Nonpolar Monolayers Research Articles

Sliding-reversible bandgap modulation in irreversible asymmetric multilayers

The electronic bandgap of a material is often fixed after fabrication. The capability to realize on-demand and nonvolatile control over the bandgap will unlock exciting opportunities for adaptive devices with enhanced functionalities and efficiency. We introduce a general design principle for on-demand and nonvolatile control of bandgap values, which utilizes reversible sliding-induced polarization driven by an external electric field to modulate the irreversible background polarization in asymmetric two-dimensional (2D) multilayers. The structural asymmetry can be conveniently achieved in homobilayers of Janus monolayers and heterobilayers of nonpolar monolayers, making the design principle applicable to a broad range of 2D materials. We demonstrate the versatility of this design principle using experimentally synthesized Janus metal dichalcogenide multilayers as examples. Our first-principles calculations show that the bandgap modulation can reach up to 0.3 eV and even support a semimetal-to-semiconductor transition. By integrating a ferroelectric monolayer represented by 1T″′-MoS2 into a bilayer, we show that the combination of intrinsic ferroelectricity and sliding ferroelectricity leads to multi-bandgap systems coupled to multi-step polarization switching. The sliding-reversible bandgap modulation offers an avenue to dynamically adjust the optical, thermal, and electronic properties of 2D materials through mechanical and electrical stimuli.

General Theory for Bilayer Stacking Ferroelectricity.

Two-dimensional (2D) ferroelectrics, which are rare in nature, enable high-density nonvolatile memory with low energy consumption. Here, we propose a theory of bilayer stacking ferroelectricity (BSF), in which two stacked layers of the same 2D material, with different rotation and translation, exhibit ferroelectricity. By performing systematic group theory analysis, we find all the possible BSF in all 80 layer groups (LGs) and discover the rules about the creation and annihilation of symmetries in the bilayer. Our general theory can not only explain all the previous findings (including sliding ferroelectricity), but also provide a new perspective. Interestingly, the direction of the electric polarization of the bilayer could be totally different from that of the single layer. In particular, the bilayer could become ferroelectric after properly stacking two centrosymmetric nonpolar monolayers. By means of first-principles simulations, we predict that the ferroelectricity and thus multiferroicity can be introduced to the prototypical 2D ferromagnetic centrosymmetric material CrI_{3} by stacking. Furthermore, we find that the out-of-plane electric polarization in bilayer CrI_{3} is interlocked with the in-plane electric polarization, suggesting that the out-of-plane polarization can be manipulated in a deterministic way through the application of an in-plane electric field. The present BSF theory lays a solid foundation for designing a large number of bilayer ferroelectrics and thus colorful platforms for fundamental studies and applications.

Emerging van der Waals ferroelectrics: Unique properties and novel devices

The past few decades have witnessed extensive and intensive studies on ferroelectric materials with switchable electric polarization due to their broad device applications. Emerging van der Waals (vdW) layered ferroelectrics ingeniously assemble strong covalent-bonded polar or non-polar monolayers through weak vdW forces. These atom arrangements contrast with the stacking of conventional oxide ferroelectrics, enabling unprecedented ferroelectric physics in terms of polarization origin, polar stabilization, and switching kinetics. Combined with other inherent optical and electrical features, the vdW ferroelectrics can undoubtedly provide a new, versatile platform for advancing fundamental physics and revolutionizing device technology. In this review, we summarize the unique ferroelectric properties in experimentally confirmed vdW ferroelectrics, particularly those properties that expand our understanding of ferroelectric switching. We also elucidate how some of these properties can intrinsically reduce depolarized instability at the atomic limit. Finally, we discuss innovative devices enabled by distinct properties of vdW ferroelectrics for electronic, optoelectronic, and energy-harvesting applications, and highlight possible future research lines.

Influence of Order within Nonpolar Monolayers on Hydrophobic Interactions.

We report an experimental investigation of the influence of molecular-level order (crystallinity) within nonpolar monolayers on hydrophobic interactions. The measurements were performed using gold film-supported monolayers formed from alkanethiols (CH3(CH2)nSH, with n ranging from 3 to 17), which we confirmed by using polarization-modulation infrared reflection-adsorption spectroscopy to exhibit chain-length-dependent order (methylene peak moves from 2926 to 2919 cm-1, corresponding to a transition from liquid- to quasi-crystalline-like order) in the absence of substantial changes in chain density (constant methyl peak intensity). By using monolayer-covered surfaces immersed in either aqueous triethanolamine (TEA, 10 mM, pH 7.0) or pure methanol, we quantified hydrophobic and van der Waals contributions to adhesive interactions between identical pairs of surfaces (measured using an atomic force microscope) as a function of the length and order of the aliphatic chains within the monolayers. In particular, we measured pull-off forces arising from hydrophobic adhesion to increase in a nonlinear manner with chain length (abrupt increase between n = 5 and 6 from 2.1 ± 0.3 to 14.1 ± 0.7 nN) and to correlate closely with a transition from a liquid-like to crystalline-like monolayer phase. In contrast, adhesion in methanol increased gradually with chain length from 0.3 ± 0.1 to 3.2 ± 0.3 nN for n = 3 to 7 and then did not change further with an increase in chain length. These results lead to the hypothesis that order within nonpolar monolayers influences hydrophobic interactions. Additional support for this hypothesis was obtained from measurements reported in this paper using long-chain alkanethiols (ordered) and alkenethiols (disordered). The results are placed into the context of recent spectroscopic studies of hydrogen bonding of water at nonpolar monolayers. Overall, our study provides new insight into factors that influence hydrophobic interactions at nonpolar monolayers.

