Piezoelectric properties of CH3NH3PbI3perovskite thin films and their applications in piezoelectric generators

Kim, Yun-Jeong; Dang, Tran-Van; Choi, Hyung-Jin; Park, Byeong-Ju; Eom, Ji‐Ho; Song, Hyun-A; Seol, Daehee; Kim, Yunseok; Shin, Sung Yong; Nah, Junghyo; Yoon, Soon‐Gil

doi:10.1039/c5ta09662f

Cited by 140 publications

(132 citation statements)

References 22 publications

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“…the domain structure that typifies a ferroelectric material are found to be quite contradictory (22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35). To analyze the question whether HaPs are actually ferroelectric, we need to test for the presence/absence of several fundamental phenomena that are tightly related to it.…”

Section: Significancementioning

confidence: 99%

Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric

Rakita

Bar-Elli

Meirzadeh

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

262

221

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Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with HaPs, especially tetragonal methylammonium lead triiodide (MAPbI 3 ). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to the spatial separation of electrons and holes, a possibility if MAPbI 3 is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step, we show that, in operando, MAPbI 3 (unlike MAPbBr 3 ) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material's relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop, to prove ferroelectricity's hallmark switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI 3 , we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is stable at room temperature). By chemical etching, we also can image the structural fingerprint for ferroelectricity, polar domains, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second harmonic generation, direct evidence for the material's noncentrosymmetry. We note that the material's ferroelectric nature, can, but need not be important in a PV cell at room temperature.halide perovskites | photovoltaics | semiconductors | ferroelectricity | pyroelectricity N ew optoelectronic materials are of interest for producing solar cells with higher power and voltage efficiencies, lower costs, and improved long-term reliability. A very recent entry is the family of halide perovskites (HaPs), in particular those based on methylammonium (MA) lead iodide (MAPbI 3 ), MAPbBr 3 , and its inorganic analog CsPbBr 3 . Devices based on these perform remarkably well as solar cells (1, 2), as well as in other optoelectronic applications, such as LEDs and electromagnetic radiation detectors (3-5). Understanding possible unique characteristics of HaPs may show the way to other materials with similar key features.The ABX 3 (X = I, Br, Cl) HaP semiconductors (SCs), that is, with perovskite or perovskite-like structures, reach, via a steep absorption edge, a high optical absorption coefficient (∼10 5 cm −1 ) (6, 7), long charge carrier lifetimes (∼0.1-1 μs) (8), and reasonable carrier mobilities (less than or equal to ∼100 cm 2 ·V −1 ·s −1 ) (9), and have a low exciton binding energy (10). With these characteristics, the thickness of the optical absorber layer can be ≤0.5 μm, which allows the charge carriers (separated electrons and holes) to diffuse/d...

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Section: Significancementioning

confidence: 99%

Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric

Rakita

Bar-Elli

Meirzadeh

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

262

221

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“…For example, the piezoelectric coefficient decreased by replacing I with Cl or Br because the covalent bond strength between Pb and X is reduced . A typical piezoelectric energy generator and its working mechanism are described in Figure …”

Section: Applications Beyond Photovoltaicsmentioning

confidence: 99%

Halide Perovskites for Applications beyond Photovoltaics

et al. 2018

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In recent years, halide perovskites have been attracting intense attention as novel materials for photovoltaic applications due to their high carrier mobility, extraordinarily long carrier diffusion lengths, and suitable optical bandgaps. Furthermore, there are extensive applications of halide perovskites owing to their exceptional attributes in different areas, such as light‐emitting diodes, lasers, X‐ray detectors, memory devices, and more. Here, the unique characteristics of halide perovskite materials are described, including their electrical and optical properties, to explain why these materials are so exciting for a wide variety of applications. After introducing the synthesis techniques used to prepare halide perovskite films, recent advances on the applications of halide perovskites beyond photovoltaics are addressed. The challenges to be overcome for several applications are described and it is suggested that halide perovskites are equivalent to a gold standard in developing next‐generation optoelectronic and electronic devices.

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“…[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. 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. 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.…”

mentioning

confidence: 99%

“…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. 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. 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.…”

mentioning

confidence: 99%

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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Piezoelectric properties of CH₃NH₃PbI₃perovskite thin films and their applications in piezoelectric generators

Abstract: CH3NH3PbI3(MAPbI3) perovskite thin films were applied for piezoelectric generators under various applied pressures, poling field conditions, and switching polarity test.

Cited by 140 publications

References 22 publications

Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric

Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric

Halide Perovskites for Applications beyond Photovoltaics

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

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Piezoelectric properties of CH3NH3PbI3perovskite thin films and their applications in piezoelectric generators

Abstract: CH3NH3PbI3(MAPbI3) perovskite thin films were applied for piezoelectric generators under various applied pressures, poling field conditions, and switching polarity test.

Cited by 140 publications

References 22 publications

Tetragonal CH 3 NH 3 PbI 3 is ferroelectric

Tetragonal CH 3 NH 3 PbI 3 is ferroelectric

Halide Perovskites for Applications beyond Photovoltaics

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

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Piezoelectric properties of CH₃NH₃PbI₃perovskite thin films and their applications in piezoelectric generators

Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric

Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric