Self-Assembly Propensity Dictates Lifetimes in Transient Naphthalimide-Dipeptide Nanofibers.

Transient self-assembly of dipeptide nanofibers with lifetimes that are predictably variable through dipeptide sequence design are presented. This was achieved using 1,8-naphthalimide (NI) amino acid methyl-esters (Phe, Tyr, Leu) that are biocatalytically coupled to amino acid-amides (Phe, Tyr, Leu, Val, Ala, Ser) to form self-assembling NI-dipeptides. However, competing hydrolysis of the dipeptides results in disassembly. It was demonstrated that the kinetic parameters like lifetimes of these nanofibers can be predictably regulated by the thermodynamic parameter, namely the self-assembly propensity of the constituent dipeptide sequence. These lifetimes could vary from minutes, to hours, to permanent gels that do not degrade. Moreover, the in-built NI fluorophore was utilized to image the transient nanostructures in solution with stimulated emission depletion (STED) based super-resolution fluorescence microscopy.

High-throughput protein nanopatterning.

High-throughput and large-scale patterning of enzymes with sub-10 nm resolution, the size range of individual protein molecules, is crucial for propelling advancement in a variety of areas, from the development of chip-based biomolecular nano-devices to molecular-level studies of cell biology. Despite recent developments in bio-nanofabrication technology, combining 10 nm resolution with high-throughput and large-scale patterning of enzymes is still an open challenge. Here, we demonstrate a high resolution and high-throughput patterning method to generate enzyme nanopatterns with sub-10 nm resolution by using thermochemical scanning probe lithography (tc-SPL). First, tc-SPL is used to generate amine patterns on a methacrylate copolymer film. Thermolysin enzymes functionalized with sulfonate-containing fluorescent labels (Alexa-488) are then directly immobilized onto the amine patterns through electrostatic interaction. Enzyme patterns with sub-10 nm line width are obtained as evidenced by atomic force microscopy (AFM) and fluorescence microscopy. Moreover, we demonstrate large-scale and high throughput (0.13 × 0.1 mm2 at a throughput of 5.2 × 104 µm2 h-1) patterning of enzymes incorporating 10 nm detailed pattern features. This straightforward and high-throughput method of fabricating enzyme nanopatterns will have a significant impact on future bio-nanotechnology applications and molecular-level biological studies. By scaling up using parallel probes, tc-SPL is promising for implementation to scale up the fabrication of nano-biodevices.

Elastic coupling between layers in two-dimensional materials.

Two-dimensional materials, such as graphene and MoS2, are films of a few atomic layers in thickness with strong in-plane bonds and weak interactions between the layers. The in-plane elasticity has been widely studied in bending experiments where a suspended film is deformed substantially; however, little is known about the films' elastic modulus perpendicular to the planes, as the measurement of the out-of-plane elasticity of supported 2D films requires indentation depths smaller than the films' interlayer distance. Here, we report on sub-ångström-resolution indentation measurements of the perpendicular-to-the-plane elasticity of 2D materials. Our indentation data, combined with semi-analytical models and density functional theory, are then used to study the perpendicular elasticity of few-layer-thick graphene and graphene oxide films. We find that the perpendicular Young's modulus of graphene oxide films reaches a maximum when one complete water layer is intercalated between the graphitic planes. This non-destructive methodology can map interlayer coupling and intercalation in 2D films.

Understanding How Charged Nanoparticles Electrostatically Assemble and Distribute in 1-D.

The effects of increasing the driving forces for a 1-D assembly of nanoparticles onto a surface are investigated with experimental results and models. Modifications, which take into account not only the particle-particle interactions but also particle-surface interactions, to previously established extended random sequential adsorption simulations are tested and verified. Both data and model are compared against the heterogeneous random sequential adsorption simulations, and finally, a connection between the two models is suggested. The experiments and models show that increasing the particle-surface interaction leads to narrower particle distribution; this narrowing is attributed to the surface interactions compensating against the particle-particle interactions. The long-term advantage of this work is that the assembly of nanoparticles in solution is now understood as controlled not only by particle-particle interactions but also by particle-surface interactions. Both particle-particle and particle-surface interactions can be used to tune how nanoparticles distribute themselves on a surface.

