Tetramethylbenzidine-TetrafluoroTCNQ (TMB-TCNQF(4)) : a narrow-gap semiconducting salt with room-temperature relaxor ferroelectric behavior
| Autor: | Jonas K. H. Fischer, Raphael Pfattner, Ruggero Frison, Elena Ferrari, Matteo Masino, Alberto Girlando, Peter Lunkenheimer, Stefano Canossa, Concepció Rovira, Pit Sippel, Marta Mas-Torrent |
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| Přispěvatelé: | German Research Foundation, Ministerio de Ciencia e Innovación (España), Generalitat de Catalunya, Ministero dell'Istruzione, dell'Università e della Ricerca |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Materials science Condensed matter physics Physics Salt (chemistry) Surfaces Coatings and Films Electronic Optical and Magnetic Materials Chemistry General Energy chemistry Narrow gap ddc:530 Physical and Theoretical Chemistry Engineering sciences. Technology Relaxor ferroelectric |
| Zdroj: | The journal of physical chemistry: C : nanomaterials and interfaces Digital.CSIC. Repositorio Institucional del CSIC instname |
| ISSN: | 1932-7447 |
| Popis: | We present an extension and revision of the spectroscopic and structural data of the mixed-stack charge-transfer (CT) crystal 3,3′,5,5′-tetramethylbenzidine–tetrafluorotetracyanoquinodimethane (TMB–TCNQF4), associated with new electric and dielectric measurements. Refinement of synchrotron structural data at low temperature has led to revise the previously reported C2/m structure. The revised structure is P21/m, with two dimerized stacks per unit cell, and is consistent with the low-temperature vibrational data. However, polarized Raman data in the low-frequency region also indicate that by increasing temperature above 200 K, the structure presents an increasing degree of disorder, mainly along the stack axis. X-ray diffraction data at room temperature have confirmed that the correct structure is P21/m─no phase transitions─but did not allow substantiating the presence of disorder. On the other hand, dielectric measurements have evidenced a typical relaxor ferroelectric behavior already at room temperature, with a peak in the real part of dielectric constant ϵ′(T,ν) around 200 K and 0.1 Hz. The relaxor behavior is explained in terms of the presence of spin solitons separating domains of opposite polarity that yield to ferroelectric nanodomains. TMB–TCNQF4 is confirmed to be a narrow-gap band semiconductor (Ea ∼ 0.3 eV) with a room-temperature conductivity of ∼10–4 Ω–1 cm–1. A.G. thanks Prof. Pascale Foury-Leylekian for very helpful discussions about the crystallographic issues. R.F. thanks Prof. Anthony Linden for his help in the X-ray diffraction data collection. J.K.H.F. and P.L. acknowledge funding from the Deutsche Forschungsgemeinschaft (DFG) via the Transregional Collaborative Research Center TRR80 (Augsburg, Munich). R.P. and M.M.-T. acknowledge support from the Marie Curie Cofund, Beatriu de Pinós Fellowships (Grant nos. AGAUR 2017 BP 00064). This work was also supported by the Spanish Ministry project GENESIS PID2019-111682RB-I00, the “Severo Ochoa” Programme for Centers of Excellence in R&D (FUNFUTURE, CEX2019-000917-S), and the Generalitat de Catalunya (2017-SGR-918). The Elettra Synchrotron (CNR Trieste) is acknowledged for granting the beamtime at the single-crystal diffraction beamline XRD1 (Proposal ID 20185483). In Parma, the work has benefited from the equipment and support of the COMP-HUB Initiative, funded by the “Departments of Excellence” program of the Italian Ministry for Education, University and Research (MIUR, 2018-2022). |
| Databáze: | OpenAIRE |
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