Hanyu Zhu

Observation of piezoelectricity in free-standing monolayer MoS2

Piezoelectricity allows precise and robust conversion between electricity and mechanical force, and arises from the broken inversion symmetry in the atomic structure. Reducing the dimensionality of bulk materials has been suggested to enhance piezoelectricity. However, when the thickness of a material approaches a single molecular layer, the large surface energy can cause piezoelectric structures to be thermodynamically unstable. Transition-metal dichalcogenides can retain their atomic structures down to the single-layer limit without lattice reconstruction, even under ambient conditions. Recent calculations have predicted the existence of piezoelectricity in these two-dimensional crystals due to their broken inversion symmetry. Here, we report experimental evidence of piezoelectricity in a free-standing single layer of molybdenum disulphide (MoS₂) and a measured piezoelectric coefficient of e₁₁ = 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 MoS₂ 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.

Weaving of organic threads into a crystalline covalent organic framework

Weaving organic threads Woven fabrics are inherently flexible. Liu et al. created a molecular fabric analog using metal-organic frameworks (see the Perspective by Gutierrez-Puebla). Phenanthroline ligands on a copper metal complex directed the addition of organic linkers via imine bonds to create helical organic threads with woven texture. Removing the copper allowed the strands to slide against each other and increased the elasticity of the material 10-fold. Science, this issue p. 365; see also p. 336 A metal-organic framework templates the synthesis of a material made of woven organic polymers. [Also see Perspective by Gutierrez-Puebla] A three-dimensional covalent organic framework (COF-505) constructed from helical organic threads, designed to be mutually weaving at regular intervals, has been synthesized by imine condensation reactions of aldehyde functionalized copper(I)-bisphenanthroline tetrafluoroborate, Cu(PDB)2(BF4), and benzidine (BZ). The copper centers are topologically independent of the weaving within the COF structure and serve as templates for bringing the threads into a woven pattern rather than the more commonly observed parallel arrangement. The copper(I) ions can be reversibly removed and added without loss of the COF structure, for which a tenfold increase in elasticity accompanies its demetalation. The threads in COF-505 have many degrees of freedom for enormous deviations to take place between them, throughout the material, without undoing the weaving of the overall structure.

Large-scale chemical assembly of atomically thin transistors and circuits

Next-generation electronics calls for new materials beyond silicon, aiming at increased functionality, performance and scaling in integrated circuits. In this respect, two-dimensional gapless graphene and semiconducting transition-metal dichalcogenides have emerged as promising candidates due to their atomic thickness and chemical stability. However, difficulties with precise spatial control during their assembly currently impede actual integration into devices. Here, we report on the large-scale, spatially controlled synthesis of heterostructures made of single-layer semiconducting molybdenum disulfide contacting conductive graphene. Transmission electron microscopy studies reveal that the single-layer molybdenum disulfide nucleates at the graphene edges. We demonstrate that such chemically assembled atomic transistors exhibit high transconductance (10 µS), on-off ratio (∼106) and mobility (∼17 cm2 V-1 s-1). The precise site selectivity from atomically thin conducting and semiconducting crystals enables us to exploit these heterostructures to assemble two-dimensional logic circuits, such as an NMOS inverter with high voltage gain (up to 70).Next-generation electronics calls for new materials beyond silicon for increased functionality, performance, and scaling in integrated circuits. Carbon nanotubes and semiconductor nanowires are at the forefront of these materials, but have challenges due to the complex fabrication techniques required for large-scale applications. Two-dimensional (2D) gapless graphene and semiconducting transition metal dichalcogenides (TMDCs) have emerged as promising electronic materials due to their atomic thickness, chemical stability and scalability. Difficulties in the assembly of 2D electronic structures arise in the precise spatial control over the metallic and semiconducting atomic thin films. Ultimately, this impedes the maturity of integrating atomic elements in modern electronics. Here, we report the large-scale spatially controlled synthesis of the single-layer semiconductor molybdenum disulfide (MoS2) laterally in contact with conductive graphene. Transition electron microscope (TEM) studies reveal that the single-layer MoS2 nucleates at the edge of the graphene, creating a lateral 2D heterostructure. We demonstrate such chemically assembled 2D atomic transistors exhibit high transconductance (10 uS), on-off ratios (10^6), and mobility (20 cm^2 V^-1 s^-1). We assemble 2D logic circuits, such as a heterostructure NMOS inverter with a high voltage gain, up to 70, enabled by the precise site selectivity from atomically thin conducting and semiconducting crystals. This scalable chemical assembly of 2D heterostructures may usher in a new era in two-dimensional electronic circuitry and computing.

