Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

Monolayers of transition-metal dichalcogenides (TMDs) exhibit numerous crystal phases with distinct structures, symmetries and physical properties. Exploring the physics of transitions between these different structural phases in two dimensions may provide a means of switching material properties, with implications for potential applications. Structural phase transitions in TMDs have so far been induced by thermal or chemical means; purely electrostatic control over crystal phases through electrostatic doping was recently proposed as a theoretical possibility, but has not yet been realized. Here we report the experimental demonstration of an electrostatic-doping-driven phase transition between the hexagonal and monoclinic phases of monolayer molybdenum ditelluride (MoTe). We find that the phase transition shows a hysteretic loop in Raman spectra, and can be reversed by increasing or decreasing the gate voltage. We also combine second-harmonic generation spectroscopy with polarization-resolved Raman spectroscopy to show that the induced monoclinic phase preserves the crystal orientation of the original hexagonal phase. Moreover, this structural phase transition occurs simultaneously across the whole sample. This electrostatic-doping control of structural phase transition opens up new possibilities for developing phase-change devices based on atomically thin membranes.

Piezoelectricity allows precise and robust conversion between electricity and mechanical force, and arises from the broken inversion symmetry in the atomic structure [1][2][3] . Reducing the dimensionality of bulk materials has been suggested to enhance piezoelectricity 4 . However, when the thickness of a material approaches a single molecular layer, the large surface energy can cause piezoelectric structures to be thermodynamically unstable 5 . Transition-metal dichalcogenides can retain their atomic structures down to the single-layer limit without lattice reconstruction, even under ambient conditions 6 . Recent calculations have predicted the existence of piezoelectricity in these two-dimensional crystals due to their broken inversion symmetry 7 . Here, we report experimental evidence of piezoelectricity in a free-standing single layer of molybdenum disulphide (MoS 2 ) and a measured piezoelectric coefficient of e 11 = 2.9 × 10 -10 C m −1 . The measurement of the intrinsic piezoelectricity in such free-standing crystals is free from substrate effects such as doping and parasitic charges. We observed a finite and zero piezoelectric response in MoS 2 in odd and even number of layers, respectively, in sharp contrast to bulk piezoelectric materials. This oscillation is due to the breaking and recovery of the inversion symmetry of the two-dimensional crystal. Through the angular dependence of electromechanical coupling, we determined the two-dimensional crystal orientation. The piezoelectricity discovered in this single molecular membrane promises new applications in low-power logic switches for computing and ultrasensitive biological sensors scaled down to a single atomic unit cell 8,9 .Since its discovery in 1880, piezoelectricity has found a wide range of applications in actuation, sensing and energy harvesting. The rapidly growing demand for high-performance and miniaturized devices in micro-electro-mechanical systems (MEMS) and electronics 10-12 calls for nanoscale piezoelectric materials, motivating theoretical investigations into novel low-dimensional systems such as nanotubes and single molecules 13,14 . Transition-metal dichalcogenides (TMDCs) are ideal candidates as low-dimensional piezoelectric materials because of their structural non-centrosymmetry 7 . Although there has been extensive research interest in the unique properties originating from such symmetry breaking, including circular dichroism and second harmonic generation (SHG) [15][16][17][18][19] , experimental quantitative determination of the intrinsic piezoelectric properties of these two-dimensional crystals has yet to be demonstrated. Here, we report the observation of piezoelectricity in freestanding monolayer MoS 2 membranes. Interestingly, we found that this molecular piezoelectricity only exists when there are an odd number of layers in the two-dimensional crystal where inversion symmetry breaking occurs. We observed an angular dependence of the piezoelectric response in agreement with the three-fold symmetry of the crystal, and based...

The critical size limit of electric polarization remains a fundamental question in nanoscale ferroelectric research 1 . As such, the viability of ultrathin ferroelectricity greatly impacts emerging low-power logic and nonvolatile memories 2 . Size effects in ferroelectrics have been thoroughly investigated for perovskite oxides -the archetypal ferroelectric system 3 . Perovskites, however, have so far proved unsuitable for thickness-scaling and integration with modern semiconductor processes 4 . Here, we report ultrathin ferroelectricity in doped-HfO2, a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to 1 nm. Our results indicate not only the absence of a ferroelectric critical thickness, but also enhanced polar distortions as film thickness is reduced, contradictory to perovskite ferroelectrics. This work shifts the focus on the fundamental limits of ferroelectricity to simpler transition metal oxide systems -from perovskite-derived complex oxides to fluoritestructure binary oxides -in which 'reverse' size effects counter-intuitively stabilize polar symmetry in the ultrathin regime.Ferroelectric materials exhibit stable states of collectively ordered electrical dipoles whose polarization can be reversed under an applied electric field 5 . Consequently, ultrathin ferroelectrics are of great technological interest for high-density electronics, particularly field-effect transistors and nonvolatile memories 2 . However, ferroelectricity is typically suppressed at the few nanometer scale in the ubiquitous perovskite oxides 6 . First-principles calculations predict six unit cells as the critical thickness in perovskite ferroelectrics 1 due to incomplete screening of depolarization fields 3 . Atomic-scale ferroelectricity in perovskites often fail to demonstrate polarization switching 7,8 , a crucial ingredient for application. Furthermore, attempts to synthesize ferroelectric perovskite films on silicon 9,10 are plagued by chemical incompatibility 4,11 and high temperatures required for epitaxial growth. Since the discovery of ferroelectricity in HfO2-based thin films in 2011 12 , fluorite-structure binary oxides (fluorites) have attracted considerable interest 13 as they enable lowtemperature synthesis and conformal growth in three-dimensional (3D) structures on silicon 14,15 , thereby overcoming many of the issues that restrict its perovskite counterparts in terms of complementary metal-oxide-semiconductor (CMOS) compatibility and thickness scaling 16 .