Directionally-Resolved Phononic Properties of Monolayer 2D Molybdenum Ditelluride (MoTe2) under Uniaxial Elastic Strain.

Understanding the phonon characteristics of two-dimensional (2D) molybdenum ditelluride (MoTe2) under strain is critical to manipulating its multiphysical properties. Although there have been numerous computational efforts to elucidate the strain-coupled phonon properties of monolayer MoTe2, empirical validation is still lacking. In this work, monolayer 1H-MoTe2 under uniaxial strain is studied via in situ micro-Raman spectroscopy. Directionally dependent monotonic softening of the doubly degenerate in-plane E2g1 phonon mode is observed with increasing uniaxial strain, where the E2g1 peak red-shifts -1.66 ± 0.04 cm-1/% along the armchair direction and -0.80 ± 0.07 cm-1/% along the zigzag direction. The corresponding Grüneisen parameters are calculated to be 1.09 and 0.52 along the armchair and zigzag directions, respectively. This work provides the first empirical quantification and validation of the orientation-dependent strain-coupled phonon response in monolayer 1H-MoTe2 and serves as a benchmark for other prototypical 2D transition-metal tellurides.

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.

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.

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.

Long-term oil contamination causes similar changes in microbial communities of two distinct soils.

Since total petroleum hydrocarbons (TPH) are toxic and persistent in environments, studying the impact of oil contamination on microbial communities in different soils is vital to oil production engineering, effective soil management and pollution control. This study analyzed the impact of oil contamination on the structure, activity and function in carbon metabolism of microbial communities of Chernozem soil from Daqing oil field and Cinnamon soil from Huabei oil field through both culture-dependent techniques and a culture-independent technique-pyrosequencing. Results revealed that pristine microbial communities in these two soils presented disparate patterns, where Cinnamon soil showed higher abundance of alkane, (polycyclic aromatic hydrocarbons) PAHs and TPH degraders, number of cultivable microbes, bacterial richness, bacterial biodiversity, and stronger microbial activity and function in carbon metabolism than Chernozem soil. It suggested that complicated properties of microbes and soils resulted in the difference in soil microbial patterns. However, the changes of microbial communities caused by oil contamination were similar in respect of two dominant phenomena. Firstly, the microbial community structures were greatly changed, with higher abundance, higher bacterial biodiversity, occurrence of Candidate_division_BRC1 and TAO6, disappearance of BD1-5 and Candidate_division_OD1, dominance of Streptomyces, higher percentage of hydrocarbon-degrading groups, and lower percentage of nitrogen-transforming groups. Secondly, microbial activity and function in carbon metabolism were significantly enhanced. Based on the characteristics of microbial communities in the two soils, appropriate strategy for in situ bioremediation was provided for each oil field. This research underscored the usefulness of combination of culture-dependent techniques and next-generation sequencing techniques both to unravel the microbial patterns and understand the ecological impact of contamination.

Nanoscale goldbeating: Solid-state transformation of 0D and 1D gold nanoparticles to anisotropic 2D morphologies.

Goldbeating is the ancient craft of thinning bulk gold (Au) into gossamer leaves. Pioneered by ancient Egyptian craftsmen, modern mechanized iterations of this technique can fabricate sheets as thin as ∼100 nm. We take inspiration from this millennia-old craft and adapt it to the nanoscale regime, using colloidally synthesized 0D/1D Au nanoparticles (AuNPs) as highly ductile and malleable nanoscopic Au ingots and subjecting them to solid-state, uniaxial compression. The applied stress induces anisotropic morphological transformation of AuNPs into 2D leaf form and elucidates insights into metal nanocrystal deformation at the extreme length scales. The induced 2D morphology is found to be dependent on the precursor 0D/1D NP morphology, size (0D nanosphere diameter and 1D nanorod diameter and length), and their on-substrate arrangement (e.g., interparticle separation and packing order) prior to compression. Overall, this versatile and generalizable solid-state compression technique enables new pathways to synthesize and investigate the anisotropic morphological transformation of arbitrary NPs and their resultant emergent phenomena.

Effects of hydrodynamics on the cross-sectional distribution and transport of plastic in an urban coastal river.