Electrical generation and control of the valley carriers in a monolayer transition metal dichalcogenide

Electrically controlling the flow of charge carriers is the foundation of modern electronics. By accessing the extra spin degree of freedom (DOF) in electronics, spintronics allows for information processes such as magnetoresistive random-access memory. Recently, atomic membranes of transition metal dichalcogenides (TMDCs) were found to support unequal and distinguishable carrier distribution in different crystal momentum valleys. This valley polarization of carriers enables a new DOF for information processing. A variety of valleytronic devices such as valley filters and valves have been proposed, and optical valley excitation has been observed. However, to realize its potential in electronics it is necessary to electrically control the valley DOF, which has so far remained a significant challenge. Here, we experimentally demonstrate the electrical generation and control of valley polarization. This is achieved through spin injection via a diluted ferromagnetic semiconductor and measured through the helicity of the electroluminescence due to the spin-valley locking in TMDC monolayers. We also report a new scheme of electronic devices that combine both the spin and valley DOFs. Such direct electrical generation and control of valley carriers opens up new dimensions in utilizing both the spin and valley DOFs for next-generation electronics and computing.

Janus monolayers of transition metal dichalcogenides

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 MoS2 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.

Demonstration of a large-scale optical exceptional point structure

We report a large-size (4-inch) optical exceptional point structure at visible frequencies by designing a multilayer structure of absorbing and non-absorbing dielectrics. The optical exceptional point was implemented as indicated by the realized unidirectional reflectionless light transport at a wafer scale. The associated abrupt phase transition is theoretically and experimentally confirmed when crossing over the exceptional point in wavelengths. The large scale demonstration of phase transition around exceptional points will open new possibilities in important applications in free space optical devices.

Exciton-dominant electroluminescence from a diode of monolayer MoS2

We studied the microscopic origin of the electroluminescence from monolayer MoS2 fabricated on a heavily p-type doped silicon substrate. Auger recombination of the exciton-exciton annihilation of bound exciton emission is observed.

Valley photonic crystals for control of spin and topology

Photonic crystals offer unprecedented opportunity for light manipulation and applications in optical communication and sensing. Exploration of topology in photonic crystals and metamaterials with non-zero gauge field has inspired a number of intriguing optical phenomena such as one-way transport and Weyl points. Recently, a new degree of freedom, valley, has been demonstrated in two-dimensional materials. Here, we propose a concept of valley photonic crystals with electromagnetic duality symmetry but broken inversion symmetry. We observe photonic valley Hall effect originating from valley-dependent spin-split bulk bands, even in topologically trivial photonic crystals. Valley-spin locking behaviour results in selective net spin flow inside bulk valley photonic crystals. We also show the independent control of valley and topology in a single system that has been long pursued in electronic systems, resulting in topologically-protected flat edge states. Valley photonic crystals not only offer a route towards the observation of non-trivial states, but also open the way for device applications in integrated photonics and information processing using spin-dependent transportation.

Structural phase transition in monolayer MoTe 2 driven by electrostatic doping

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 (MoTe2). 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.

Atomically phase-matched second-harmonic generation in a 2D crystal

Second-harmonic generation (SHG) has found extensive applications from hand-held laser pointers to spectroscopic and microscopic techniques. Recently, some cleavable van der Waals (vdW) crystals have shown SHG arising from a single atomic layer, where the SH light elucidated important information such as the grain boundaries and electronic structure in these ultra-thin materials. However, despite the inversion asymmetry of the single layer, the typical crystal stacking restores inversion symmetry for even numbers of layers leading to an oscillatory SH response, drastically reducing the applicability of vdW crystals such as molybdenum disulfide (MoS2). Here, we probe the SHG generated from the noncentrosymmetric 3R crystal phase of MoS2. We experimentally observed quadratic dependence of second-harmonic intensity on layer number as a result of atomically phase-matched nonlinear dipoles in layers of the 3R crystal that constructively interfere. By studying the layer evolution of the A and B excitonic transitions in 3R-MoS2 using SHG spectroscopy, we also found distinct electronic structure differences arising from the crystal structure and the dramatic effect of symmetry and layer stacking on the nonlinear properties of these atomic crystals. The constructive nature of the SHG in this 2D crystal provides a platform to reliably develop atomically flat and controllably thin nonlinear media.