Ferroelectricity and Rashba Effect in a Two-Dimensional Dion-Jacobson Hybrid Organic–Inorganic Perovskite

Park, In‐Hyeok; Zhang, Qiannan; Kwon, Ki Chang; Zhu, Ziyu; Yu, Wei; Leng, Kai; Giovanni, David; Abdelwahab, Ibrahim; Xu, Qing‐Hua; Sum, Tze Chien; Loh, Kian Ping

doi:10.1021/jacs.9b07776

Cited by 123 publications

(123 citation statements)

References 33 publications

Supporting

Mentioning

112

Contrasting

Order By: Relevance

“…We start our simulations with the experimental ferroelectric phase of (AMP)PbI 4 refined at T = 298 K having space group Pc (#7, C 2 s ) with monoclinic b-axis in ref. 32 . Two nearby AMP 2+ cations located in the space between [PbI 4 ] 2− layers have alternating orientations when they are adjacent along the b or c axes, but common orientations when adjacent along with diagonal b + c or b − c directions, as shown in Fig.…”

Section: Structural Analysismentioning

confidence: 99%

“…Although the long-range ordering of AMP-cation orientations should be associated with a strong FE polarization along the a-axis at the first glance, this alone is not sufficient for understanding the overall polarization of a hybrid system, which typically has several different contributions to the polarization, as explained in details in ref. 32 . According to the modern theory of polarization 40 , we introduce a centrosymmetric anti-ferroelectric (AFE) phase by enforcing the existence of an inversion point and define a suitable path connecting the AFE and FE state via atomic rotations or/and displacements in order to estimate the polarization by first-principles calculations.…”

Section: Structural Analysismentioning

confidence: 99%

“…Very recently, Sum et al demonstrated the presence of both FE and a Rashba effect in a layered Dion-Jacobson (DJ) phase HOIP with formula (AMP)PbI 4 , where AMP is the divalent 4aminomethyl-piperidinium cation (Fig. 1, FE state) 32 . Its measured value of spontaneous polarization (P s ) is 9.8 μC cm −2 , which is very high among HOIPs 33,34 , and more comparable to those of conventional inorganic perovskites such as BaTiO 3 (15-26 μC cm −2 ) 35,36 .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Switchable Rashba anisotropy in layered hybrid organic–inorganic perovskite by hybrid improper ferroelectricity

et al. 2020

View full text Add to dashboard Cite

Hybrid organic–inorganic perovskites (HOIPs) are introducing exotic directions in the photovoltaic materials landscape. The coexistence of inversion symmetry breaking and spin–orbit interactions play a key role in their optoelectronic properties. We perform a detailed study on a recently synthesized ferroelectric layered HOIP, (AMP)PbI4 (AMP = 4-aminomethyl-piperidinium). The calculated polarization and Rashba parameters are in excellent agreement with experimental values. Moreover, we report a striking effect, i.e., an extraordinarily large Rashba anisotropy that is tunable by ferroelectric polarization: as polarization is reversed, not only the spin texture chirality is inverted, but also the major and minor axes of the Rashba anisotropy ellipse in k-space are interchanged—a pseudo rotation. A k·p model Hamiltonian and symmetry-mode analysis reveal a quadrilinear coupling between the cation-rotation modes responsible for the Rashba ellipse pseudo-rotation, the framework rotation, and the polarization. These findings may provide different avenues for spin-optoelectronic devices such as spin valves or spin FETs.

show abstract

Section: Structural Analysismentioning

confidence: 99%

Section: Structural Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Switchable Rashba anisotropy in layered hybrid organic–inorganic perovskite by hybrid improper ferroelectricity

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs) are natural quantum wells built of alternating layers of organic cations and inorganic anion cages. The appeal of RPP stems from its tunable chemical structure and dimensionality, which underpins its increasingly competitive performance in photovoltaics, light-emitting devices and ferroelectrics 1 – 6 . Heterostructure of 2D perovskites with other 2D materials is useful for fabricating functional devices 7 , 8 .…”

