Spatial Tuning of Light-Matter Interaction via Strain-Gradient-Induced Polarization in Freestanding Wrinkled 2D Materials.

To date, controlled deformation of two-dimensional (2D) materials has been extensively demonstrated with substrate-supported structures. However, interfacial effects arising from these supporting materials may suppress or alter the unique behavior of the deformed 2D materials. To address interfacial effects, we report, for the first time, the formation of a micrometer-scale freestanding wrinkled structure of 2D material without any encapsulation layers where we observed the enhanced light-matter interactions with a spatial modulation. Freestanding wrinkled monolayer WSe2 exhibited about a 330% enhancement relative to supported wrinkled WSe2 quantified through photoinduced force microscopy. Spatial modulation and enhancement of light interaction in the freestanding wrinkled structures are attributed to the enhanced strain-gradient effect (i.e., out-of-plane polarization) enabled by removing the constraining support and proximate dielectrics. Our findings offer an additional degree of freedom to modulate the out-of-plane polarization and enhance the out-of-plane light-matter interaction in 2D materials.

MoS2 Passivated Multilayer Graphene Membranes for Li-Ion Extraction From Seawater.

Abundant Li resources in the ocean are promising alternatives to refining ore, whose supplies are limited by the total amount and geopolitical imbalance of reserves in Earth's crust. Despite advances in Li+ extraction using porous membranes, they require screening other cations on a large scale due to the lack in precise control of pore size and inborn defects. Herein, MoS2 nanoflakes on a multilayer graphene membrane (MFs-on-MGM) that possess ion channels comprising i) van der Waals interlayer gaps for optimal Li+ extraction and ii) negatively charged vertical inlets for cation attraction, are reported. Ion transport measurements across the membrane reveal ≈6- and 13-fold higher selectivity for Li+ compared to Na+ and Mg2+ , respectively. Furthermore, continuous, stable Li+ extraction from seawater is demonstrated by integrating the membrane into a H2 and Cl2 evolution system, enabling more than 104 -fold decrease in the Na+ concentration and near-complete elimination of other cations.

Highly Strain-Tunable Interlayer Excitons in MoS2/WSe2 Heterobilayers.

Interlayer excitons in heterobilayers of transition-metal dichalcogenides (TMDCs) have generated enormous interest due to their permanent vertical dipole moments and long lifetimes. However, the effects of mechanical strain on the optoelectronic properties of interlayer excitons in heterobilayers remain relatively uncharacterized. Here, we experimentally demonstrate strain tuning of Γ-K interlayer excitons in molybdenum disulfide and tungsten diselenide (MoS2/WSe2) wrinkled heterobilayers and obtain a deformation potential constant of ∼107 meV/% uniaxial strain, which is approximately twice that of the intralayer excitons in the constituent monolayers. We further observe a nonmonotonic dependence of the interlayer exciton photoluminescence intensity with strain, which we interpret as being due to the sensitivity of the Γ point to band hybridization arising from the competition between in-plane strain and out-of-plane interlayer coupling. Strain engineering with interlayer excitons in TMDC heterobilayers offers higher strain tunability and new degrees of freedom compared to their monolayer counterparts.

Role of Thin Film Adhesion on Capillary Peeling.

The capillary force can peel off a substrate-attached film if the adhesion energy (Gw) is low. Capillary peeling has been used as a convenient, rapid, and nondestructive method for fabricating free-standing thin films. However, the critical value of Gw, which leads to the transition between peeling and sticking, remains largely unknown. As a result, capillary peeling remains empirical and applicable to a limited set of materials. Here, we investigate the critical value of Gw and experimentally show the critical adhesion (Gw,c) to scale with the water-film interfacial energy (≈0.7γfw), which corresponds well with our theoretical prediction of Gw,c = γfw. Based on the critical adhesion, we propose quantitative thermodynamic guidelines for designing thin film interfaces that enable successful capillary peeling. The outcomes of this work present a powerful technique for thin film transfer and advanced nanofabrication in flexible photovoltaics, battery materials, biosensing, translational medicine, and stretchable bioelectronics.

Polarization Control of Deterministic Single-Photon Emitters in Monolayer WSe2.

