A lead-halide perovskite molecular ferroelectric semiconductor

Liao, Wei‐Qiang; Zhang, Wan-Ying; Hu, Chun‐Li; Mao, Jiang‐Gao; Li, Pengfei; Huang, Songping D.; Xiong, Ren‐Gen

doi:10.1038/ncomms8338

Cited by 600 publications

(411 citation statements)

References 69 publications

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“…[51][52][53] More ferroelectric structures have been proposed for various metal, cation or halogen, among which one can find simple examples in Amm2, R3m or Cmc2 1 . 27,47,50,[54][55][56] For 3D materials containing Ge, the tolerance factor is more compatible with the onset of a polar distortion, and a sizable SOC may also be present, especially with the contribution of heavy halogen atoms. 57 More complex cases may correspond to combinations of both antiferrodistortions and ferroelectric behavior.…”

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confidence: 95%

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Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics

Képénékian

Even

2017

J. Phys. Chem. Lett.

174

181

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In halide hybrid organic-inorganic perovskites (HOP), spin-orbit coupling (SOC) presents a well-documented large influence on band structure. However, SOC may also present more exotic effects, such as Rashba and Dresselhaus couplings. In this perspective, we start by recalling the main features of this effect and what makes HOP materials ideal candidates for the generation and tuning of spin-states. Then, we detail the main spectroscopy techniques able to characterize these effects and their application to HOP. Finally, we discuss potential applications in spintronics and in spin-orbitronics in those non-magnetic systems, that would complete the skill set of HOP and perpetuate its ride on the crest of the wave of popularity started with optoelectronics and photovoltaics. Graphical TOC EntryPage 2 of 29 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 A c c e p t e d m a n u s c r i p tThe continuous success of halide hybrid organic-inorganic perovskites (HOP) as solar cell active materials follows several paths. The main activity after 2012 consisted in the search for improvement of the power conversion efficiency (PCE) in typical laboratory configuration (small area, controlled environment). It led to an unprecedented growth of the PCE that has repeatedly reached record values over 22%. 1,2 Meanwhile, another branch of HOP studies have been focused on improving the stability of those cells unfortunately sensitive to light and moisture. 3,4 Opting for various mixtures of halide and cations, 2 various forms, e.g. layered HOP, [5][6][7] or by encapsulating the materials, the stability went from few hours to several thousands hours. Encouraged by these breakthroughs, a third path has pushed the area of hight performance solar cells from less than 1 cm 2 up to 50 cm 2 with a PCE of 12.6%, 8 bringing the perovskite solar cells even closer to commercial use.A common point to all these record HOP materials is the presence of lead. Even though a large effort has been and still is dedicated to the search for efficient lead-free HOP materials, 9,10 their current record PCE remains around 6.4%. 11 It is certainly unfortunate for solar cells because of the known toxicity of lead, 12 even though solutions have early been proposed, 13,14 however, due to the large spin-orbit coupling (SOC) exhibited by Pb, it represents a great opportunity for optoelectronics, spintronics and spin-orbitronics applications where undesired heavy elements can find a place (e.g. arsenic, cadmium).The first identified effect of SOC in HOP materials has been a surprising giant splitting of conduction bands, 15,16 instead of the usual valence band splitting observed in classical semiconductors. 17 It has a strong influence on the band gap energy as well as on the effective masses and the oscillator strength of the optical transitions at the band gap. The chan...

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confidence: 95%

“…Indeed, several compounds belong to polar groups and have been scrutinized. 7,29,56,64,65 One should notice that the above examples have a symmetry axis perpendicular to the staking direction. As a consequence, the Rashba effect is incomplete, i.e.…”

mentioning

confidence: 99%

Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics

Képénékian

Even

2017

J. Phys. Chem. Lett.

174

181

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“…The (ammoniomethyl)pyridinium cation has a structure similar to that of the benzylammonium cation, and the same rotation in the phase transition has been observed. 14 Therefore, the alignment of the organic cations is responsible for the ferroelectricity in 1. This is different from that in the three-dimensional methylammonium lead-halide perovskites.…”

Section: Resultsmentioning

confidence: 99%

“…We recently demonstrated that photoferroelectricity can be achieved in lead-halide perovskite-type ferroelectrics. 13,14 Although these compounds show excellent ferroelectricity, they have two drawbacks: a relatively high bandgap (42.7 eV) and toxicity from the Pb element. …”

