A chiral switchable photovoltaic ferroelectric 1D perovskite

Abstract

Spin and valley degrees of freedom in materials without inversion symmetry promise previously unknown device functionalities, such as spin-valleytronics. Control of material symmetry with electric fields (ferroelectricity), while breaking additional symmetries, including mirror symmetry, could yield phenomena where chirality, spin, valley, and crystal potential are strongly coupled. Here we report the synthesis of a halide perovskite semiconductor that is simultaneously photoferroelectricity switchable and chiral. Spectroscopic and structural analysis, and first-principles calculations, determine the material to be a previously unknown low-dimensional hybrid perovskite (R)-(−)-1-cyclohexylethylammonium/(S)-(+)-1 cyclohexylethylammonium) PbI3. Optical and electrical measurements characterize its semiconducting, ferroelectric, switchable pyroelectricity and switchable photoferroelectric properties. Temperature dependent structural, dielectric and transport measurements reveal a ferroelectric-paraelectric phase transition. Circular dichroism spectroscopy confirms its chirality. The development of a material with such a combination of these properties will facilitate the exploration of phenomena such as electric field and chiral enantiomer–dependent Rashba-Dresselhaus splitting and circular photogalvanic effects.

Chirality‐Dependent Second‐Order Nonlinear Optical Effect in 1D Organic–Inorganic Hybrid Perovskite Bulk Single Crystal

“…It is noteworthy that the [PbI 6 ] 2− octahedra of 1 R and 1 S are mirror images of each other as the Pb‐I bonds in 1 R changes anticlockwise from longest bond to secondary longest bond, while it rotates clockwise in 1 S . These distorted [PbI 6 ] 2− octahedra are further connected through edge‐sharing to generate 1D chain running along the a‐axis, similar with other reported 1D lead halides [17, 18] . Additionally, the infinite lead iodide chains [PbI 6 ] ∞ 2− are spirally surrounded by R ‐3‐aminopiperidine via N−H⋅⋅⋅I hydrogen bonds (Figure S2) to form a right‐handed helix (Figure 1 a).…”

Chirality‐Dependent Second‐Order Nonlinear Optical Effect in 1D Organic–Inorganic Hybrid Perovskite Bulk Single Crystal

“…As an ew kind of multifunction materials,o rganicinorganic hybrid perovskites (OIHPs) with chemical designability,s tructural diversity,l ow-cost and low-temperature solution-processability have been widely concerned in many fields, [1,2] such as solar cells, [3,4] nonlinear optics (NLO), [5,6] ferroelectrics, [7,8] light emitting diodes [9,10] and photodetectors. [11][12][13] Meanwhile,OIHPs not only have the obvious grains and grain boundaries like ceramics,b ut also possess the rotation of organic ions like polymer.A mong these,c hiral OIHPs with asymmetric centers have exceptional attractive properties,s uch as circular dichroism, [14,15] chiroptoelectronics, [16] optical rotation, [16] second-harmonic generation (SHG), [5] and ferroelectricity, [17,18] which have attracted more and more attentions in many fields.The influence of chirality on the properties of OIHPs is mainly focused on the chiralitydependent circular photogalvanic effect, [19,20] spin transport, [21] optical selection rules [22] and chirality-induced ferroelectrics. [23] Due to the inherent noncentrosymmetry of chiral OIHPs,which endowing the chiral OIHPs produce asecondorder doubling frequency response by NLO effects.F urthermore,anideal NLO crystal must satisfy two conditions,one is non-centrosymmetric and the other one is phase matching (PM).…”

Ferroic Halide Perovskite Optoelectronics

“…As demonstrated by Hu et al., designing the organic molecule with chiral (R‐−)‐1‐cyclohexylethylamine (R‐CYHEA, C 8 H 15 NH 2 ) or (S‐+)‐1‐cyclohexylethylamine (S‐CYHEA, C 8 H 15 NH 2 ), result in enantiomers R‐CYHEAPbI 3 and S‐CYHEAPbI 3 nanowires to be chiral and photoferroelectrics, where the chiral organic groups are responsible for the chirality and the ferroelectricity. [ 122 ]…”

“…The polarization of the chiral hybrid halide nanowire is around 0.03 µC cm −2 , which can reach 1.2 µC cm −2 for the corresponding single‐crystal sample. [ 122 ] The experimentally measured polarization of CsPbBr 3 quantum dot is 0.25 µC cm −2 at 77 K and 0.018 µC cm −2 at 293 K. [ 123 ] It was seen that these polarization values are smaller than those reported in LHHs (as discussed above). However, it is still unclear if this is a general trend; and if so, why the polarization of chiral halide nanowires and MHP quantum dots is smaller than LHHs.…”