Ferroelectric Metal–Organic Frameworks

Hybrid halide perovskites have become the “next big thing” in emerging semiconductor materials, as the past decade witnessed their successful application in high-performance photovoltaics. This resurgence has encompassed enormous and widespread development of the three-dimensional (3D) perovskites, spearheaded by CH3NH3PbI3. The next generation of halide perovskites, however, is characterized by reduced dimensionality perovskites, emphasizing the two-dimensional (2D) perovskite derivatives which expand the field into a more diverse subgroup of semiconducting hybrids that possesses even higher tunability and excellent photophysical properties. In this Perspective, we begin with a historical flashback to early reports before the “perovskite fever”, and we follow this original work to its fruition in the present day, where 2D halide perovskites are in the spotlight of current research, offering characteristics desirable in high-performance optoelectronics. We approach the evolution of 2D halide perovskites f...

Two-Dimensional Hybrid Halide Perovskites: Principles and Promises.

Hybrid organic–inorganic perovskites (HOIPs) can have a diverse range of compositions including halides, azides, formates, dicyanamides, cyanides and dicyanometallates. These materials have several common features, including their classical ABX3 perovskite architecture and the presence of organic amine cations that occupy the A-sites. Current research in HOIPs tends to focus on metal halide HOIPs, which show promise for use in solar cells and optoelectronic devices; however, the other subclasses also exhibit a diverse range of physical properties. In this Review, we summarize the chemical variability and structural diversity of all known HOIP subclasses. We also present a comprehensive account of their intriguing physical properties, including photovoltaic and optoelectronic properties, dielectricity, magnetism, ferroelectricity, ferroelasticity and multiferroicity. Moreover, we discuss the current challenges and future opportunities in this exciting field. Hybrid organic–inorganic perovskites (HOIPs) comprise a diverse range of chemical compositions from halides and azides to formates, dicyanamides, cyanides and dicyanometallates. In this Review, advances in the synthesis, structures and properties of all HOIP subclasses are summarized and their future opportunities are discussed.

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Chemically diverse and multifunctional hybrid organic–inorganic perovskites

Molecular ferroelectrics are highly desirable for their easy and environmentally friendly processing, light weight, and mechanical flexibility. We found that diisopropylammonium bromide (DIPAB), a molecular crystal processed from aqueous solution, is a ferroelectric with a spontaneous polarization of 23 microcoulombs per square centimeter [close to that of barium titanate (BTO)], high Curie temperature of 426 kelvin (above that of BTO), large dielectric constant, and low dielectric loss. DIPAB exhibits good piezoelectric response and well-defined ferroelectric domains. These attributes make it a molecular alternative to perovskite ferroelectrics and ferroelectric polymers in sensing, actuation, data storage, electro-optics, and molecular or flexible electronics.

https://science.sciencemag.org/content/sci/339/6118/425.full.pdf

Diisopropylammonium Bromide Is a High-Temperature Molecular Ferroelectric Crystal

The development of molecular materials whose physical properties can be controlled by external stimuli - such as light, electric field, temperature, and pressure - has recently attracted much attention owing to their potential applications in molecular devices. There are a number of ways to alter the physical properties of crystalline materials. These include the modulation of the spin and redox states of the crystal's components, or the incorporation within the crystalline lattice of tunable molecules that exhibit stimuli-induced changes in their molecular structure. A switching behaviour can also be induced by changing the molecular orientation of the crystal's components, even in cases where the overall molecular structure is not affected. Controlling intermolecular interactions within a molecular material is also an effective tool to modulate its physical properties. This Review discusses recent advances in the development of such stimuli-responsive, switchable crystalline compounds - referred to here as dynamic molecular crystals - and suggests how different approaches can serve to prepare functional materials.

