abstract

    Organic–inorganic hybrid perovskites (OIHPs) have been explosively investigated mainly due to their potential applications in optoelectronics. Despite the electronic charge transport, phenomena regarding the spin‐polarized electronic transport in OIHPs‐based spintronic devices and the role of ferromagnet/OIHP spinterfaces remain unclear. In this work, the spin injection, accumulation, transport, and detection at room temperature for a vertical perovskite spin valve (PeSV) consisting of Ni/CH3NH3PbI3−xClx/Ni is reported. An in‐plane anisotropic magnetoresistance (AMR) and a PeSV related magnetoresistance (MR) show remarkable magnetic switching behaviors due to the formation of Ni/CH3NH3PbI3−xClxspinterfaces, and the ferromagnetic coupling between two spin quantization axes of the spinterfaces. With assists of capacitance–frequency (C− −f) measurements under magnetic fields, the spin accumulation that occurs at the Ni/CH3NH3PbI3−xClxinterface can be detected at the spin parallel (↑↑) and antiparallel (↑↓) configurations. Owing to a strong orbital interaction at the Ni/CH3NH3PbI3−xClxhybrid interface, the spin‐sensitive electron paramagnetic spectroscopy (EPR) reveals significant change of the magnetic moment (µ). It is believed that the solution processed CH3NH3PbI3−xClxand the formation of the Ni/CH3NH3PbI3−xClxspinterface may hold an exceptionally important role for future hybrid optospintronic applications.

     
    more » « less
  4. Abstract

    Semiconducting molecules have been employed to passivate traps extant in the perovskite film for enhancement of perovskite solar cells (PSCs) efficiency and stability. A molecular design strategy to passivate the defects both on the surface and interior of the CH3NH3PbI3perovskite layer, using two phthalocyanine (Pc) molecules (NP‐SC6‐ZnPc andNP‐SC6‐TiOPc) is demonstrated. The presence of lone electron pairs on S, N, and O atoms of the Pc molecular structures provides the opportunity for Lewis acid–base interactions with under‐coordinated Pb2+sites, leading to efficient defect passivation of the perovskite layer. The tendency of bothNP‐SC6‐ZnPc andNP‐SC6‐TiOPc to relax on the PbI2terminated surface of the perovskite layer is also studied using density functional theory (DFT) calculations. The morphology of the perovskite layer is improved due to employing the Pc passivation strategy, resulting in high‐quality thin films with a dense and compact structure and lower surface roughness. UsingNP‐SC6‐ZnPc andNP‐SC6‐TiOPc as passivating agents, it is observed considerably enhanced power conversion efficiencies (PCEs), from 17.67% for the PSCs based on the pristine perovskite film to 19.39% forNP‐SC6‐TiOPc passivated devices. Moreover, PSCs fabricated based on the Pc passivation method present a remarkable stability under conditions of high moisture and temperature levels.

     
    more » « less
  5. Abstract

    Following the rejuvenation of 3D organic–inorganic hybrid perovskites, like CH3NH3PbI3, (quasi)‐2D Ruddlesden–Popper soft halide perovskites R2An−1PbnX3n+1have recently become another focus in the optoelectronic and photovoltaic device community. Although quasi‐2D perovskites were first introduced to stabilize optoelectronic/photovoltaic devices against moisture, more interesting properties and device applications, such as solar cells, light‐emitting diodes, white‐light emitters, lasers, and polaritonic emission, have followed. While delicate engineering design has pushed the performance of various devices forward remarkably, understanding of the fundamental properties, especially the charge‐transfer process, electron–phonon interactions, and the growth mechanism in (quasi)‐2D halide perovskites, remains limited and even controversial. Here, after reviewing the current understanding and the nexus between optoelectronic/photovoltaic properties of 2D and 3D halide perovskites, the growth mechanisms, charge‐transfer processes, vibrational properties, and electron–phonon interactions of soft halide perovskites, mainly in quasi‐2D systems, are discussed. It is suggested that single‐crystal‐based studies are needed to deepen the understanding of the aforementioned fundamental properties, and will eventually contribute to device performance.

     
    more » « less