Speed dependence of thermochemical nanolithography for gray-scale patterning.

Thermochemical nanolithography (TCNL) is a high-resolution lithographic technique and, owing to its fast speed, versatility, and unique ability to fabricate arbitrary, gray-scale nanopatterns, this scanning probe technique is relevant both for fundamental scientific research as well as for nanomanufacturing applications. In this work, we study the dependence of the TCNL driven chemical reactions on the translation speed of the thermal cantilever. The experimental data compares well with a model of the chemical kinetics for a first-order reaction. The impact of higher order reactions on the optimization of TCNL is addressed. The reported quantitative description of the speed dependence of TCNL is exploited and illustrated by fabricating controlled gradients of chemical concentration.

Impact of metastable graphene-diamond coatings on the fracture toughness of silicon carbide.

Silicon carbide has excellent mechanical properties such as high hardness and strength, but its applications for body armor and protective coating solutions are limited by its poor toughness. It has been demonstrated that epitaxial graphene-coated SiC can enhance SiC mechanical properties due to the pressure-activated phase transition into a sp3 diamond structure. Here, we show that atomically thin graphene coatings increase the hardness of SiC even for indentation depths of ∼10 µm. Very importantly, the graphene coating also causes an increase of the fracture toughness by 11% compared to bare SiC, which is in contradiction with the general indirect variation of hardness and fracture toughness. This is explained in terms of the presence of a diamond phase under the indenter while the rest of the coating remains in the ultra-tough graphene phase. This study opens new venues for understanding hardness and toughness in metastable systems and for the applications of graphene-coatings.

Probing the Mechanical Properties of 2D Materials via Atomic-Force-Microscopy-Based Modulated Nanoindentation.

As the field of low-dimensional materials (1D or 2D) grows and more complex and intriguing structures are continuing to be found, there is an emerging need for techniques to characterize the nanoscale mechanical properties of all kinds of 1D/2D materials, in particular in their most practical state: sitting on an underlying substrate. While traditional nanoindentation techniques cannot accurately determine the transverse Young's modulus at the necessary scale without large indentations depths and effects to and from the substrate, herein an atomic-force-microscopy-based modulated nanomechanical measurement technique with Angstrom-level resolution (MoNI/ÅI) is presented. This technique enables non-destructive measurements of the out-of-plane elasticity of ultra-thin materials with resolution sufficient to eliminate any contributions from the substrate. This method is used to elucidate the multi-layer stiffness dependence of graphene deposited via chemical vapor deposition and discover a peak transverse modulus in two-layer graphene. While MoNI/ÅI has been used toward great findings in the recent past, here all aspects of the implementation of the technique as well as the unique challenges in performing measurements at such small resolutions are encompassed.

Dedoping of Intraband Silver Selenide Colloidal Quantum Dots through Strong Electronic Coupling at Organic/Inorganic Hybrid Interfaces.

Colloidal quantum dot (CQD) infrared (IR) photodetectors can be fabricated and operated with larger spectral tunability, fewer limitations in terms of cooling requirements and substrate lattice matching, and at a potentially lower cost than detectors based on traditional bulk materials. Silver selenide (Ag2Se) has emerged as a promising sustainable alternative to current state-of-the-art toxic semiconductors based on lead, cadmium, and mercury operating in the IR. However, an impeding gap in available absorption bandwidth for Ag2Se CQDs exists in the short-wave infrared (SWIR) region due to degenerate doping by the environment, switching the CQDs from intrinsic interband semiconductors in the near-infrared (NIR) to intraband absorbing CQDs in the mid-wave infrared (MWIR). Herein, we show that the small molecular p-type dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) can be used to extract electrons from the 1Se state of MWIR active Ag2Se CQDs to activate their intrinsic energy gap in the SWIR window. We demonstrate quenching of the MWIR Ag2Se absorbance peak, shifting of nitrile vibrational peaks characteristic of charge-neutral F4-TCNQ, as well as enhanced CQD absorption around ∼2500 nm after doping both in ambient and under air-free conditions. We elucidate the doping mechanism to be one that involves an integer charge transfer akin to doping in semiconducting polymers. These indications of charge transfer are promising milestones on the path to achieving sustainable SWIR Ag2Se CQD photodetectors.

