Multiscale modeling of fracture in 2D materials

Theoretical study on the interaction of nucleotides on two-dimensional atomically thin graphene and molybdenum disulfide

This research investigates the mechanical behavior and damage evolution in cross-ply basalt fiber composites subjected to different loading modes. A modified Arcan rig for simultaneous acoustic emission (AE) monitoring was designed and manufactured to apply quasi-isotropic shear, combined tensile and shear loading, and pure tensile loading on specimens with a central notch. Digital image correlation (DIC) was applied for high-resolution strain measurements. The measured failure strengths of the bio-composite specimens under different loading angles are presented. The different competing failure mechanisms that contribute to the local reduction in stress concentration are described. Different damage mechanisms trigger elastic waves in the composite, with distinct AE signatures that closely follow the sequence of fracture mechanisms. AE monitoring is employed to capture signals associated with structural damage initiation and progression. The characteristic parameters of AE signals are correlated with crack modes and damage mechanisms. The evolution of AE parameters during the peak load transition is presented, which enables the timely AE detection of the maximum load transition. The combination of DIC and AE monitoring improves understanding of the mechanical response and failure mechanisms in cross-ply basalt fiber composites, offering valuable insights for possible performance monitoring and structural reliability in diverse engineering applications.

Two-dimensional (2D) materials are considered for numerous applications in microelectronics, although several challenges remain when integrating them into functional devices. Weak adhesion is one of them, caused by their chemical inertness. Quantifying the adhesion of 2D materials on three-dimensional surfaces is, therefore, an essential step toward reliable 2D device integration. To this end, button shear testing is proposed and demonstrated as a method for evaluating the adhesion of 2D materials with the examples of graphene, hexagonal boron nitride (hBN), molybdenum disulfide, and tungsten diselenide on silicon dioxide and silicon nitride substrates. We propose a fabrication process flow for polymer buttons on the 2D materials and establish suitable button dimensions and testing shear speeds. We show with our quantitative data that low substrate roughness and oxygen plasma treatments on the substrates before 2D material transfer result in higher shear strengths. Thermal annealing increases the adhesion of hBN on silicon dioxide and correlates with the thermal interface resistance between these materials. This establishes button shear testing as a reliable and repeatable method for quantifying the adhesion of 2D materials.

The performance of two-dimensional (2D) materials ispromisingfor electronic, photonic, and sensing devices since they possess largesurface-to-volume ratios, high mechanical strength, and broadbandlight sensitivity. While significant advances have been made in synthesizingand transferring 2D materials onto different substrates, there isstill the need for scalable patterning of 2D materials with nanoscaleprecision. Conventional lithography methods require protective layerssuch as resist or metals that can contaminate or degrade the 2D materialsand deteriorate the final device performance. Current resist-freepatterning methods are limited in throughput and typically requirecustom-made equipment. To address these limitations, we demonstratethe noncontact and resist-free patterning of platinum diselenide (PtSe2), molybdenum disulfide (MoS2), and graphene layerswith nanoscale precision at high processing speed while preservingthe integrity of the surrounding material. We use a commercial, off-the-shelftwo-photon 3D printer to directly write patterns in the 2D materialswith features down to 100 nm at a maximum writing speed of 50 mm/s.We successfully remove a continuous film of 2D material from a 200μm × 200 μm substrate area in less than 3 s. Sincetwo-photon 3D printers are becoming increasingly available in researchlaboratories and industrial facilities, we expect this method to enablefast prototyping of devices based on 2D materials across various researchareas.

ABSTRACTThe emergence of 2-dimensional (2D) materials could herald numerous advanced scientific methodologies for both fundamental and applied research. These ultrathin materials can be functionalized and, thus, have the potential to make new devices and sensors that are both highly efficient and sensitive. In addition to being mechanically robust, the 2D materials can be engineered to provide sensor architectures that further increase their inherent high surface area by creating 3D geometries using layer by layer assembly to make stacked devices that could potentially be transparent. The increased sensor surface area would deliver increased signal-to-noise and sensitivity. Here highly sensitive and selective electrochemical detection of bio-analytes using some of engineered 2D materials such as graphene nano-ribbons, fluorinated graphene, and molybdenum disulfide is presented. It is found that surface moieties, defects and surface charges in these ultra-thin layers result in enhanced electron transfer kinetics between the electrodes and biomolecules. This in turn results in an oxidation or reduction of biomolecules with a high peak current, indicating the possible uses of 2D materials for various point-of-care devices. A novel stable 3D electrode geometry has been found to have enhanced heterogeneous electron transfer properties compared to 2D electrodes and provides evidence that electrode geometry and surface area could significantly impact the performance of biosensors.