Single-photon emitters, the basic building blocks of quantum communication and information, have been developed using atomically thin transition metal dichalcogenides (TMDCs). Although the bandgap of TMDCs was spatially engineered in artificially created defects for single-photon emitters, it remains a challenge to precisely align the emitter's dipole moment to optical cavities for the Purcell enhancement. Here, we demonstrate position- and polarization-controlled single-photon emitters in monolayer WSe2. A tensile strain of ∼0.2% was applied to monolayer WSe2 by placing it onto a dielectric rod structure with a nanosized gap. Excitons were localized in the nanogap sites, resulting in the generation of linearly polarized single-photon emission with a g(2) of ∼0.1 at 4 K. Additionally, we measured the abrupt change in polarization of single photons with respect to the nanogap size. Our robust spatial and polarization control of emission provides an efficient way to demonstrate deterministic and scalable single-photon sources by integrating with nanocavities.

Tunable Wettability of Graphene through Nondestructive Hydrogenation and Wettability-Based Patterning for Bioapplications.

The wettability of graphene has been extensively studied and successfully modified by chemical functionalization. Nevertheless, the unavoidable introduction of undesired defects and the absence of systematic and local control over wettability by previous methods have limited the use of graphene in applications. In addition, microscale patterning, according to wettability, has not been attempted. Here, we demonstrate that the wettability of graphene can be systematically controlled and surface patterned into microscale sections based on wettability without creating significant defects, possible by nondestructive hydrogen plasma. Hydrophobic graphene is progressively converted to hydrophilic hydrogenated graphene (H-Gr) that reaches superhydrophilicity. The great contrast in wettability between graphene and H-Gr makes it possible to selectively position and isolate human breast cancer cells on arrays of micropatterns since strong hydrophilicity facilitates the adsorption of the cells. We believe that our method will provide an essential technique for enabling surface and biological applications requiring microscale patterns with different wettability.

Heterogeneous deformation of two-dimensional materials for emerging functionalities.

Atomically thin 2D materials exhibit strong intralayer covalent bonding and weak interlayer van der Waals interactions, offering unique high in-plane strength and out-of-plane flexibility. While atom-thick nature of 2D materials may cause uncontrolled intrinsic/extrinsic deformation in multiple length scales, it also provides new opportunities for exploring coupling between heterogeneous deformations and emerging functionalities in controllable and scalable ways for electronic, optical, and optoelectronic applications. In this review, we discuss (i) the mechanical characteristics of 2D materials, (ii) uncontrolled inherent deformation and extrinsic heterogeneity present in 2D materials, (iii) experimental strategies for controlled heterogeneous deformation of 2D materials, (iv) 3D structure-induced novel functionalities via crumple/wrinkle structure or kirigami structures, and (v) heterogeneous strain-induced emerging functionalities in exciton and phase engineering. Overall, heterogeneous deformation offers unique advantages for 2D materials research by enabling spatial tunability of 2D materials' interactions with photons, electrons, and molecules in a programmable and controlled manner.

Ultraviolet to Mid-Infrared Emissivity Control by Mechanically Reconfigurable Graphene.

Spectral emissivity control is critical for optical and thermal management in the ambient environment because solar irradiance and atmospheric transmissions occur at distinct wavelength regions. For instance, selective emitters with low emissivity in the solar spectrum but high emissivity in the mid-infrared can lead to significant radiative cooling. Ambient variations require not only spectral control but also a mechanism to adjust the emissivity. However, most selective emitters are fixed to specific wavelength ranges and lack dynamic control mechanisms. Here we show ultraviolet to mid-infrared emissivity control by mechanically reconfiguring graphene, in which stretching and releasing induce dynamic topographic changes. We fabricate crumpled graphene with pitches ranging from 40 nm to 10 µm using deformable substrates. Our measurements and computations show that 140 nm-pitch crumpled graphene offers ultraviolet emissivity control in 200-300 nm wavelengths whereas 10 µm-pitch crumpled graphene offers mid-infrared emissivity control in 7-19 µm wavelengths. Significant emissivity changes arise from interference induced by the periodic topography and selective transmissivity reductions. Dynamic stretching and releasing of 140 nm and 10 µm pitch crumpled graphene show reversible emissivity peak changes at 250 nm and at 9.9 µm wavelengths, respectively. This work demonstrates the unique potential of crumpled graphene as a reconfigurable optical and thermal management platform.

Electrical Double Layer of Supported Atomically Thin Materials.

The electrical double layer (EDL), consisting of two parallel layers of opposite charges, is foundational to many interfacial phenomena and unique in atomically thin materials. An important but unanswered question is how the "transparency" of atomically thin materials to their substrates influences the formation of the EDL. Here, we report that the EDL of graphene is directly affected by the surface energy of the underlying substrates. Cyclic voltammetry and electrochemical impedance spectroscopy measurements demonstrate that graphene on hydrophobic substrates exhibits an anomalously low EDL capacitance, much lower than what was previously measured for highly oriented pyrolytic graphite, suggesting disturbance of the EDL ("disordered EDL") formation due to the substrate-induced hydrophobicity to graphene. Similarly, electrostatic gating using EDL of graphene field-effect transistors shows much lower transconductance levels or even no gating for graphene on hydrophobic substrates, further supporting our hypothesis. Molecular dynamics simulations show that the EDL structure of graphene on a hydrophobic substrate is disordered, caused by the disruption of water dipole assemblies. Our study advances understanding of EDL in atomically thin limit.