On the origin of the improved hydrogen evolution reaction in Mn- and Co-doped MoS2.

In the field of hydrogen production, MoS2 demonstrates good catalytic properties for the hydrogen evolution reaction (HER) which improve when doped with metal cations. However, while the role of sulfur atoms as active sites in the HER is largely reported, the role of metal atoms (i.e. molybdenum or the dopant cations) has yet to be studied in depth. To understand the role of the metal dopant, we study MoS2 thin films doped with Co and Mn ions. We identify the contribution of the electronic bands of the Mn and Co dopants to the integral valence band of the material using in situ resonant photoemission measurements. We demonstrate that Mn and Co dopants act differently: Mn doping favors the shift of the S-Mo hybridized band towards the Fermi level, while in the case of Co doping it is the less hybridized Co band that shifts closer to the Fermi level. Doping with Mn increases the effectiveness of S as the active site, thus improving the HER, while doping with Co introduces the metallic site of Co as the active site, which is less effective in improving HER properties. We therefore clarify the role of the dopant cation in the electronic structure determining the active site for hydrogen adsorption/desorption. Our results pave the way for the design of efficient materials for hydrogen production via the doping route, which can be extended to different catalytic reactions in the field of energy applications.

Elucidating Local Structure and Positional Effect of Dopants in Colloidal Transition Metal Dichalcogenide Nanosheets for Catalytic Hydrogenolysis.

Tailoring nanoscale catalysts to targeted applications is a vital component in reducing the carbon footprint of industrial processes; however, understanding and controlling the nanostructure influence on catalysts is challenging. Molybdenum disulfide (MoS2), a transition metal dichalcogenide (TMD) material, is a popular example of a nonplatinum-group-metal catalyst with tunable nanoscale properties. Doping with transition metal atoms, such as cobalt, is one method of enhancing its catalytic properties. However, the location and influence of dopant atoms on catalyst behavior are poorly understood. To investigate this knowledge gap, we studied the influence of Co dopants in MoS2 nanosheets on catalytic hydrodesulfurization (HDS) through a well-controlled, ligand-directed, tunable colloidal doping approach. X-ray absorption spectroscopy and density functional theory calculations revealed the nonmonotonous relationship between dopant concentration, location, and activity in HDS. Catalyst activity peaked at 21% Co:Mo as Co saturates the edge sites and begins basal plane doping. While Co prefers to dope the edges over basal sites, basal Co atoms are demonstrably more catalytically active than edge Co. These findings provide insight into the hydrogenolysis behavior of doped TMDs and can be extended to other TMD materials.

Room-temperature metastability of multilayer graphene oxide films.

Graphene oxide potentially has multiple applications. The chemistry of graphene oxide and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This understanding is crucial to enable future applications of this material. Here, a combined experimental and density functional theory study shows that multilayer graphene oxide produced by oxidizing epitaxial graphene through the Hummers method is a metastable material whose structure and chemistry evolve at room temperature with a characteristic relaxation time of about one month. At the quasi-equilibrium, graphene oxide reaches a nearly stable reduced O/C ratio, and exhibits a structure deprived of epoxide groups and enriched in hydroxyl groups. Our calculations show that the structural and chemical changes are driven by the availability of hydrogen in the oxidized graphitic sheets, which favours the reduction of epoxide groups and the formation of water molecules.

Fabricating nanoscale chemical gradients with ThermoChemical NanoLithography.