Devices based on two-dimensional (2D) materials such as graphene and molybdenum disulfide have shown extraordinary potential in physics, nanotechnology, and electronics. The performances of these applications are heavily affected by defects in utilized materials. Although great efforts have been spent in studying the formation and property of various defects in 2D materials, the long-term evolution of vacancies is still unclear. Here, using a designed program based on the kinetic Monte Carlo method, we systematically investigate the vacancy evolution in monolayer graphene on a long-time and large spatial scale, focusing on the variation of the distribution of different vacancy types. In most cases, the vacancy distribution remains nearly unchanged during the whole evolution, and most of the evolution events are vacancy migrations with a few being coalescences, while it is extremely difficult for multiple vacancies to dissolve. The probabilities of different categories of vacancy evolutions are determined by their reaction rates, which, in turn, depend on corresponding energy barriers. We further study the influences of different factors such as the energy barrier for vacancy migration, coalescence, and dissociation on the evolution, and the coalescence energy barrier is found to be dominant. These findings indicate that vacancies (also subnanopores) in graphene are thermodynamically stable for a long period of time, conducive to subsequent characterizations or applications. Besides, this work provides hints to tune the ultimate vacancy distribution by changing related factors and suggests ways to study the evolution of other defects in various 2D materials.

A perpendicularly magnetized spin injector with a high Curie temperature is a prerequisite for developing spin optoelectronic devices on two-dimensional (2D) materials working at room temperature (RT) with zero applied magnetic field. Here, we report the growth of Ta/CoFeB/MgO structures with large perpendicular magnetic anisotropy (PMA) on full-coverage monolayer (ML) molybdenum disulfide (MoS2). A large perpendicular interface anisotropy energy of 0.975 mJ/m2 has been obtained at the CoFeB/MgO interface, comparable to that observed in magnetic tunnel junction systems. It is found that the insertion of MgO between the ferromagnetic (FM) metal and the 2D material can effectively prevent the diffusion of the FM atoms into the 2D material. Moreover, the MoS2 ML favors a MgO(001) texture and plays a critical role in establishing the large PMA. First-principles calculations on a similar Fe/MgO/MoS2 structure reveal that the MgO thickness can modify the MoS2 band structure, from a direct band gap with 3ML-MgO to an indirect band gap with 7 ML-MgO. The proximity effect induced by Fe results in splitting of 10 meV in the valence band at the Γ point for the 3ML-MgO structure, while it is negligible for the 7 ML-MgO structure. These results pave the way to develop RT spin optoelectronic devices based on 2D transition-metal dichalcogenide materials.

Resistance to crack growth in human cortical bone is greater in shear than in tension

We propose surface plasmon resonance biosensors based on crumpled graphene and molybdenum disulphide (MoS2) flakes supported on stretchable polydimethylsiloxane (PDMS) or silicon substrates. Accumulation of specific biomarkers resulting in measurable shifts in the resonance wavelength of the plasmon modes of two-dimensional (2D) material structures, with crumpled structures demonstrating large refractive index shifts. Using theoretical calculations based on the semiclassical Drude model, combined with the finite element method, we demonstrate that the interaction between the surface plasmons of crumpled graphene/MoS2 layers and the surrounding analyte results in high sensitivity to biomarker driven refractive index shifts, up to 7499 nm/RIU for structures supported on silicon substrates. We can achieve a high figure of merit (FOM), defined as the ratio of the refractive index sensitivity to the full width at half maximum of the resonant peak, of approximately 62.5 RIU-1. Furthermore, the sensing properties of the device can be tuned by varying crumple period and aspect ratio through simple stretching and integrating material interlayers. By stacking multiple 2D materials in heterostructures supported on the PDMS layer, we produced hybrid plasmon resonances detuned from the PDMS absorbance region allowing higher sensitivity and FOM compared to pure crumpled graphene structures on the PDMS substrates. The high sensitivity and broad mechanical tunability of these crumpled 2D material biosensors considerable advantages over traditional refractive index sensors, providing a new platform for ultrasensitive biosensing.

