Molecularly thin, two-dimensional all-organic perovskites.

Recently, the emergence of all-organic perovskites with three-dimensional (3D) structures has expanded the potential applications of perovskite materials. However, the synthesis and utilization of all-organic perovskites in 2D form remain largely unexplored because the design principle has not been developed. We present the successful synthesis of a metal-free 2D layered perovskite, denoted as the Choi-Loh van der Waals phase (CL-v phase), with the chemical formula A2B2X4, where A represents a larger-sized cation compared to B and X denotes an anion. The CL-v phase exhibits a van der Waals gap enabled by interlayer hydrogen bonding and can be exfoliated or grown as molecularly thin 2D organic crystals. The dielectric constants of the CL-v phase range from 4.8 to 5.5 and we demonstrate their potential as gate dielectrics for thin-film transistors.

Tailoring the coercive field in ferroelectric metal-free perovskites by hydrogen bonding.

The miniaturization of ferroelectric devices in non-volatile memories requires the device to maintain stable switching behavior as the thickness scales down to nanometer scale, which requires the coercive field to be sufficiently large. Recently discovered metal-free perovskites exhibit advantages such as structural tunability and solution-processability, but they are disadvantaged by a lower coercive field compared to inorganic perovskites. Herein, we demonstrate that the coercive field (110 kV/cm) in metal-free ferroelectric perovskite MDABCO-NH4-(PF6)3 (MDABCO = N-methyl-N'-diazabicyclo[2.2.2]octonium) is one order larger than MDABCO-NH4-I3 (12 kV/cm) owing to the stronger intermolecular hydrogen bonding in the former. Using isotope experiments, the ferroelectric-to-paraelectric phase transition temperature and coercive field are verified to be strongly influenced by hydrogen bonds. Our work highlights that the coercive field of organic ferroelectrics can be tailored by tuning the strength of hydrogen bonding.

In-Plane Ferroelectric Tin Monosulfide and Its Application in a Ferroelectric Analog Synaptic Device.

Two-dimensional ferroelectrics is attractive for synaptic device applications because of its low power consumption and amenability to high-density device integration. Here, we demonstrate that tin monosulfide (SnS) films less than 6 nm thick show optimum performance as a semiconductor channel in an in-plane ferroelectric analogue synaptic device, whereas thicker films have a much poorer ferroelectric response due to screening effects by a higher concentration of charge carriers. The SnS ferroelectric device exhibits synaptic behaviors with highly stable room-temperature operation, high linearity in potentiation/depression, long retention, and low cycle-to-cycle/device-to-device variations. The simulated device based on ferroelectric SnS achieves ∼92.1% pattern recognition accuracy in an artificial neural network simulation. By switching the ferroelectric domains partially, multilevel conductance states and the conductance ratio can be obtained, achieving high pattern recognition accuracy.

Rapid, Scalable Construction of Highly Crystalline Acylhydrazone Two-Dimensional Covalent Organic Frameworks via Dipole-Induced Antiparallel Stacking.

Covalent organic frameworks are an emerging class of porous crystalline organic materials that can be designed and synthesized from the bottom up. Despite progress made in synthesizing COFs of diverse topologies, the synthesis methods are often tedious and unscalable, hampering practical applications. Herein, we demonstrate a scalable, robust method of producing highly crystalline acylhydrazone two-dimensional (2D) COFs with diversified structures (six examples) under open and stirred conditions, with growth typically completed in only 30 min. Our strategy involves selecting molecular building blocks that have bond dipole moments with spatial orientations that favor antiparallel stacking and whose structure allows the restriction of intramolecular bond rotation (RIR) via intra- and interlayer hydrogen bonding. This method is widely applicable for hydrazide linkers containing various side-chain functionalities and topicities. By this strategy, the gram-scale synthesis of two highly crystalline COFs (up to 1.4 g yield) was obtained in a one-pot reaction within 30 min.

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

Hybrid organic-inorganic perovskites (HOIPs) are a new generation of high-performance materials for solar cells and light emitting diodes. Beyond these applications, ferroelectricity and spin-related properties of HOIPs are increasingly attracting interests. The presence of strong spin-orbit coupling, allied with symmetry breaking ensured by remanent polarization, should give rise to Rashba-type splitting of electronic bands in HOIP. However, the report of both ferroelectricity and Rashba effect in HOIP is rare. Here we report the observation of robust ferroelectricity and Rashba effect in two-dimensional Dion-Jacobson perovskites.

Tailoring open metal sites for selective capture of CO2 in isostructural metalloporphyrin porous organic networks.

Porphyrin-based isostructural porous organic networks have been synthesized by varying the central metal atoms to cobalt, nickel and copper. Their selectivities for CO2 capture over N2 and Ar are found to be enhanced as the heats of adsorption for CO2 are increased in the order of Co, Ni and Cu, while the pore structures are well maintained.