A molecular dynamics study of the ionic and molecular permeability of alkanethiol monolayers on the gold electrode surface

Ionic and molecular permeability of monolayers of alkanethiols on the Au(111) surface in an aqueous NaF solution is investigated using the molecular dynamics (MD) method. The surface charge-driven penetration of the electrolyte components into the monolayer was found to have a threshold. The mechanism of ion permeation comprises two steps, (1) the formation of a polar channel of water molecules which are drawn into the nonpolar monolayer due to local electric field fluctuations (2) transport of ions through the polar channel to the Au(111) surface. It is concluded that the defect-free monolayers are impermeable for the electrolyte components at electrode potentials related to the stability region of the monolayer. The monolayer of hexadecanethiols (—SC16H33) is less permeable with that of hexanethiols (—SC6H13), this is explained in terms of a closer packing structure for longer hydrocarbon tails.

Critical behavior of a nonpolar smectogen from high-resolution birefringence measurements

We report high-sensitivity and high-temperature resolution experimental data for the temperature dependence of the optical birefringence of a nonpolar monolayer smectogen 4-butyloxyphenyl-4'-decyloxybenzoate (10[over ¯].O.4[over ¯]) liquid crystal by using a rotating-analyzer technique. The birefringence data cover nematic and smectic-A phases of the 10[over ¯].O.4[over ¯] compound. The birefringence data are used to probe the temperature behavior of the nematic order parameter S(T) in the vicinity of both the nematic-isotropic (N-I) and the nematic-smectic-A (N-SmA) transitions. For the N-I transition, from the data sufficiently far away from the smectic-A phase, the average value of the critical exponent β describing the limiting behavior of S(T) is found to be 0.2507±0.0010, which is in accordance with the so-called tricritical hypothesis, which predicts β=0.25 and excludes higher theoretical values. The critical behavior of S(T) at the N-I transition is discussed in detail by comparing our results with the latest reports in the literature and we conclude that by comparing with the previously reported results, the isotropic internal field assumption by the Vuks-Chandrasekhar-Madhusudana model is adequate to extract the critical behavior of S(T) from the optical birefringence data. We observe that there is no discontinuous behavior in the optical birefringence, signaling the second-order nature of the N-SmA transition. The effect of the coupling between the nematic and smectic-A order parameters on the optical birefringence near the N-SmA transition is also discussed. In a temperature range of about 4K above and below the N-SmA transition, the pretransitional evidence for the N-SmA coupling have been detected. From the analysis of the optical birefringence data above and below the N-SmA transition by means of various fitting expressions we test the validity of the scaling relation λ=1-α between the critical exponent λ describing the limiting behavior of the nematic order parameter and the specific heat capacity exponent α. We then show that the temperature derivative of the nematic order parameter S(T) near T(NA) exhibits the same power-law divergence as the specific heat capacity with an effective critical exponent of 0.2303±0.0035.

THE EFFECT OF SURFACES ON THE ORIENTATIONAL PROPERTIES AND PHASE TRANSITIONS PECULIARITIES OF A NONPOLAR SMECTOGEN

The effect of thin films on the orientational and optical properties of nonpolar monolayer smectogen 4-butoxyphenyl-4′-decyloxybenzoate [Formula: see text] liquid crystal has been studied by polarizing microscopy and high-resolution photon transmission method. The uniform planar textures of [Formula: see text] on the surfaces coated with WO3, VO2, and WO3– VO2mixture thin films have been obtained. No significant shifts in the phase transition temperatures to lower values under the influence of the surfaces have been observed. We have also presented the new experimental data on the critical behavior of the layer compression modulus B near the nematic–smectic A transition. It was observed that the data in the vicinity of the transition can be described by a power law expression after the introduction of a first-order correction-to-scaling term within the limit of experimental error. The resulting critical exponent was found to be 0.34∓0.01 which is good agreement with the previously reported values for other investigated compounds in literature.

Wetting study of imidazolium ionic liquids

In this work, we present a systematic contact angles study of a series of 1-alkyl, 3-methyl-imidazolium ionic liquids (ILs) on well-defined polar and nonpolar monolayer surfaces supported on Si wafers. The advancing and receding contact angles of ILs were used to determine the surface energy of the monolayer surfaces using Neumann's equation-of-state and Zisman's critical surface tension approaches. In parallel, the contact angles of conventional probe fluids (molecular liquids) including water, formamide, methylene iodide, ethylene glycol, and hexadecane were determined on the same surfaces. The results obtained showed a great deal of similarity in wetting behavior of ionic vs molecular probe fluids: the contact angles of both sets of liquids followed the same patterns in accord with the surface tension of the fluid. A good agreement was found between the surface energy determined by different sets of liquids.