The possibility to engineer (GeTe)m (Sb2 Te3 )n phase-change materials to co-host ferroelectricity is extremely attractive. The combination of these functionalities holds great technological impact, potentially enabling the design of novel multifunctional devices. Here an experimental and theoretical study of epitaxial (GeTe)m (Sb2 Te3 )n with GeTe-rich composition is presented. These layered films feature a tunable distribution of (GeTe)m (Sb2 Te3 )1 blocks of different sizes. Breakthrough evidence of ferroelectric displacement in thick (GeTe)m (Sb2 Te3 )1 lamellae is provided. The density functional theory calculations suggest the formation of a tilted (GeTe)m slab sandwiched in GeTe-rich blocks. That is, the net ferroelectric polarization is confined almost in-plane, representing an unprecedented case between 2D and bulk ferroelectric materials. The ferroelectric behavior is confirmed by piezoresponse force microscopy and electroresistive measurements. The resilience of the quasi van der Waals character of the films, regardless of their composition, is also demonstrated. Hence, the material developed hereby gathers in a unique 2D platform the phase-change and ferroelectric switching properties, paving the way for the conception of innovative device architectures.

CNR Institute for Microelectronics and Microsystems IMM Consiglio Nazionale delle Ricerche Via del Fosso del Cavaliere 100 00133 Roma Italy

Department of Condensed Matter Physics Faculty of Mathematics and Physics Charles University Ke Karlovu 5 12116 Praha Czech Republic

Department of Materials Science University of Milano Bicocca via R Cozzi 55 20125 Milano Italy

Dipartimento di Fisica Politecnico di Milano P zza Leonardo da Vinci 32 20133 Milano Italy

Dipartimento di Fisica Università di Roma Tor Vergata Via della Ricerca Scientifica 1 00133 Rome Italy

Institute of Condensed Matter Physics Faculty of Science Masaryk University Kotlářská 2 611 37 Brno Czech Republic

Institute of Physics Czech Academy of Sciences Cukrovarnická 10 112 16200 Praha 6 Czech Republic

Institute of Solid State and Materials Physics Technische Universität Dresden Helmholtzstr 10 01069 Dresden Germany

Paul Drude Institut für Festkörperelektronik Leibniz Institut im Forschungsverbund Berlin e 5 Hausvogteiplatz 5 7 10117 Berlin Germany

Zernike Institute for Advanced Materials University of Groningen Nijenborgh 4 9747 AG Groningen The Netherlands

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