Bandgap Engineering of Lead‐Halide Perovskite‐Type Ferroelectrics

Ye, Heng‐Yun; Liao, Wei‐Qiang; Hu, Chun‐Li; You, Yu‐Meng; Mao, Jiang‐Gao; Li, Pengfei; Xiong, Ren‐Gen

doi:10.1002/adma.201505224

Cited by 307 publications

(246 citation statements)

References 61 publications

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“…Therefore, the phase transition is attributable to the order−disorder transition of the organic cation, as found in the (benzylammonium) 2 PbCl 4 23 and (cyclohexylammonium) 2 PbBr 4−4x I 4x (x = 0−1). 24 The octahedra of the inorganic layers also show slight titling compared to each other during the phase transition (Figures 2 and S4, Supporting Information). The tilting may also lead to the breaking of the mmm symmetry.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Liao

Wang

et al. 2016

Crystal Growth & Design

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Following our recent finding of interesting dielectric and ferroelectric properties in semiconducting organic−inorganic layered perovskites (benzylammonium) 2 PbCl 4 and (cyclohexylammonium) 2 PbBr 4−4x I 4x (x = 0−1), we designed a new layered perovskite-type crystal (cyclohexylmethylammonium) 2 CdCl 4 . By systematic characterizations, including differential scanning calorimetry measurements, dielectric measurements, and variable-temperature structural analysis, this crystal was found to undergo a reversible first-order phase transition at around T c = 342 K. The origin of the phase transition is associated with the order− disorder change of the organic cation as expected. The phase transition is accompanied by the anticipated large dielectric constant change and remarkable dielectric anisotropy. These dielectric performances reveal potential application of the crystal as a high-temperature dielectric material. More interesting dielectric crystals are expected to be tailored in the future by taking advantage of the richness of layered perovskites. ■ INTRODUCTIONOwing to the high potential of producing materials with novel properties, organic−inorganic hybrid compounds are currently a hot topic of research. 1−5 Recently, their study was extended to structural phase transitions, and a few interesting phase transition properties were found. 6−12 The key components are the included organic cations, which have a large degree of motion in the cavities enclosed by the inorganic parts, exhibit dynamical disorder at relatively high temperatures, and become ordered below particular temperatures, giving rise to symmetry breaking and structural phase transitions. 13−16 Structural phase transitions in crystals are generally accompanied by changes of physical properties and, in many cases, can lead to intriguing physical properties, such as ferroelectric, dielectric, and electromechanical properties. 17,18 Therefore, the design of organic−inorganic hybrid crystals with structural phase transitions is very important, not only for the theoretical study of structure−property relationships, but also for the exploration of novel physical properties. 19−22 We have recently demonstrated that structural phase transitions in two-dimensional (2D) lead-halide layered perovskites can lead to interesting ferroelectric and dielectric properties, which produces molecular semiconducting ferroelectricity. 23,24 2D metal-halide layered perovskites with the general formula (R-NH 3 ) 2 MX 4 , where R is any alkyl or aromatic group and M is any divalent metal, have been intensely studied in the last two decades, because these crystals exhibit a number of appealing features suitable for a wide range of applications, such as solid-state batteries, ionic conductors, sensors, photovoltaic cells, luminescent devices, and so on. 25−28 Combination of the phase transition properties and physical properties of the 2D perovskites may lead to new materials and devices for photovoltaics, spintronics, and electrical-mechanical sensing. However, the study i...

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…We found that this crystal exhibits striking dielectric responses different from those previously observed in the lead analogues. 23,24 We here report the crystal structures and phase transition properties of 1. …”

mentioning

confidence: 99%

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Liao

Wang

et al. 2016

Crystal Growth & Design

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“…[1][2][3][4][5] Recently, research on molecular ferroelectrics have attracted much interest since they have great advantages such as being lightweight, easy to prepare and environmentally friendly, in comparison with the conventional inorganic ferroelectric materials. [6][7][8][9][10][11][12][13] Although a great progress has been made in the last few decades, few cases about metallo-organic molecular ferroelectrics have been documented. Moreover, the accurate design and construction of a molecular ferroelectric by facile structural modication on an existing metallo-organic molecule system is still a huge challenge.…”