The electrocatalytic N2 reduction reaction (eNRR) - which can occur under ambient conditions with renewable energy input - became a promising synthetic pathway for ammonia (NH3) and has attracted growing attention in the past few years. Some achievements have been made in the eNRR; however, there remain significant challenges to realize satisfactory NH3 production. Therefore, the rational design of highly efficient and durable eNRR catalysts with N[triple bond, length as m-dash]N bond activating and breaking ability is highly desirable. Two-dimensional (2D) materials have shown great potential in electrocatalysis for energy conversion and storage. Although most 2D materials are inactive toward the eNRR, they can be activated by various modification methods. Heteroatom doping engineering can impact the charge distribution and spin states on catalytic sites, therefore accelerating the dinitrogen adsorption and protonation process. This review summarises the recent research progress of heteroatom-doped 2D materials, including carbon, molybdenum disulfide (MoS2) and metal carbides (MXenes), for the eNRR. In addition, some existing opportunities and future research directions in electrocatalytic nitrogen fixation for ammonia production are discussed.

Two-dimensional (2D) materials such as graphene, molybdenum disulfide (MoS2), tungsten diselenide (WSe2), and black phosphorous are being developed for sensing applications with excellent selectivity and high sensitivity. In such applications, 2D materials extensively interact with various analytes including biological molecules. Understanding the interfacial molecular interactions of 2D materials with various targets becomes increasingly important for the progression of better-performing 2D-material based sensors. In this research, molecular interactions between several de novo designed alpha-helical peptides and monolayer MoS2 have been studied. Molecular dynamics simulations were used to validate experimental data. The results suggest that, in contrast to peptide-graphene interactions, peptide aromatic residues do not interact strongly with the MoS2 surface. It is also found that charged amino acids are important for ensuring a standing-up pose for peptides interacting with MoS2. By performing site-specific mutations on the peptide, we could mediate the peptide-MoS2 interactions to control the peptide orientation on MoS2.

