A Chiral B−N Adduct as a New Frontier in Ferroelectrics and Piezoelectric Energy Harvesting

Abstract

Within the burgeoning field of electronic materials, B‐N Lewis acid‐base pairs, distinguished by their partial charge distribution across boron and nitrogen centers, represent an underexplored class with significant potential. These materials exhibit inherent dipoles and are excellent candidates for ferroelectricity. However, the challenge lies in achieving the optimal combination of hard‐soft acid‐base pairs to yield B‐N adducts with stable dipoles. Herein, we present an enantiomeric pair of B‐N adducts [R/SC6H5CH(CH3)NH2BF3] (R/SMBA‐BF3) crystallizing in the polar monoclinic P21 space group. The ferroelectric measurements on RMBA‐BF3 gave a rectangular P‐E hysteresis loop with a remnant polarization of 7.65 µC cm‐2, a value that aligns with the polarization derived from the extensive density‐functional theory computations. The PFM studies on the drop‐casted film of RMBA‐BF3 further corroborate the existence of ferroelectric domains, displaying characteristic amplitude‐bias butterfly and phase‐bias hysteresis loops. The piezoelectric nature of the RMBA‐BF3 was confirmed by its direct piezoelectric coefficient (d33) value of 3.5 pC N‐1 for its pellet. The piezoelectric energy harvesting applications on the sandwich devices fabricated from the as‐made crystals of RMBA‐BF3 gave an open circuit voltage (VPP) of 6.2 V. This work thus underscores the untapped potential of B‐N adducts in the field of piezoelectric energy harvesting.

Ferroelectric Organic–Inorganic Hybrid Ammonium Halogenobismuthate(III) for Piezoelectric Energy Harvesting

“…Technological applications increasingly rely on multifunctional materials due to their unique physical and chemical properties . Within this domain, ferroelectrics, a subset of dielectric materials, have garnered significant attention for their potential in various applications, including ferroelectric random-access memories, microelectromechanical devices, wireless electronics, transducers, wearable memory devices, robotics, energy harvesting, etc. − For instance, the multifunctional nature of ferroelectric materials is evident from their utility for piezoelectric energy harvesting, wherein a sizable ferroelectric polarization aids in the efficient conversion of mechanical energy into electrical outputs. − Over the years, ceramic oxide materials such as barium titanate, lithium niobate, lead titanate, lead zirconate titanate (PZT), zinc oxide, etc., have been the focus of extensive research due to their excellent ferroelectric and piezoelectric attributes. − However, their brittleness and toxic metal content limit their suitability for low-power, wearable electronics . On the other hand, semicrystalline organic polymers, such as polyvinylidene fluoride and its copolymers, offer a flexible, metal-free alternative, showing ferroelectricity and potential for device applications .…”

“… 2 − 5 For instance, the multifunctional nature of ferroelectric materials is evident from their utility for piezoelectric energy harvesting, wherein a sizable ferroelectric polarization aids in the efficient conversion of mechanical energy into electrical outputs. 6 − 8 Over the years, ceramic oxide materials such as barium titanate, lithium niobate, lead titanate, lead zirconate titanate (PZT), zinc oxide, etc., have been the focus of extensive research due to their excellent ferroelectric and piezoelectric attributes. 9 − 13 However, their brittleness and toxic metal content limit their suitability for low-power, wearable electronics.…”

A Highly Electrostrictive Salt Cocrystal and the Piezoelectric Nanogenerator Application of Its 3D-Printed Polymer Composite

“… 28 , 29 Hence, single- and two-component organic compounds are attractive candidates for obtaining piezoelectrics with high electromechanical properties. 30 − 32 Over the years, a variety of organic molecules, including croconic acid, 33 diisopropylammonium chloride (DIPAC), 34 diisopropylammonium bromide (DIPAB), 35 imidazolium perchlorate (Im-ClO 4 ), 36 [Hdabco]ClO 4 (dabco = 1,4-diazabicyclo[2.2.2]octane), 37 MDABCO–NH 4 I 3 (MDABCO = N -methyl- N′ -diazabicyclo[2.2.2]octonium), 38 trimethylamine borane (TMAB), 31 and R MBA-BF 3 ( R MBA = R C 6 H 5 CH(CH 3 )NH 2 ), 39 were found to exhibit ferroelectric properties. These compounds can be classified as single-component, two-component and zwitterionic forms.…”

“…Cocrystal engineering is well known for the creation of new organic materials with extraordinary properties that enable comprehensive studies on their structure–property relationships. , In this regard, noncovalent interactions such as π···π stacking, hydrogen bonds, halogen bonds, and ion–dipole interactions play a pivotal role in the design of organic cocrystals. − These interactions provide significant stability and directional preference, leading to enhanced physiochemical properties desired for functional organic materials . Materials possessing ferroelectric, dielectric, and piezoelectric properties are extensively explored as ferroelectric random access memory devices, actuators, wearable electronics, electromechanical transducers, medical devices, robotics, and energy storage materials. − Among these, ferroelectric materials possessing piezoelectric characteristics are particularly useful for their ability to convert mechanical stimuli into electrical voltage, making them suitable for use in piezoelectric nanogenerators (PENGs). − PENGs have become increasingly important in modern high-tech electronics, particularly for energy harvesting, storage, and dissipation. − However, the electrostrictive coefficient ( Q 33 ), the measure of PENG output for any piezoelectric material, is low for traditional ceramic materials (0.034–0.096 m 4 C –2 ) in comparison with organic piezoelectrics such as polyvinylidene difluoride (1.3 m 4 C –2 ). , Hence, single- and two-component organic compounds are attractive candidates for obtaining piezoelectrics with high electromechanical properties. − Over the years, a variety of organic molecules, including croconic acid, diisopropylammonium chloride (DIPAC), diisopropylammonium bromide (DIPAB), imidazolium perchlorate (Im-ClO 4 ), [Hdabco]­ClO 4 (dabco = 1,4-diazabicyclo[2.2.2]­octane), MDABCO–NH 4 I 3 (MDABCO = N -methyl- N′ -diazabicyclo­[2.2.2]­octonium), trimethylamine borane (TMAB), and R MBA-BF 3 ( R MBA = R C 6 H 5 CH­(CH 3 )­NH 2 ), were found to exhibit ferroelectric properties. These compounds can be classified as single-component, two-component and zwitterionic forms.…”

Homochirality-Induced Piezoelectricity in a Single-Component Molecular System

“…Nanogenerators play an important role in the Internet of Things era (IoTs), with applications in e-skin, biomedical devices, and various other wearable electronics. − Harvesting mechanical energy is an attractive green energy generation source with a high potential for powering miniature electronic devices. − Piezoelectric energy harvesting is an efficient way to convert the input mechanical energy into usable electrical energy using the piezoelectric effect of the materials. − Over the past decade, molecular piezoelectric nanogenerators (PENG) have found applications in numerous practical sectors, including optics, microelectronics, precision mechanics, life sciences, etc. − …”