The mechanisms of plastic transport in rivers remain an important knowledge gap in global plastic pollution research and management. We investigated how river flows and plastics' properties affect transport with a five-point cross-sectional field study in the Hillsborough River in Tampa (Florida, USA) using a 500-µm Neuston net and an Acoustic Doppler Current Profiler. We conducted in-depth analysis of water velocity profiles as well as plastics' concentrations and properties, determining advective, vertical, and lateral transport fluxes. Under calm flow conditions, advective fluxes were two orders of magnitude higher than lateral and vertical fluxes. Under turbulent conditions, enhanced particle exchange in the cross-section resulted in a three to tenfold increase in lateral and vertical plastic fluxes. The impact of turbulence on plastic particles depended on properties such as size, shape, and composition. This study presents a unique assessment of flow conditions driving plastic pollution in an urban coastal river setting. PRACTITIONERS POINTS: Multipoint, cross-sectional sampling and onsite flow profile collection should be adopted as a common practice for plastic field data collection to reduce uncertainty. Varying flow conditions affect the drivers of plastic transport in rivers. Advective surface fluxes govern plastic transport under calm flow conditions, while turbulent flow conditions enhance cross-sectional mixing and particle exchange. Larger and more irregular-shaped plastics are more affected by turbulence.

Large scale self-assembly of plasmonic nanoparticles on deformed graphene templates.

Hierarchical heterostructures of two-dimensional (2D) nanomaterials are versatile platforms for nanoscale optoelectronics. Further coupling of these 2D materials with plasmonic nanostructures, especially in non-close-packed morphologies, imparts new metastructural properties such as increased photosensitivity as well as spectral selectivity and range. However, the integration of plasmonic nanoparticles with 2D materials has largely been limited to lithographic patterning and/or undefined deposition of metallic structures. Here we show that colloidally synthesized zero-dimensional (0D) gold nanoparticles of various sizes can be deterministically self-assembled in highly-ordered, anisotropic, non-close-packed, multi-scale morphologies with templates designed from instability-driven, deformed 2D nanomaterials. The anisotropic plasmonic coupling of the particle arrays exhibits emergent polarization-dependent absorbance in the visible to near-IR regions. Additionally, controllable metasurface arrays of nanoparticles by functionalization with varying polymer brushes modulate the plasmonic coupling between polarization dependent and independent assemblies. This self-assembly method shows potential for bottom-up nanomanufacturing of diverse optoelectronic components and can potentially be adapted to a wide array of nanoscale 0D, 1D, and 2D materials.

A Flexible a-SiC-Based Neural Interface Utilizing Pyrolyzed-Photoresist Film (C) Active Sites.

Carbon containing materials, such as graphene, carbon-nanotubes (CNT), and graphene oxide, have gained prominence as possible electrodes in implantable neural interfaces due to their excellent conductive properties. While carbon is a promising electrochemical interface, many fabrication processes are difficult to perform, leading to issues with large scale device production and overall repeatability. Here we demonstrate that carbon electrodes and traces constructed from pyrolyzed-photoresist-film (PPF) when combined with amorphous silicon carbide (a-SiC) insulation could be fabricated with repeatable processes which use tools easily available in most semiconductor facilities. Directly forming PPF on a-SiC simplified the fabrication process which eliminates noble metal evaporation/sputtering and lift-off processes on small features. PPF electrodes in oxygenated phosphate buffered solution at pH 7.4 demonstrated excellent electrochemical charge storage capacity (CSC) of 14.16 C/cm2, an impedance of 24.8 ± 0.4 kΩ, and phase angle of -35.9 ± 0.6° at 1 kHz with a 1.9 kµm2 recording site area.

Ångström- and Nano-scale Pore-Based Nucleic Acid Sequencing of Current and Emergent Pathogens.

State-of-the-art nanopore sequencing enables rapid and real-time identification of novel pathogens, which has wide application in various research areas and is an emerging diagnostic tool for infectious diseases including COVID-19. Nanopore translocation enables de novo sequencing with long reads (> 10 kb) of novel genomes, which has advantages over existing short-read sequencing technologies. Biological nanopore sequencing has already achieved success as a technology platform but it is sensitive to empirical factors such as pH and temperature. Alternatively, ångström- and nano-scale solid-state nanopores, especially those based on two-dimensional (2D) membranes, are promising next-generation technologies as they can surpass biological nanopores in the variety of membrane materials, ease of defining pore morphology, higher nucleotide detection sensitivity, and facilitation of novel and hybrid sequencing modalities. Since the discovery of graphene, atomically-thin 2D materials have shown immense potential for the fabrication of nanopores with well-defined geometry, rendering them viable candidates for nanopore sequencing membranes. Here, we review recent progress and future development trends of 2D materials and their ångström- and nano-scale pore-based nucleic acid (NA) sequencing including fabrication techniques and current and emerging sequencing modalities. In addition, we discuss the current challenges of translocation-based nanopore sequencing and provide an outlook on promising future research directions.