Recent Advances in Graphene Oxide Membranes for Gas Separation Applications.

Graphene oxide (GO) can dramatically enhance the gas separation performance of membrane technologies beyond the limits of conventional membrane materials in terms of both permeability and selectivity. Graphene oxide membranes can allow extremely high fluxes because of their ultimate thinness and unique layered structure. In addition, their high selectivity is due to the molecular sieving or diffusion effect resulting from their narrow pore size distribution or their unique surface chemistry. In the first part of this review, we briefly discuss different mechanisms of gas transport through membranes, with an emphasis on the proposed mechanisms for gas separation by GO membranes. In the second part, we review the methods for GO membrane preparation and characterization. In the third part, we provide a critical review of the literature on the application of different types of GO membranes for CO2, H2, and hydrocarbon separation. Finally, we provide recommendations for the development of high-performance GO membranes for gas separation applications.

Hierarchical, Dual-Scale Structures of Atomically Thin MoS2 for Tunable Wetting.

Molybdenum disulfide (MoS2), a well-known solid lubricant for low friction surface coatings, has recently drawn attention as an analogue two-dimensional (2D) material beyond graphene. When patterned to produce vertically grown, nanoflower-structures, MoS2 shows promise as a functional material for hydrogen evolution catalysis systems, electrodes for alkali metal-ion batteries, and field-emission arrays. Whereas the wettability of graphene has been substantially investigated, that of MoS2 structures, especially nanoflowers, has remained relatively unexplored despite MoS2 nanoflower's potential in future applications. Here, we demonstrate that the wettability of MoS2 can be controlled by multiscale modulation of surface roughness through (1) tuning of the nanoflower structures by chemical vapor deposition synthesis and (2) tuning of microscale topography via mechanical strain. This multiscale modulation offers broadened tunability (80-155°) compared to single-scale tuning (90-130°). In addition, surface adhesion, determined from contact angle hysteresis (CAH), can also be tuned by multiscale surface roughness modulation, where the CAH is changed in range of 20-40°. Finally, the wettability of crumpled MoS2 nanoflowers can be dynamically and reversibly controlled through applied strain (∼115-150° with 0-200% strain), and remains robust over 1000 strain cycles. These studies on the tunable wettability of MoS2 will contribute to future MoS2-based applications, such as tunable wettability coatings for desalination and hydrogen evolution.

Programmable nanowire circuits for nanoprocessors.

A nanoprocessor constructed from intrinsically nanometre-scale building blocks is an essential component for controlling memory, nanosensors and other functions proposed for nanosystems assembled from the bottom up. Important steps towards this goal over the past fifteen years include the realization of simple logic gates with individually assembled semiconductor nanowires and carbon nanotubes, but with only 16 devices or fewer and a single function for each circuit. Recently, logic circuits also have been demonstrated that use two or three elements of a one-dimensional memristor array, although such passive devices without gain are difficult to cascade. These circuits fall short of the requirements for a scalable, multifunctional nanoprocessor owing to challenges in materials, assembly and architecture on the nanoscale. Here we describe the design, fabrication and use of programmable and scalable logic tiles for nanoprocessors that surmount these hurdles. The tiles were built from programmable, non-volatile nanowire transistor arrays. Ge/Si core/shell nanowires coupled to designed dielectric shells yielded single-nanowire, non-volatile field-effect transistors (FETs) with uniform, programmable threshold voltages and the capability to drive cascaded elements. We developed an architecture to integrate the programmable nanowire FETs and define a logic tile consisting of two interconnected arrays with 496 functional configurable FET nodes in an area of ∼960 µm(2). The logic tile was programmed and operated first as a full adder with a maximal voltage gain of ten and input-output voltage matching. Then we showed that the same logic tile can be reprogrammed and used to demonstrate full-subtractor, multiplexer, demultiplexer and clocked D-latch functions. These results represent a significant advance in the complexity and functionality of nanoelectronic circuits built from the bottom up with a tiled architecture that could be cascaded to realize fully integrated nanoprocessors with computing, memory and addressing capabilities.

Doping-Induced Tunable Wettability and Adhesion of Graphene.