Section: Introductionmentioning

confidence: 99%

Electron tunneling at the molecularly thin 2D perovskite and graphene van der Waals interface

et al. 2020

Self Cite

View full text Add to dashboard Cite

Quasi-two-dimensional perovskites have emerged as a new material platform for optoelectronics on account of its intrinsic stability. A major bottleneck to device performance is the high charge injection barrier caused by organic molecular layers on its basal plane, thus the best performing device currently relies on edge contact. Herein, by leveraging on van der Waals coupling and energy level matching between two-dimensional Ruddlesden-Popper perovskite and graphene, we show that the plane-contacted perovskite and graphene interface presents a lower barrier than gold for charge injection. Electron tunneling across the interface occurs via a gate-tunable, direct tunneling-to-field emission mechanism with increasing bias, and photoinduced charge transfer occurs at femtosecond timescale (~50 fs). Field effect transistors fabricated on molecularly thin Ruddlesden-Popper perovskite using graphene contact exhibit electron mobilities ranging from 0.1 to 0.018 cm2V−1s−1 between 1.7 to 200 K. Scanning tunneling spectroscopy studies reveal layer-dependent tunneling barrier and domain size on few-layered Ruddlesden-Popper perovskite.

show abstract

“…For instance, a few 2D lead-iodide ferroelectrics, such as (4,4-di uorocyclohexylammnium) 2 PbI 4 and [4-(aminomethyl) piperidinium] 2 PbI 4 have been recently reported. 17,18 Nevertheless, owing to the monolayered inorganic perovskite sheets (n = 1), they still possess the relatively wide bandgap (E g >2.3 eV) along with the lacking of ferroelectric BPVEs. One effective pathway is to increase thickness of inorganic sheets (the n value) while retaining ferroelectricity of 2D lead-iodide hybrid perovskites.…”

Section: Introductionmentioning

confidence: 99%

Tailoring of a Visible-Light-Absorbing Biaxial Ferroelectric towards Broadband Self-Driven Photodetection

Han

Liu

et al. 2020

Preprint

View full text Add to dashboard Cite

In term of strong light-polarization coupling, ferroelectric materials with bulk photovoltaic effects (BPVEs) afford a promising avenue for newly-conceptual optoelectronic devices. However, due to severe polarization deterioration caused by leakage current of photoexcited carriers, most of ferroelectrics are merely capable of absorbing 8 ~ 20% of visible-light spectra. BPVE-active ferroelectrics with the narrow bandgap (Eg < 2.0 eV) are still scarce, hindering their practical applications. Here, we present a new 2D lead-iodide hybrid biaxial ferroelectric, [(CH3)2CH(CH2)2NH3]2(CH3CH2NH3)2Pb3I10 (1), which shows large spontaneous polarization (Ps = 5.2 µC/cm2) and the narrow direct bandgap (Eg = 1.80 eV). To the best of our knowledge, this Eg value of 1 is the smallest figure ever observed for the existing molecular ferroelectrics. Particularly, the symmetry breaking of 4/mmmFmm2 species results in its biaxial attributes, that is, four equivalent Ps directions for 1. Accordingly, exceptional in-plane BPVEs are exploited along the crystallographic [001] and [010] axes directions inside the crystallographic bc-plane, of which the directions can be facilely switched through external electric poling. At zero bias, the intriguing self-driven photoactivities were created in a wide range of 365–670 nm, including large switching ratio (> 105), high-density photocurrent (~ 1.5 µA/cm2) and ultrafast transient responding time (~ 2.7 ns). It is the coupling between ferroelectricity and in-plane BPVEs that endows great potentials of 1 toward broadband self-driven photodetection. This innovative study on in-plane ferroelectric BPVEs is unprecedent, which sheds light on new properties for their future optoelectronic device applications.

show abstract

Ferroelectricity and Rashba Effect in a Two-Dimensional Dion-Jacobson Hybrid Organic–Inorganic Perovskite

Cited by 123 publications

References 33 publications

Switchable Rashba anisotropy in layered hybrid organic–inorganic perovskite by hybrid improper ferroelectricity

Switchable Rashba anisotropy in layered hybrid organic–inorganic perovskite by hybrid improper ferroelectricity

Electron tunneling at the molecularly thin 2D perovskite and graphene van der Waals interface

Tailoring of a Visible-Light-Absorbing Biaxial Ferroelectric towards Broadband Self-Driven Photodetection

Contact Info

Product

Resources

About