Production of chemical concentration gradients on the submicrometer scale remains a formidable challenge, despite the broad range of potential applications and their ubiquity throughout nature. We present a strategy to quantitatively prescribe spatial variations in functional group concentration using ThermoChemical NanoLithography (TCNL). The approach uses a heated cantilever to drive a localized nanoscale chemical reaction at an interface, where a reactant is transformed into a product. We show using friction force microscopy that localized gradients in the product concentration have a spatial resolution of ~20 nm where the entire concentration profile is confined to sub-180 nm. To gain quantitative control over the concentration, we introduce a chemical kinetics model of the thermally driven nanoreaction that shows excellent agreement with experiments. The comparison provides a calibration of the nonlinear dependence of product concentration versus temperature, which we use to design two-dimensional temperature maps encoding the prescription for linear and nonlinear gradients. The resultant chemical nanopatterns show high fidelity to the user-defined patterns, including the ability to realize complex chemical patterns with arbitrary variations in peak concentration with a spatial resolution of 180 nm or better. While this work focuses on producing chemical gradients of amine groups, other functionalities are a straightforward modification. We envision that using the basic scheme introduced here, quantitative TCNL will be capable of patterning gradients of other exploitable physical or chemical properties such as fluorescence in conjugated polymers and conductivity in graphene. The access to submicrometer chemical concentration and gradient patterning provides a new dimension of control for nanolithography.

Giant Increase of Hardness in Silicon Carbide by Metastable Single Layer Diamond-Like Coating.

Silicon carbide (SiC) is one of the hardest known materials. Its exceptional mechanical properties combined with its high thermal conductivity make it a very attractive material for a variety of technological applications. Recently, it is discovered that two-layer epitaxial graphene films on SiC can undergo a pressure activated phase transition into a sp3 diamene structure at room temperature. Here, it is shown that epitaxial graphene films grown on SiC can increase the hardness of SiC up to 100% at low loads (up to 900 µN), and up to 30% at high loads (10 mN). By using a Berkovich diamond indenter and nanoindentation experiments, it is demonstrated that the 30% increase in hardness is present even for indentations depths of 175 nm, almost three hundred times larger than the graphene film thickness. The experiments also show that the yield point of SiC increases up to 77% when the SiC surface is coated with epitaxial graphene. These improved mechanical properties are explained with the formation of diamene under the indenter's pressure.

A Polymer Canvas with the Stiffness of the Bone Matrix to Study and Control Mesenchymal Stem Cell Response.

Reproducing in vitro the complex multiscale physical features of human tissues creates novel biomedical opportunities and fundamental understanding of cell-environment interfaces and interactions. While stiffness has been recognized as a key driver of cell behavior, systematic studies on the role of stiffness have been limited to values in the KPa-MPa range, significantly below the stiffness of bone. Here, a platform enabling the tuning of the stiffness of a biocompatible polymeric interface up to values characteristic of human bone is reported, which are in the GPa range, by using extremely thin polymer films on glass and cross-linking the films using ultraviolet (UV) light irradiation. It is shown that a higher stiffness is related to better adhesion, proliferation, and osteogenic differentiation, and that it is possible to switch on/off cell attachment and growth by solely tuning the stiffness of the interface, without any surface chemistry or topography modification. Since the stiffness is tuned directly by UV irradiation, this platform is ideal for rapid and simple fabrication of stiffness patterns and gradients, thus representing an innovative tool for combinatorial studies of the synergistic effect of tissue environmental cues on cell behavior, and creates new opportunities for next-generation biosensors, single-cell patterning, and lab-on-a-chip devices.

Adhesion and size dependent friction anisotropy in boron nitride nanotubes.

The frictional properties of individual multiwalled boron nitride nanotubes (BN-NTs) synthesized by chemical vapour deposition (CVD) and deposited on a silicon substrate are investigated using an atomic force microscope tip sliding along (longitudinal sliding) and across (transverse sliding) the tube's principal axis. Because of the tube's transverse deformations during the tip sliding, a larger friction coefficient is found for the transverse sliding as compared to the longitudinal sliding. Here, we show that the friction anisotropy in BN-NTs, defined as the ratio between transverse and longitudinal friction forces per unit area, increases with the nanotube-substrate contact area, estimated to be proportional to (L(NT)R(NT))(1/2), where L(NT) and R(NT) are the length and the radius of the nanotube, respectively. Larger contact area denotes stronger surface adhesion, resulting in a longitudinal friction coefficient closer to the value expected in the absence of transverse deformations. Compared to carbon nanotubes (C-NTs), BN-NTs display a friction coefficient in each sliding direction with intermediate values between CVD and arc discharge C-NTs. CVD BN-NTs with improved tribological properties and higher oxidation temperature might be a better candidate than CVD C-NTs for applications in extreme environments.