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confidence: 99%

A semiconducting molecular ferroelectric with a bandgap much lower than that of BiFeO3

Tang

Liao

et al. 2017

NPG Asia Mater

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Ferroelectrics have been attracting increasing attention as good candidates for multifunctional materials because of their fascinating properties. However, their large bandgap has been a roadblock limiting their application in optoelectronics and photovoltaics, among other applications. Hybrid ferroelectrics have the potential to combine the advantages of both molecular materials and ferroelectrics. In this context, we designed a hybrid ferroelectric: (2-(ammoniomethyl)pyridinium)SbI 5 . It shows an above-room-temperature Curie temperature (T c = 360 K), a large spontaneous polarization (P s = 4 μC cm − 2 ) and a small bandgap (2.03 eV) that is much smaller than the recently reported 2.7-3.65 eV for the lead-halide perovskite ferroelectrics. The implementation of ferroelectricity in hybrid semiconducting materials may be a feasible way to realize high-performance ferroelectric optoelectronic and photovoltaic devices. NPG Asia Materials (2017) 9, e342; doi:10. 1038/am.2016.193; published online 20 January 2017 INTRODUCTIONIntensive research on photovoltaic (PV) materials over the past six decades has been driven by the increasingly serious energy crisis. Among the emerging PV technologies, hybrid perovskite solar cells demonstrate extraordinary power conversion efficiencies and very low cost. 1-5 The high power conversion efficiency (up to 20.1%) is because of the strong light absorption and high carrier mobility of hybrid perovskites. Nevertheless, much work needs to be done to overcome their instability in moisture and the toxicity of lead. Thus, researchers have begun to explore related materials with a lower toxicity and/or better stability. [6][7][8] Meanwhile, the past few years have seen the renaissance of photoferroelectric materials for PV applications. [9][10][11][12] Photoferroelectric materials, such as BiFeO 3 and SbSI, are semiconducting ferroelectrics that show both photosensitive and ferroelectric properties. They adopt a newly described mechanism known as the anomalous PV effect, where photogenerated electrons and holes are directly separated by the spontaneous electric field from the intrinsic ferroelectric polarization, resulting in an open circuit voltage above the bandgap. However, the power conversion efficiency of conventional inorganic ferroelectrics remains low because of the poor light absorption ability that is limited by their large bandgaps.Organic-inorganic hybrid ferroelectrics have the potential to combine advantages from both hybrid materials and ferroelectrics. We recently demonstrated that photoferroelectricity can be achieved in lead-halide perovskite-type ferroelectrics. 13,14 Although these compounds show excellent ferroelectricity, they have two drawbacks: a relatively high bandgap (42.7 eV) and toxicity from the Pb element.

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“…From both theoretical and applied viewpoints, phase-transition compounds are popular and valuable in increasing the general understanding of structure-property relations and exploring functional materials with novel physical properties [1][2][3][4][5][6][7][8][9][10]. Phase-transition crystalline materials are usually accompanied by an abrupt change in some physical properties around the transition temperature.…”

Section: Introductionmentioning

confidence: 99%

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

et al. 2017

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Two novel inorganic-organic hybrid supramolecular assemblies, namely, (4-HNA) (18-crown-6)(HSO 4 ) (1) and (4-HNA) 2 (18-crown-6) 2 (PF 6 ) 2 (CH 3 OH) (2) (4-HNA = 4-nitroanilinium), were synthesized and characterized by infrared spectroscopy, single X-ray diffraction, differential scanning calorimetry (DSC), and temperature-dependent dielectric measurements. The two compounds underwent reversible phase transitions at about 255 K and 265 K, respectively. These phase transitions were revealed and confirmed by the thermal anomalies in DSC measurements and abrupt dielectric anomalies during heating. The phase transition may have originated from the [(4-HNA)(18-crown-6)] + supramolecular cation. The inorganic anions tuned the crystal packings, and thus influenced the phase-transition points and types. The variable-temperature X-ray diffraction data for crystal 1 revealed the occurrence of a phase transition in the high-temperature phase with the space group of P2 1 /c and in the low-temperature phase with the space group of P2 1 /n. Crystal 2 exhibited the same space group P2 1 /c at different temperatures. The results indicated that crystals 1 and 2 both underwent an iso-structural phase transition.

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A lead-halide perovskite molecular ferroelectric semiconductor

Cited by 600 publications

References 69 publications

Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics

Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics

A semiconducting molecular ferroelectric with a bandgap much lower than that of BiFeO3

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

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