Enhanced Electrical and Mechanical Properties of Chemically Cross-Linked Carbon-Nanotube-Based Fibers and Their Application in High-Performance Supercapacitors.

The electrical conductivity and mechanical strength of fibers constructed from single-walled carbon nanotubes (CNTs) are usually limited by the weak interactions between individual CNTs. In this work, we report a significant enhancement of both of these properties through chemical cross-linking of individual CNTs. The CNT fibers are made by wet-spinning a CNT solution that contains 1,3,5-tris(2'-bromophenyl)benzene (2TBB) molecules as the cross-linking agent, and the cross-linking is subsequently driven by Joule heating. Cross-linking with 2TBB increases the conductivity of the CNT fibers by a factor of ∼100 and increases the tensile strength on average by 47%; in contrast, the tensile strength of CNT fibers fabricated without 2TBB decreases after the same Joule heating process. Symmetrical supercapacitors made from the 2TBB-treated CNT fibers exhibit a remarkably high volumetric energy density of ∼4.5 mWh cm-3 and a power density of ∼1.3 W cm-3.

Slippery and Sticky Graphene in Water.

Understanding modulation of water molecule slippage along graphene surfaces is crucial for many promising applications of two-dimensional materials. Here, we examine normal and shear forces on supported single-layer graphene using atomic force microscopy and find that the electrolyte composition affects the molecular slippage of nanometer thick films of aqueous electrolytes along the graphene surface. In light of the shear-assisted thermally activated theory, water molecules along the graphene plane are very mobile when subjected to shear. However, upon addition of an electrolyte, the cations can make water stick to graphene, while ion-specific and concentration effects are present. Recognizing the tribological and tribochemical utility of graphene, we also evaluate the impact of this behavior on its frictional response in the presence of water. It appears that the addition of an electrolyte to pure water causes a reduction of the thermal activation energy and of the shear-activation length at several concentrations, both results conversely affecting the friction force. Further, this work can inspire innovation in research areas where changes of the molecular slippage through the modulation of the doping characteristics of graphene in liquid environment can be of use, including molecular sensing, lubrication, and energy storage.

Crumpled Graphene Photodetector with Enhanced, Strain-Tunable, and Wavelength-Selective Photoresponsivity.

A stretchable photodetector with enhanced, strain-tunable photoresponsivity is developed based on crumpled graphene by engineering 2D graphene into 3D structures. This crumpled graphene photodetector demonstrates ≈400% enhanced photoresponsivity led by an order-of-magnitude enhanced extinction of graphene and 100% modulation in photoresponsivity with 200% applied strain. Finally, strain-tunable, wavelength-selective photodetection is shown by integrated colloidal photonic crystals-crumpled graphene photodetector devices.

The importance of neutral and niche processes for bacterial community assembly differs between habitat generalists and specialists.

The mechanisms of community assembly are a central focus in the field of microbial ecology. However, to what extent these mechanisms differ in importance by traits of groups is poorly understood. Here we quantified the importance of neutral and niche processes in community assembly for bacteria, habitat specialists and generalists in 21 plateau lakes of China. Results showed that both neutral and niche processes played a critical role in the assembly of entire bacterial communities, shaping a unique biogeographical pattern. A few habitat generalists and many specialists were identified. Interestingly, habitat specialists were only governed by niche process, with seven significant environmental variables-salinity, dissolved oxygen, water transparency, total phosphorus, ammonium-nitrogen, temperature and total nitrogen-independently explaining 40.3% of the biological variation. By contrast, habitat generalists were strongly driven by neutral process, with 50.9% of the variation of detection frequency explained in neutral community model. Only three environmental variables-salinity, total nitrogen and dissolved oxygen-significantly affected the distribution of habitat generalists, independently explaining 13.6% of the variation. Governed by different assembly mechanisms, habitat specialists and generalists presented disparate biogeographical patterns. Our result emphasizes the importance of investigating the bacterial community assembly at more refined levels than entire communities.