Role of Ferroelectric Nanodomains in the Transport Properties of Perovskite Solar Cells

Pecchia, Alessandro; Gentilini, Desirée; Rossi, Daniele; Maur, Matthias Auf der; Carlo, Aldo Di

doi:10.1021/acs.nanolett.5b03957

Cited by 76 publications

(85 citation statements)

References 25 publications

(45 reference statements)

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“…[13] Some dense organic-inorganic frameworks exhibit wide range of ferroelectric and multiferroic properties. [14,15] High PSC powerc onversion efficiency in photovoltaics is ar esult of ac ombination of different properties, such as favorable balance between stronga bsorption and long carrier lifetimes, [16,17] outstanding transport, [18][19][20] and excellent fault tolerance. [21] It wasa lso suggested that defect tolerance in these perovskites as well as in othero rganic-inorganic frameworks may be relatedt ot he presence of van der Waals interactions and hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding and Stability of Hybrid Organic–Inorganic Perovskites

et al. 2016

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In the past few years, the efficiency of solar cells based on hybrid organic-inorganic perovskites has exceeded the level needed for commercialization. However, existing perovskites solar cells (PSCs) suffer from several intrinsic instabilities, which prevent them from reaching industrial maturity, and stabilizing PSCs has become a critically important problem. Here we propose to stabilize PSCs chemically by strengthening the interactions between the organic cation and inorganic anion of the perovskite framework. In particular, we show that replacing the methylammonium cation with alternative protonated cations allows an increase in the stability of the perovskite by forming strong hydrogen bonds with the halide anions. This interaction also provides opportunities for tuning the electronic states near the bandgap. These mechanisms should have a universal character in different hybrid organic-inorganic framework materials that are widely used.

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Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding and Stability of Hybrid Organic–Inorganic Perovskites

et al. 2016

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“…Fore xample,arecent report shows that the band gap values of CH 3 NH 3 PbX 3 (X = Cl, Br,I )c an be controlled by chemical substitution. [12] In this context, development of new photoferroelectrics is crucial to improve our collective understanding of ferroelectric PVEs and to ascertain the applicability of these materials in photovoltaics. 20 mA cm À2 )w as obtained with aC H 3 NH 3 PbI 3 photovoltaic device.…”

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confidence: 99%

A Photoferroelectric Perovskite‐Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects

et al. 2016

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Perovskite-type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because of their unique photovoltaic effects (PVEs). A new layered perovskite-type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead (1), is presented. The material exhibits an exceptional anisotropy of bulk PVEs. Upon photoexcitation, superior photovoltaic behaviors are created along its inorganic layers, which are composed of corner-sharing PbBr6 octahedra. Semiconducting activity with remarkable photoconductivity is achieved in the vertical direction, showing sizeable on/off current ratios (>10(4) ), which compete with the most active photovoltaic material CH3 NH3 PbI3 . In 1 the temperature-dependence of photovoltage coincides fairly well with that of polarization, confirming the dominant role of ferroelectricity in such highly anisotropic PVEs. This finding sheds light on bulk PVEs in ferroelectric materials, and promotes their application in optoelectronic devices.

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“…[2][3][4] While the experimental results reviewed here prove the existence of ferroelectricity in semiconducting MAPbI 3 thin-films, experimental evidence for an effect of the polar domains on the charge carrier recombination has not been achieved yet. This is pivotally important, not only for optimizing existing OMH perovskites, but in particular as a design criterion for new, more stable, and eco-friendly light-harvesting perovskites.…”

Section: Implications For Materials Designmentioning

confidence: 73%

“…[2][3][4] However, whether or not OMH perovskites are ferroelectric materials or exhibit other ferroic properties, and which effects might result from these properties have been a subject of debate for several years. An often proposed idea to explain the enhanced separation and transport of photogenerated charge carriers describes the formation of ferroelectric domains, i.e., domains with alternating polarization.…”

mentioning

confidence: 99%

“…[2][3][4] However, whether or not OMH perovskites are ferroelectric materials or exhibit other ferroic properties, and which effects might result from these properties have been a subject of debate for several years. [2][3][4] However, whether or not OMH perovskites are ferroelectric materials or exhibit other ferroic properties, and which effects might result from these properties have been a subject of debate for several years.…”

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confidence: 99%

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Ferroelectric Properties of Perovskite Thin Films and Their Implications for Solar Energy Conversion

et al. 2019

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Yet, as of today, the microscopic origin of the remarkable charge carrier dynamics in perovskite solar cells remains unclear. An often proposed idea to explain the enhanced separation and transport of photogenerated charge carriers describes the formation of ferroelectric domains, i.e., domains with alternating polarization.Ferroelectric domains would provide local internal electric fields that assist with the separation of charge carriers and hence reduce recombination. [2][3][4] However, whether or not OMH perovskites are ferroelectric materials or exhibit other ferroic properties, and which effects might result from these properties have been a subject of debate for several years. A multitude of measurement techniques was employed in order to probe ferroic properties of single crystal samples, [5,6] pressed powder pellets, [7] and polycrystalline thin-films [8] of OMH perovskites. Scanning microscopy techniques such as atomic force microscopy (AFM), [9][10][11][12] scanning electron microscopy (SEM), [13] and tunneling electron microscopy (TEM) [14] were extensively used in order to reveal the microstructure of OMH-perovskite thinfilm samples with subgrain resolution. Some of these studies revealed ordered domains within crystal grains, but no consensus has been reached about the interpretation of their ferroic and crystallographic origins. Claims included piezoelectricity, [15][16][17] pyroelectricity, [5] ferroelasticity, [9,12,18] antiferroelectricity [19] as well as ferroelectricity, [10,11,15,16,20] and the seemingly contradictory reports on these ferroic properties have heated up the discussion. Techniques that probe large areas of specimens such as X-ray diffraction (XRD), [21] impedance spectroscopy, [22,23] and J-V characterization [5,7] added a rather spatially averaged picture of the samples' microstructure. For example, second harmonic generation (SHG) measurements were employed in order to identify whether or not OMH perovskites form polar crystals, but their interpretation led to ambiguous results. [5,24] In order to clarify some of the confusion and seemingly contradictory reports on the ferroic and, in particular, ferroelectric features of OMH perovskites, we review and discuss some of the fundamental properties of this material class and correlate them with our own observations on perovskite thin-films. We deliberately focus on the ferroic properties of archetypical methylammonium lead iodide (MAPbI 3 ), representing the class of light-harvesting perovskites.Whether or not methylammonium lead iodide (MAPbI 3 ) is a ferroelectric semiconductor has caused controversy in the literature, fueled by many misunderstandings and imprecise definitions. Correlating recent literature reports and generic crystal properties with the authors' experimental evidence, the authors show that MAPbI 3 thin-films are indeed semiconducting ferroelectrics and exhibit spontaneous polarization upon transition from the cubic high-temperature phase to the tetragonal phase at room temperature. The polarization is predomina...

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Role of Ferroelectric Nanodomains in the Transport Properties of Perovskite Solar Cells

Cited by 76 publications

References 25 publications

Hydrogen Bonding and Stability of Hybrid Organic–Inorganic Perovskites

Hydrogen Bonding and Stability of Hybrid Organic–Inorganic Perovskites

A Photoferroelectric Perovskite‐Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects

Ferroelectric Properties of Perovskite Thin Films and Their Implications for Solar Energy Conversion

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