In-plane ferroelectricity in few-layered GeS and its van der Waals ferroelectric diodes

Two-dimensional ferroelectric semiconductors (2DFeSs) have been attracting extensive research attention on account of their unique properties and versatile applications in random-access memory, digital signal processors, and neuromorphic computing. Germanium sulfide (GeS) is predicted as a typical 2DFeS with a large spontaneous polarization of 484 pC m^-1. Furthermore, the moderate band gap equivalent to 1.63 eV of GeS provides it with significant potential to create a strong bulk photovoltage in the visible light range. However, the fabrication of chemically stable few-to-monolayer GeS has not been reported so far, owing to the strong interlayer force and high chemical reactivity of the surface. Herein we demonstrate a new method for fabricating high quality, air-stable, ultrathin GeS nanoflakes. The electrical characterization confirms the formation of few-layered GeS with a remarkable in-plane ferroelectric hysteresis, which is forbidden by the inversion symmetry in bulk GeS crystals. After applying a coercive field of about 18.1 kV cm^-1, a switchable shift current can also be observed in the polarized GeS nanoflakes under light irradiation. To further enhance the photoresponsivity, few-layered InSe was transferred onto the GeS nanoflakes to form van der Waals ferroelectric diodes. The interfacial perturbation breaking the inversion symmetry results in the enhancement of robust dipoles in the GeS side along the interface, which can be tuned by the in-plane electric field. Overall, this work opens the door for exploring the low-dimensional ferroelectric memory and energy conversion applications based on 2D GeS nanoflakes and provides a deeper understanding of the photovoltaic mechanism with in-plane 2D ferroelectric diodes.