We report that substrate doping-induced charge carrier density modulation leads to the tunable wettability and adhesion of graphene. Graphene's water contact angle changes by as much as 13° as a result of a 300 meV change in doping level. Upon either n- or p-type doping with subsurface polyelectrolytes, graphene exhibits increased hydrophilicity. Adhesion force measurements using a hydrophobic self-assembled monolayer-coated atomic force microscopy probe reveal enhanced attraction toward undoped graphene, consistent with wettability modulation. This doping-induced wettability modulation is also achieved via a lateral metal-graphene heterojunction or subsurface metal doping. Combined first-principles and atomistic calculations show that doping modulates the binding energy between water and graphene and thus increases its hydrophilicity. Our study suggests that the doping-induced modulation of the charge carrier density in graphene influences its wettability and adhesion [corrected]. This opens up unique and new opportunities for the tunable wettability and adhesion of graphene for advanced coating materials and transducers.

Mechanically Self-Assembled, Three-Dimensional Graphene-Gold Hybrid Nanostructures for Advanced Nanoplasmonic Sensors.

Hybrid structures of graphene and metal nanoparticles (NPs) have been actively investigated as higher quality surface enhanced Raman spectroscopy (SERS) substrates. Compared with SERS substrates, which only contain metal NPs, the additional graphene layer provides structural, chemical, and optical advantages. However, the two-dimensional (2D) nature of graphene limits the fabrication of the hybrid structure of graphene and NPs to 2D. Introducing three-dimensionality to the hybrid structure would allow higher detection sensitivity of target analytes by utilizing the three-dimensional (3D) focal volume. Here, we report a mechanical self-assembly strategy to enable a new class of 3D crumpled graphene-gold (Au) NPs hybrid nanoplasmonic structures for SERS applications. We achieve a 3D crumpled graphene-Au NPs hybrid structure by the delamination and buckling of graphene on a thermally activated, shrinking polymer substrate. We also show the precise control and optimization of the size and spacing of integrated Au NPs on crumpled graphene and demonstrate the optimized NPs' size and spacing for higher SERS enhancement. The 3D crumpled graphene-Au NPs exhibits at least 1 order of magnitude higher SERS detection sensitivity than that of conventional, flat graphene-Au NPs. The hybrid structure is further adapted to arbitrary curvilinear structures for advanced, in situ, nonconventional, nanoplasmonic sensing applications. We believe that our approach shows a promising material platform for universally adaptable SERS substrate with high sensitivity.

Heterogeneous, three-dimensional texturing of graphene.

We report a single-step strategy to achieve heterogeneous, three-dimensional (3D) texturing of graphene and graphite by using a thermally activated shape-memory polymer substrate. Uniform arrays of graphene crumples can be created on the centimeter scale by controlling simple thermal processing parameters without compromising the electrical properties of graphene. In addition, we show the capability to selectively pattern crumples from otherwise flat graphene and graphene/graphite in a localized manner, which has not been previously achievable using other methods. Finally, we demonstrate 3D crumpled graphene field-effect transistor arrays in a solution-gated configuration. The presented approach has the capability to conform onto arbitrary 3D surfaces, a necessary prerequisite for adaptive electronics, and will enable facile large-scale topography engineering of not only graphene but also other thin-film and 2D materials in the future.

Three-Dimensional Integration of Graphene via Swelling, Shrinking, and Adaptation.

The transfer of graphene from its growth substrate to a target substrate has been widely investigated for its decisive role in subsequent device integration and performance. Thus far, various reported methods of graphene transfer have been mostly limited to planar or curvilinear surfaces due to the challenges associated with fractures from local stress during transfer onto three-dimensional (3D) microstructured surfaces. Here, we report a robust approach to integrate graphene onto 3D microstructured surfaces while maintaining the structural integrity of graphene, where the out-of-plane dimensions of the 3D features vary from 3.5 to 50 µm. We utilized three sequential steps: (1) substrate swelling, (2) shrinking, and (3) adaptation, in order to achieve damage-free, large area integration of graphene on 3D microstructures. Detailed scanning electron microscopy, atomic force microscopy, Raman spectroscopy, and electrical resistance measurement studies show that the amount of substrate swelling as well as the flexural rigidities of the transfer film affect the integration yield and quality of the integrated graphene. We also demonstrate the versatility of our approach by extension to a variety of 3D microstructured geometries. Lastly, we show the integration of hybrid structures of graphene decorated with gold nanoparticles onto 3D microstructure substrates, demonstrating the compatibility of our integration method with other hybrid nanomaterials. We believe that the versatile, damage-free integration method based on swelling, shrinking, and adaptation will pave the way for 3D integration of two-dimensional (2D) materials and expand potential applications of graphene and 2D materials in the future.