Dynamic molecular crystals with switchable physical properties

A Multiferroic Perdeutero Metal–Organic Framework

A simple organic salt, diisopropylammonium chloride, shows the highest ferroelectric phase transition temperature among molecule-based ferroelectrics with a large spontaneous polarization, making it a candidate for practical technological applications.

Diisopropylammonium Chloride: A Ferroelectric Organic Salt with a High Phase Transition Temperature and Practical Utilization Level of Spontaneous Polarization

Molecular motion is one of the structural foundations for the development of functional molecular materials such as artificial motors and molecular ferroelectrics. Herein, we show that pendulum-like motion of the terminal group of a molecule causes a ferroelectric phase transition. Complex 4-methoxyanilinium tetrafluoroborate-18-crown-6 ([C7H10NO(18-crown-6)]+[BF4]−, 1) shows a second-order ferroelectric phase transition at 127 K, together with an abrupt dielectric anomaly, Debye-type relaxation behavior, and the symmetry breaking confirmed by temperature dependence of second harmonic generation effect. The origin of the polarization is due to the order–disorder transition of the pendulum-like motions of the terminal para-methyl group of the 4-methoxyanilinium guest cation; that is, the freezing of pendulum motion at low temperature forces significant orientational motions of the guest molecules and thus induces the formation of the ferroelectric phase. The supramolecular bola-like ferroelectric is distin...

Supramolecular bola-like ferroelectric: 4-methoxyanilinium tetrafluoroborate-18-crown-6.

Compound [H2dbco]2·[Cl3]·[CuCl3(H2O)2]·H2O undergoes a sharp dielectric anomaly and a paraelectric-to-ferroelectric phase transition at approximately −23 °C with a spontaneous polarization of 1.04 μC cm−2, being the first molecular metal coordination compound ferroelectrics with a large dielectric response involving a 2 orders of magnitude enhancement and distinct Curie phase transition point. This work has proved an effective way for exploration of new ferroelectrics based on a five-coordinated divalent metal through the combination of crystal engineering and Landau phase transition theory.

Discovery of New Ferroelectrics: [H2dbco]2·[Cl3]·[CuCl3(H2O)2]·H2O (dbco = 1,4-Diaza-bicyclo[2.2.2]octane)

Piezoelectric sensors that can work under various conditions with superior performance are highly desirable with the arrival of the Internet of Things. For practical applications, a large piezoelectric voltage coefficient g and a high Curie temperature Tc are critical to the performance of piezoelectric sensors. Here, we report a two-dimensional perovskite ferroelectric (4-aminotetrahydropyran)2PbBr4 [(ATHP)2PbBr4] with a saturated polarization of 5.6 μC cm-2, high Tc of 503 K [above that of BaTiO3 (BTO, 393 K)], and extremely large g33 of 660.3 × 10-3 V m N-1 [much beyond that of Pb(Zr,Ti)O3 (PZT) ceramics (20 to 40 × 10-3 V m N-1), more than 2 times higher than that of poly(vinylidene fluoride) (PVDF, about 286.7 × 10-3 V m N-1)]. Combined with the advantages of molecular ferroelectrics, such as light weight, easy and environmentally friendly processing, and mechanical flexibility, (ATHP)2PbBr4 would be a competitive candidate for next-generation smart piezoelectric sensors in flexible devices, soft robotics, and biomedical devices.

Jia-Zhen Ge

Papers

A Multiferroic Perdeutero Metal–Organic Framework

Diisopropylammonium Chloride: A Ferroelectric Organic Salt with a High Phase Transition Temperature and Practical Utilization Level of Spontaneous Polarization

Supramolecular bola-like ferroelectric: 4-methoxyanilinium tetrafluoroborate-18-crown-6.

Discovery of New Ferroelectrics: [H2dbco]2·[Cl3]·[CuCl3(H2O)2]·H2O (dbco = 1,4-Diaza-bicyclo[2.2.2]octane)

Two-Dimensional Layered Perovskite Ferroelectric with Giant Piezoelectric Voltage Coefficient