Tetramethylbenzidine–TetrafluoroTCNQ (TMB–TCNQF4): A Narrow-Gap Semiconducting Salt with Room-Temperature Relaxor Ferroelectric Behavior

Abstract

We present an extension and revision of the spectroscopic and structural data of the mixed stack charge transfer (CT) crystal 3,3$^\prime$,5,5$^\prime$-tetramethylbenzidine--tetrafluoro-tetracyanoquinodimethane (TMB-TCNQF4), associated with new electric and dielectric measurements. Refinement of syncrotron structural data at low temperature has led to revise the previously reported [Phys. Rev. Mat. 2, 024602 (2018)] $C2/m$ structure. The revised structure is $P2_1/m$, with two dimerized stacks per unit cell, and is consistent with the 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 $P2_1/m$ -- no phase transitions -- but did not allow to definitely substantiate the presence of disorder. On the other hand, dielectric measurement have evidenced a typical relaxor ferroelectric behavior already at room temperature, with a peak in real part of dielectric constant $\epsilon'(T,\nu)$ 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 ($E_a \sim 0.3$ eV) with room temperature conductivity of $\sim 10^{-4}~ \Omega^{-1}$ cm$^{-1}$.