Graphene nanopore with a self-integrated optical antenna.

We report graphene nanopores with integrated optical antennae. We demonstrate that a nanometer-sized heated spot created by photon-to-heat conversion of a gold nanorod resting on a graphene membrane forms a nanoscale pore with a self-integrated optical antenna in a single step. The distinct plasmonic traits of metal nanoparticles, which have a unique capability to concentrate light into nanoscale regions, yield the significant advantage of parallel nanopore fabrication compared to the conventional sequential process using an electron beam. Tunability of both the nanopore dimensions and the optical characteristics of plasmonic nanoantennae are further achieved. Finally, the key optical function of our self-integrated optical antenna on the vicinity of graphene nanopore is manifested by multifold fluorescent signal enhancement during DNA translocation.

Assembly and densification of nanowire arrays via shrinkage.

Chemically synthesized semiconductor nanowires (NWs) have demonstrated substantial promise for nanoelectronics, nanoenergy, and nanobiotechnology, but the lack of an effective and controllable assembly process has limited the wide adoption of NWs in these areas. Here we demonstrate a facile, robust, and controllable approach to assembling and densifying a parallel array of NWs using shrinkable shape memory polymers. Using thermal-induced shrinkage of polystyrene, we were able to successfully assemble and densify NW arrays up to close-packing and, furthermore, achieve tunable density (up to ∼300% amplification of density) by controlling the shrinkage process. We also demonstrate scalable assembly and densification of NWs on a 2.5 × 6 inch scale to explore the manufacturability of the shrink-induced assembly process. Finally, we demonstrate the successful transfer of the shrink-assembled NW arrays onto various 2-dimensional and 3-dimensional substrates without compromising the integrity of NW assembly and density.

Spectroscopic investigation of the wettability of multilayer graphene using highly ordered pyrolytic graphite as a model material.

We report the intrinsic water contact angle (WCA) of multilayer graphene, explore different methods of cleaning multilayer graphene, and evaluate the efficiency of those methods on the basis of spectroscopic analysis. Highly ordered pyrolytic graphite (HOPG) was used as a model material system to study the wettability of the multilayer graphene surface by WCA measurements. A WCA value of 45° ± 3° was measured for a clean HOPG surface, which can serve as the intrinsic WCA for multilayer graphene. A 1 min plasma treatment (100 W) decreased the WCA to 6°, owing to the creation of surface defects and functionalization by oxygen-containing groups. Molecular dynamics simulations of water droplets on the HOPG surface with or without the oxygen-containing defect sites confirmed the experimental results. Heat treatment at near atmospheric pressure and wet chemical cleaning methods using hydrofluoric acid and chloroform did not change the WCA significantly. Low-pressure, high-temperature annealing under argon and hydrogen reduced the WCA to 54°, close to the intrinsic WCA of HOPG. Raman spectroscopy and atomic force microscopy did not show any significant change for the HOPG surface after this treatment, confirming low-pressure, high-temperature annealing as an effective technique to clean multilayer graphene without damaging the surface. Time-of-flight secondary ion mass spectrometry indicated the existence of hydrocarbon species on the surface of the HOPG sample that was exposed to air for <5 min and the absence of these impurities in the bulk. X-ray photoelectron spectroscopy analyses of the sample surfaces after the different cleaning techniques were performed to correlate the WCA to the surface chemistry. X-ray photoelectron spectroscopy results revealed that the WCA value changed drastically, depending on the amounts of oxygen-containing and hydrocarbon-containing groups on the surface.

High-performance, transparent, and stretchable electrodes using graphene-metal nanowire hybrid structures.

Transparent electrodes that can remain electrically conductive and stable under large mechanical deformations are highly desirable for applications in flexible and wearable electronics. This paper describes a comprehensive study of the electrical, optical, and mechanical properties of hybrid nanostructures based on two-dimensional graphene and networks of one-dimensional metal nanowires, and their use as transparent and stretchable electrodes. Low sheet resistance (33 Ω/sq) with high transmittance (94% in visible range), robust stability against electric breakdown and oxidation, and superb flexibility (27% in bending strain) and stretchability (100% in tensile strain) are observed, and these multiple functionalities of the hybrid structures suggest a future promise for next generation electronics. The use of hybrid electrodes to fabricate oxide semiconductor transistors and single-pixel displays integrated on wearable soft contact lenses with in vivo tests are demonstrated.