ABSTRACT
2D organic-inorganic hybrid perovskites (OIHPs) have become one of the hottest research topics due to their excellent environmental stability and unique optoelectronic properties. Recently, the ferroelectricity and thermochromism of 2D OIHPs have attracted increasing interests. Integrating ferroelectricity and thermochromism into perovskites can significantly promote the development of multichannel intelligent devices. Here, a novel 2D Dion-Jacobson OIHP of the formula (3AMP)PbI4 (where 3AMP is 3-(aminomethyl)pyridinium) is reported, which has a remarkable spontaneous polarization value (Ps) of 15.6 µC cm-2 and interesting thermochromism. As far it is known, such a large Ps value is the highest for 2D OIHPs recorded so far. These findings will inspire further exploration and application of multifunctional perovskites.
ABSTRACT
Two-dimensional (2D) hybrid double perovskites have attracted extensive research interest for their fascinating physical properties, such as ferroelectricity, X-ray detection, light response and so on. In addition, ferroelastics, as an important branch of ferroic materials, exhibits wide prospects in mechanical switches, shape memory and templating electronic nanostructures. Here, we designed a 2D phase-transition double perovskite ferroelastic through a structurally progressive strategy. This evolution is core to our construction process from 0D to 1D and AgBi-based 2D. In this way, we successfully synthesized 2D lead-free ferroelastic (DPA)4AgBiBr8 (DPA = 2,2-dimethylpropan-1-aminium) with a high Curie temperature (T c), which shows a narrower band gap than 0D (DPA)4Bi2Br10 and 1D (DPA)5Pb2Br9. Moreover, the mechanism of structural phase transition and molecular motion are fully characterized by temperature dependent solid-state NMR and single crystal XRD. (DPA)4AgBiBr8 injects power into the discovery of new ferroelastics or the construction and dimensional adjustment in new hybrid double perovskites.
ABSTRACT
Surface passivation via post-treatment is an important strategy for improving power conversion efficiency and operational stability of perovskite solar cells. However, so far the interaction mechanisms between passivating additive and perovskite are not well understood. Here, we report the atomic-scale interaction of surface passivating additive 2,2-difluoroethylammonium bromine (2FEABr) on the MAPbI3. It is found that the bulky 2FEA+ cations tend to distribute at film surface, while the Br- anions diffuse from surface into bulk. A combination of 19F, 207Pb, and 2H solid-state NMR further reveal the Br- anions' partial substitution for the I- sites, the restricted motion of partial MA+ cations, and the firmed perovskite lattices, which would improve charge transport and stability of the perovskite films. Optical spectroscopy and ultraviolet photoelectron spectroscopy demonstrate that the 2FEABr induced surface passivation and energetic modification suppress the nonradiative recombination loss. These findings enable the efficiency of the p-i-n structured PSC significantly increasing from 19.44 to 21.06%, accompanied by excellent stability. Our work further establishes more knowledge link between passivating additive and PSC performance.
ABSTRACT
Considerable progress has been made in improving the performance of optoelectronic devices based on hybrid organic-inorganic perovskites of the form ABX3. However, the influences of A-site doping on the structure and dynamics of the inorganic perovskite crystal lattice and, in turn, on the optoelectronic performance of the resulting devices remain poorly understood at an atomic level. This work addresses this issue by combining the results of several experimental characterization methods for three-dimensional MA1-xDMAxPbBr3 perovskite single crystals (MA, methylammonium; DMA, dimethylammonium). The results reveal a two-stage change in lattice with an increase in DMA content, which has completely opposite effects on the optoelectronic performance of the double-cation perovskite. At low DMA concentrations, fast reorientation of incorporated DMA cations strengthens the interaction between MA cations and the lattice without significant lattice distortion, which could suppress lattice fluctuation and thus improve the photovoltaic performance. At high DMA concentrations, the lattice get a severe distortion, leading to poorer photovoltaic performance.
ABSTRACT
For nearly 100 y, homochiral ferroelectrics were basically multicomponent simple organic amine salts and metal coordination compounds. Single-component homochiral organic ferroelectric crystals with high-Curie temperature (Tc) phase transition were very rarely reported, although the first ferroelectric Rochelle salt discovered in 1920 is a homochiral metal coordination compound. Here, we report a pair of single-component organic enantiomorphic ferroelectrics, (R)-3-quinuclidinol and (S)-3-quinuclidinol, as well as the racemic mixture (Rac)-3-quinuclidinol. The homochiral (R)- and (S)-3-quinuclidinol crystallize in the enantiomorphic-polar point group 6 (C6) at room temperature, showing mirror-image relationships in vibrational circular dichroism spectra and crystal structure. Both enantiomers exhibit 622F6-type ferroelectric phase transition with as high as 400 K [above that of BaTiO3 (Tc = 381 K)], showing very similar ferroelectricity and related properties, including sharp step-like dielectric anomaly from 5 to 17, high saturation polarization (7 µC/cm2), low coercive field (15 kV/cm), and identical ferroelectric domains. Their racemic mixture (Rac)-3-quinuclidinol, however, adopts a centrosymmetric point group 2/m (C2h), undergoing a nonferroelectric high-temperature phase transition. This finding reveals the enormous benefits of homochirality in designing high-Tc ferroelectrics, and sheds light on exploring homochiral ferroelectrics with great application.