Plasmonics and polarotonics of two dimensional (2D) materials have attracted significant attention due to their desirable dispersion relation. Regarding plasmons, according to the 2D dispersion equation, the cutoff frequency limit can be eliminated. Additionally, their large tuneability, high doping (ultradoping) range, and the existence of favorable depolarization factors allow for their better control. Among 2D materials, molybdenum disulfides and molybdenum oxides have recently received increased attention.1-5 The polariton propagation has also been recently shown in atomically smooth molybdenum oxides. For plasmonic propagatrions, tunable plasmon resonances in suspended 2D molybdenum oxide and molybdenum sulfide flakes are demonstrated. The 2D configuration generates a large depolarization factor and the presence of ultra-doping produces visible-light plasmon resonances. The ultra-doping process is conducted by reducing the semiconducting 2D molybdenum trioxide flakes using simulated solar irradiation. The generated plasmon resonances are controlled by the doping levels and the flakes’ lateral dimensions, as well as by exposure to model proteins and enzymes. It is also possible to reach ultradoping levels. Alternatively, by electrochemically intercalating lithium into 2D molybdenum disulfide nanoflakes, plasmon resonances in the visible and near UV wavelength ranges are achieved. These plasmon resonances are controlled by the high doping level of the nanoflakes after the intercalation, producing two distinct resonance peak areas based on the crystal arrangements. The system is also benchmarked for biosensing using bovine serum albumin. The talk will provide the foundation for developing future 2D molybdenum sulphide and oxide based biological and optical units. Polaronic propagation in full stoichiometric molybdenum oxides will also be discussed.6 References 1 Zhang, B. Y.; Zavabeti, A.; Chrimes, A. F.; Haque, F.; O'Dell, L. A.; Khan, H.; Syed, N.; Datta, R.; Wang, Y.; Chesman, A. S. R.; Daeneke, T.; Kalantar-zadeh, K.; Ou, J. Z.,. Advanced Functional Materials 2018, 28, 1706006. 2 Wang, Y.; Ou, J. Z.; Chrimes, A. F.; Carey, B. J.; Daeneke, T.; Alsaif, M. M. Y. A.; Mortazavi, M.; Zhuiykov, S.; Medhekar, N.; Bhaskaran, M.; Friend, J. R.; Strano, M. S.; Kalantar-Zadeh, K., Nano Letters 2015, 15, 883-890. 3 Ma, W.; Alonso-González, P.; Li, S.; Nikitin, A. Y.; Yuan, J.; Martín-Sánchez, J.; Taboada-Gutiérrez, J.; Amenabar, I.; Li, P.; Vélez, S.; Tollan, C.; Dai, Z.; Zhang, Y.; Sriram, S.; Kalantar-Zadeh, K.; Lee, S. T.; Hillenbrand, R.; Bao, Q., Nature 2018, 562, 557-562. 4 de Castro, I. A.; Datta, R. S.; Ou, J. Z.; Castellanos-Gomez, A.; Sriram, S.; Daeneke, T.; Kalantar-zadeh, K., Advanced Materials 2017, 29, 1701619. 5 Alsaif, M. M. Y. A.; Latham, K.; Field, M. R.; Yao, D. D.; Medhekar, N. V.; Beane, G. A.; Kaner, R. B.; Russo, S. P.; Ou, J. Z.; Kalantar-Zadeh, K., Advanced Materials 2014, 26, 3931-3937. 6 Ma W.; Alonso-González, P.; Li, S.; Nikitin, A.W.; Yuan, J.; Martín-Sánchez, J.; Taboada-Gutiérrez, J.; Amenabar, I.; Li, P., Vélez, S.; Tollan, C.; Dai, Z.; Zhang, Y.; Sriram, S.; Kalantar-Zadeh, K.; Lee. S-T., Hillenbrand, R.; Bao, Q. Nature 2018, 562, 557-562.

Two-dimensional (2D) materials have attracted much attention over the last decade due to their high performance in nanoelectronic devices. The discovery of graphene opened up many opportunities to investigate and explore other 2D materials. There has been a drive to expand the toolbox of 2D materials to also include insulators and semiconductors with a variety of bandgaps. As a result, a wide range of materials have been discovered or predicted, with molybdenum disulfide (MoS2) being particularly popular. Using the semiconducting phase of MoS2 (2H-MoS2) requires a relatively high voltage to get sufficient conductivity due to the presence of a band gap. However, for applications in batteries, supercapacitors, electrocatalysts and solar cells, a substantially increased conductivity is required in order to achieve reasonable currents.1 The most common source of conductive MoS2 is metallic MoS2 (1T-MoS2) that has been prepared via the lithium intercalation process, which requires inert atmosphere processing and safety procedures.2 Hence, there is a desire to develop a safer and more efficient process to yield conductive MoS2. Defects play a very important role in modulating the electrical properties of MoS2. Sonication of MoS2 in an appropriate solvent results in many disordered structural defects. The most common defects on MoS2 are sulfur defects. These defects increase the energy level of the gap state and eventually deteriorate the device performance. Thiol based molecules are commonly used to reduce the number of sulfur defects on MoS2. Other molecules such as oxygen or organic super acids like bis(trifluoromethane) sulfonamide (TFSI) have also been reported to passivate the surface defect.3 Past research has mainly focused on the theoretical study of defective MoS2 and how to utilize those defects for improving photoluminescent efficiency. However, those defects can also be utilized to improve the conductivity of MoS2 as a safer alternative for applications in batteries, supercapacitors, solar cells, electrocatalyst and sensors.Conductive MoS2 (c-MoS2) can be used as active material for low-cost solid-state chemiresistive pH sensors.4 In chemiresistive sensors, conductivity changes are observed based on direct interactions between the active material and the analyte.5 Even though chemiresistive pH sensors based on exfoliated graphene, carbon nanotubes, or graphitic materials are available, their sensing response is limited to less than 20%.6 On the other hand, MoS2 has attracted great attention as a promising electrocatalyst for the hydrogen evaluation reaction (HER) because of abundant active sites at edge sites and on the basal plane for facilitating hydrogen production. Water splitting is the simplest and most convenient method to generate hydrogen. In industrial applications, an electrocatalyst is commonly used to accelerate the HER and reduce the overpotential. Even though 2H-MoS2 has good catalytic activity at the edge sites, its low electrical conductivity limits the achievable current density, resulting in a high Tafel value and making it unsuitable for practical application in HER.In this work, we show a simple and effective way to prepare few layer c-MoS2 under ambient conditions using 0.06 vol% aqueous hydrogen peroxide. We have demonstrated that the bulk conductivity of the conductive MoS2 that we prepared is up to seven orders of magnitude higher than that of the semiconducting phase of MoS2. The samples were also characterized with Hall measurements, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy which showed that hydrogen molybdenum bronze (HxMoO3) and substoichiometric MoO3−y help tune the conductivity of the nanometer-scale thin films without impacting the sulfur-to-molybdenum ratio. C-MoS2 was further functionalized with thiols to determine the number of residual reactive sites. An important goal of our work is to control the conductivity of the MoS2 thin films in safe and facile ways that enable their application in low-cost chemiresistive sensors in liquid environments. We fabricated chemiresistive pH sensors with centimeter channel lengths while maintaining low measurement voltages. We further measured the catalytic activity of c-MoS2 films in 0.5 M H2SO4 electrolyte solution with three electrode systems using linear sweep voltammetry (LSV) which showed a lower Tafel value at 10 mA/cm2 current density. The lower Tafel value demonstrated that c-MoS2 has potential to use as catalyst for HER. Our study furthers the understanding of conductive forms of MoS2, and also opens up a new pathway for next generation electronic and energy conversion devices.