Relation between interfacial shear and friction force in 2D materials.

Understanding the interfacial properties between an atomic layer and its substrate is of key interest at both the fundamental and technological levels. From Fermi level pinning to strain engineering and superlubricity, the interaction between a single atomic layer and its substrate governs electronic, mechanical and chemical properties. Here, we measure the hardly accessible interfacial transverse shear modulus of an atomic layer on a substrate. By performing measurements on bulk graphite, and on epitaxial graphene films on SiC with different stacking orders and twisting, as well as in the presence of intercalated hydrogen, we find that the interfacial transverse shear modulus is critically controlled by the stacking order and the atomic layer-substrate interaction. Importantly, we demonstrate that this modulus is a pivotal measurable property to control and predict sliding friction in supported two-dimensional materials. The experiments demonstrate a reciprocal relationship between friction force per unit contact area and interfacial shear modulus. The same relationship emerges from simulations with simple friction models, where the atomic layer-substrate interaction controls the shear stiffness and therefore the resulting friction dissipation.

Pressure-Induced Formation and Mechanical Properties of 2D Diamond Boron Nitride.

Understanding phase transformations in 2D materials can unlock unprecedented developments in nanotechnology, since their unique properties can be dramatically modified by external fields that control the phase change. Here, experiments and simulations are used to investigate the mechanical properties of a 2D diamond boron nitride (BN) phase induced by applying local pressure on atomically thin h-BN on a SiO2 substrate, at room temperature, and without chemical functionalization. Molecular dynamics (MD) simulations show a metastable local rearrangement of the h-BN atoms into diamond crystal clusters when increasing the indentation pressure. Raman spectroscopy experiments confirm the presence of a pressure-induced cubic BN phase, and its metastability upon release of pressure. Å-indentation experiments and simulations show that at pressures of 2-4 GPa, the indentation stiffness of monolayer h-BN on SiO2 is the same of bare SiO2, whereas for two- and three-layer-thick h-BN on SiO2 the stiffness increases of up to 50% compared to bare SiO2, and then it decreases when increasing the number of layers. Up to 4 GPa, the reduced strain in the layers closer to the substrate decreases the probability of the sp2-to-sp3 phase transition, explaining the lower stiffness observed in thicker h-BN.

Hindered rolling and friction anisotropy in supported carbon nanotubes.

Carbon nanotubes (CNTs) are well known for their exceptional thermal, mechanical and electrical properties. For many CNT applications it is of the foremost importance to know their frictional properties. However, very little is known about the frictional forces between an individual nanotube and a substrate or tip. Here, we present a combined theoretical and experimental study of the frictional forces encountered by a nanosize tip sliding on top of a supported multiwall CNT along a direction parallel or transverse to the CNT axis. Surprisingly, we find a higher friction coefficient in the transverse direction compared with the parallel direction. This behaviour is explained by a simulation showing that transverse friction elicits a soft 'hindered rolling' of the tube and a frictional dissipation that is absent, or partially absent for chiral CNTs, when the tip slides parallel to the CNT axis. Our findings can help in developing better strategies for large-scale CNT assembling and sorting on a surface.

Optically Inspired Nanomagnonics with Nonreciprocal Spin Waves in Synthetic Antiferromagnets.

Integrated optically inspired wave-based processing is envisioned to outperform digital architectures in specific tasks, such as image processing and speech recognition. In this view, spin waves represent a promising route due to their nanoscale wavelength in the gigahertz frequency range and rich phenomenology. Here, a versatile, optically inspired platform using spin waves is realized, demonstrating the wavefront engineering, focusing, and robust interference of spin waves with nanoscale wavelength. In particular, magnonic nanoantennas based on tailored spin textures are used for launching spatially shaped coherent wavefronts, diffraction-limited spin-wave beams, and generating robust multi-beam interference patterns, which spatially extend for several times the spin-wave wavelength. Furthermore, it is shown that intriguing features, such as resilience to back reflection, naturally arise from the spin-wave nonreciprocity in synthetic antiferromagnets, preserving the high quality of the interference patterns from spurious counterpropagating modes. This work represents a fundamental step toward the realization of nanoscale optically inspired devices based on spin waves.