Photoinduced switching to metallic states in the two-dimensional organic Mott insulator dimethylphenazine-tetrafluorotetracyanoquinodimethane with anisotropic molecular stacks

Abstract

A photoinduced phase transition was investigated in an organic charge-transfer (CT) complex ${\mathrm{M}}_{2}\mathrm{P}\ensuremath{-}\mathrm{TCNQ}{\mathrm{F}}_{4}, [{\mathrm{M}}_{2}\mathrm{P}$: 5,10-dihydro-5,10-dimethylphenazine, donor (D) molecule; $\mathrm{TCNQ}{\mathrm{F}}_{4}$: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, acceptor (A) molecule] by means of femtosecond pump-probe reflection spectroscopy. This is an ionic compound and has a peculiar two-dimensional (2D) molecular arrangement; the same A (or D) molecules arrange along the [100] direction, and A and D molecules alternately arrange along the [111] direction. It results in a strongly anisotropic two-dimensional electronic structure. This compound shows a structural and magnetic phase transition at 122 K below which the two neighboring molecules are dimerized along both the [100] and [111] directions. We demonstrate that two kinds of photoinduced phase transitions occur by irradiation of a femtosecond laser pulse; in the high-temperature lattice-uniform phase, a quasi-one-dimensional (1D) metallic state along the AA(DD) stack is generated, and in the low-temperature lattice-dimerized phase, a quasi-2D metallic state is initially produced and molecular dimerizations are subsequently released. Mixed-stack CT compounds consisting of DA stacks are generally insulators or semiconductors in the ground state. Here, such a dynamical metallization in the DA stack is demonstrated. The release of the dimerizations drives several kinds of coherent oscillations which play an important role in the stabilization of the lattice-dimerized phase. The mechanisms of those photoinduced phase transitions are discussed in terms of the magnitudes of the anisotropic bandwidths and molecular dimerizations along two different directions of the molecular stacks.