Section: Introductionmentioning

confidence: 99%

Reversible structural phase transition, ferroelectric and switchable dielectric properties of an adduct molecule of hexamethylenetetramine ferrocene carboxylic acid

et al. 2017

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Metallo-organic molecules showing reversible structural phase transitions accompanied with ferroelectric and dielectric properties have seldom been reported. By making use of the "driving/controlling force" from the rotating motion of cyclopentadienyl rings for a reversible structural transition and then carrying out structural modifications on their local parts to create remnant polarization through this molecular system, we designed and constructed a new ferroelectric, which is the adduct of hexamethylenetetramine ferrocene carboxylic acid, (C 6 H 12 N 4 )[Fe(C 5 H 5 )(C 6 H 5 O 2 )] (1). Compound 1 undergoes a reversible structural phase transition at around 187 K, which is confirmed by remarkable dielectric and heat anomalies. The synergistic interactions of the twisting motions of the adduct molecules and the inner cyclopentadienyl rings lead to the reversible phase transition. A dipole moment from amine group to carboxylic acid at low temperature produces a net spontaneous polarization, which results in the ferroelectricity of 1-LTP. On further investigation, it is observed that compound 1 has a perfect ferroelectric hysteresis loop with a spontaneous polarization of 3.95 mC cm À2 .

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“…[1][2][3][4][5] Great success has been demonstrated by adopting this design strategy to achieve efficient optoelectronic property tailoring in semiconductors, which boosts the wide application of semiconductor materials in the fields of light-emitting-diode (LED), photovoltaics, biological imaging, etc. [6][7][8][9] Recently, this approach was revealed as applicable for phosphors (an insulator in nature) as well, endowing them with PersL properties, [10][11][12][13][14][15] which opens up a brand-new perspective for exploring novel phosphorescent materials that are highly desirable in security signs, night displays, optical storage media, etc.…”

Section: Introductionmentioning

confidence: 99%

Lu₂CaMg₂(Si_1−xGe_x)₃O₁₂:Ce³⁺solid-solution phosphors: bandgap engineering for blue-light activated afterglow applicable to AC-LED

et al. 2016

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Persistent luminescence (PersL) has long commanded the curiosity of researchers owing to the complicated and profound physics behind it. In this work, the PersL mechanism in a new kind of persistent garnet phosphors, Lu 2 CaMg 2 (Si 1Àx Ge x ) 3 O 12 :Ce 3+ , is studied from the new perspective of a ''solid-solution'' scheme. Different from the conventional study in pursuit of long PersL, we focus on manipulation of afterglow to the millisecond range and tentatively demonstrate its potential to compensate the flickering of the alternating current driven LED (AC-LED) in every AC cycle. Evidently, the tailored host bandgap favors efficient electron charging and facilitates electron detrapping, as well as redeploying trap distribution, which results in a blue light activated afterglow in the millisecond time range, and subsequently a reduced percent flicker of 64.1% for the AC-LED. This investigation is the first attempt to establish the design guidelines for new PersL materials with an adjustable millisecond ranged afterglow, and, hopefully, it paves a pathway to the development of burgeoning low-flickering AC-LED technology.

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Bandgap Engineering of Lead‐Halide Perovskite‐Type Ferroelectrics

Cited by 307 publications

References 61 publications

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Reversible structural phase transition, ferroelectric and switchable dielectric properties of an adduct molecule of hexamethylenetetramine ferrocene carboxylic acid

Lu₂CaMg₂(Si_1−xGe_x)₃O₁₂:Ce³⁺solid-solution phosphors: bandgap engineering for blue-light activated afterglow applicable to AC-LED

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Bandgap Engineering of Lead‐Halide Perovskite‐Type Ferroelectrics

Cited by 307 publications

References 61 publications

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)2CdCl4

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)2CdCl4

Reversible structural phase transition, ferroelectric and switchable dielectric properties of an adduct molecule of hexamethylenetetramine ferrocene carboxylic acid

Lu2CaMg2(Si1−xGex)3O12:Ce3+solid-solution phosphors: bandgap engineering for blue-light activated afterglow applicable to AC-LED

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Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Lu₂CaMg₂(Si_1−xGe_x)₃O₁₂:Ce³⁺solid-solution phosphors: bandgap engineering for blue-light activated afterglow applicable to AC-LED