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
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

    Unique optoelectronic, electronic, and sensing properties of hybrid organic–inorganic perovskites (HOIPs) are underpinned by the complex interactions between electronic and ionic states. Here, the photoinduced field ion migration in HOIPs is directly observed. Using newly developed local probe time‐resolved techniques, more significant CH3NH3+migration than I/Brmigration in HOIPs is unveiled. It is found that light illumination only induces CH3NH3+migration but not I/Brmigration. By directly observing temporal changes in bias‐induced and photoinduced ion migration in device conditions, it is revealed that light illumination suppresses the bias‐induced ion redistribution in the lateral device. These findings, being a necessary compensation of previous understandings of ion migration in HOIPs based on simulations and static and/or indirect measurements, offer advanced insights into the distinct light effects on the migration of organic cation and halides in HOIPs, which are expected to be helpful for improving the performance and the long‐term stability of HOIPs optoelectronics.

     
    more » « less
  4. 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
  5. Abstract

    Understanding interfacial reactions that occur between the active layer and charge‐transport layers can extend the stability of perovskite solar cells. In this study, the exposure of methylammonium lead iodide (CH3NH3PbI3) thin films prepared on poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)‐coated glass to 70% relative humidity (R.H.) leads to a perovskite crystal structure change from tetragonal to cubic within 2 days. Interface‐sensitive photoluminescence measurements indicate that the structural change originates at the PEDOT:PSS/perovskite interface. During exposure to 30% R.H., the same structural change occurs over a much longer time scale (>200 days), and a reflection consistent with the presence of (CH3)2NH2PbI3is detected to coexist with the cubic phase by X‐ray diffraction pattern. The authors propose that chemical interactions at the PEDOT:PSS/perovskite interface, facilitated by humidity, promote the formation of dimethylammonium, (CH3)2NH2+. The partial A‐site substitution of CH3NH3+for (CH3)2NH2+to produce a cubic (CH3NH3)1−x[(CH3)2NH2]xPbI3phase explains the structural change from tetragonal to cubic during short‐term humidity exposure. When (CH3)2NH2+content exceeds its solubility limit in the perovskite during longer humidity exposures, a (CH3)2NH2+‐rich, hexagonal phase of (CH3NH3)1−x[(CH3)2NH2]xPbI3emerges. These interfacial interactions may have consequences for device stability and performance beyond CH3NH3PbI3model systems and merit close attention from the perovskite research community.

     
    more » « less