The research presented in this paper is an experimental study and numerical analysis on mechanical behavior of the adhesively-bonded joint between FRP sandwich bridge deck and steel girder. Generally, there are three typical stress states in the adhesively-bonded joint: shear stress, tensile stress, and combination of both. To realize these stress states in the adhesively-bonded joint during tests, a specific loading device is developed with the capacity of providing six different loading angles, which are 0°(pure tension), 18°, 36°, 54°, 72° and 90°(pure shear). Failure modes of adhesively-bonded joints are investigated. It indicates that, for the pure shear loading, the failure mode is the cohesive failure (near the interface between the adhesive layer and the steel support) in the adhesive layer. For the pure tensile and combined loading conditions, the failure mode is the combination of fiber breaking, FRP delamination and interfacial adhesion failure between the FRP sandwich deck and the adhesive layer. The load-bearing capacities of adhesive joints under combined loading are much lower than those of the pure tensile and pure shear loading conditions. According to the test results of six angle loading conditions, a tensile/shear failure criterion of the adhesively-bonded joint is obtained. By using Finite Element (FE) modeling method, linear elastic simulations are performed to characterize the stress distribution throughout the adhesively-bonded joint.

A quasi-three-dimensional analysis for an elastic crack at the interface between two semi-infinite dissimilar plates is conducted. The governing equations of the Airy stress function and the out-of-plane displacement are deduced based on the kinematic assumptions for quasi-three-dimensional deformation of plates in extension of Kane and Mindlin. It is found that the quasi-three-dimensional interface crack tip stress field is a complete combination of plane strain bimaterial singular field and antiplane shear singular field under pure tensile loading or pure in-plane shear loading. Three fracture modes are coupled together even if the oscillatory index ε (in plane strain or plane stress) is zero. The oscillatory behavior of the crack tip field is completely characterised by Dundurs' parameters in plane strain no matter how thin the plate is. The effect of plate thickness on stress intensity factors (SIF) is studied. In contrast to the plane stress solution, both the Mode I SIF under in-plane shear loading and the Mode II SIF under tensile loading are nonzero and can not be neglected in the nonoscillatory case. The Mode III SIF tends to zero when the nondimensional thickness h/a, where a is half the crack length and h is half the plate thickness, becomes vanishingly small and reaches its maximum at a certain value of h/a which depends on loading conditions. The antiplane shear effect may not be neglected for plates which are not very thin.