Thickness-Dependent High-Temperature Piezo- and Ferro-Electricity in a Fluorenone-Based Molecular Crystal

resumo

Organic polar crystalline materials, featuring the merits of lightweight, flexibility, and low fabrication costs, are emerging as promising alternatives for inorganic ferroelectrics, but so far, they are not competitive. The main reasons are the moderate polar properties of such materials and the fact that the temperature of the phase transition from polar to nonpolar states (Curie point) is typically located near room temperature. The organic molecular crystal of the fluorenone derivative 2,7-diphenyl-9H-fluorene-9-one (DPFO) is demonstrated to feature robust high-temperature piezo- and ferro-electric properties, with a relatively high local piezoelectric coefficient (d(33)) of approximate to 120 pm V-1. The origin of the strong piezoelectricity is attributed to the presence of intrinsic domain structures in the DPFO microfiber crystals, originating from intramolecular co-operation between the central fluorenone backbone and the external phenyl rings that are found stable up to 423 K. Moreover, this intramolecular co-operation and the corresponding polar properties are found to depend on the thickness of the DPFO microfiber, resulting in a change from ferroelectric (<0.5 mu m) to piezoelectric (>= 0.5 mu m) behavior. Considering the low cost and flexible production of such fluorenone-based organic lead-free ferroelectrics, this is a very promising strategy toward technological applications in electromechanical actuators, sensors, energy harvesters, and non-volatile memory cells.

palavras-chave

ORBITAL METHODS; BASIS-SETS

categoria

Chemistry; Materials Science

autores

Ivanov, M; Nikitin, T; Lopes, S; Duan, YL; Xu, JL; Fausto, R; Paixao, JA; Vilarinho, PM; Rasing, T; Semin, S

nossos autores

agradecimentos

The reported study was supported by the Russian Science Foundation (Grant No. 20-79-10223) and was partly supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) and the European Research Council ERC grant agreement no. 856538 (3D-MAGiC). T.N. is grateful to the Fundacao para a Ciencia e Tecnologia (FCT) for financial support through the projects PTDC/QEQ-QFI/3284/2014 and SUSpENse (CENTRO-01-0145-FEDER-000006). J.X. is grateful to the financial support from National Natural Science Foundation of China (52172045). Y.D. acknowledges financial support from the China Scholarship Council (201409370018). The FCT projects BIOMEMs (POCI-01-0145-FEDER-032095) and MATIS -Materiais e Tecnologias Industriais Sustentaveis (CENTRO-01-0145-FEDER-000014), including access to TAIL-UC facility funded under QREN-Mais Centro project ICT_2009_02_012_1890 are gratefully acknowledged. The Coimbra Chemistry Centre and Coimbra Physics Centre are supported by FCT through the projects UIDB/00313/2020, UIDP/00313/2020, UI0313/QUI/2020, UIDB/04564/2020, and UIDP/04564/2020, respectively, co-funded by COMPETE-UE. This work was also developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020, and LA/P/0006/2020, financed by national funds through the FCT/MCTES (PIDDAC).

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