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.

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.

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.

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.

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.

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.

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.

Spatial defects nanoengineering for bipolar conductivity in MoS2.

Understanding the atomistic origin of defects in two-dimensional transition metal dichalcogenides, their impact on the electronic properties, and how to control them is critical for future electronics and optoelectronics. Here, we demonstrate the integration of thermochemical scanning probe lithography (tc-SPL) with a flow-through reactive gas cell to achieve nanoscale control of defects in monolayer MoS2. The tc-SPL produced defects can present either p- or n-type doping on demand, depending on the used gasses, allowing the realization of field effect transistors, and p-n junctions with precise sub-µm spatial control, and a rectification ratio of over 104. Doping and defects formation are elucidated by means of X-Ray photoelectron spectroscopy, scanning transmission electron microscopy, and density functional theory. We find that p-type doping in HCl/H2O atmosphere is related to the rearrangement of sulfur atoms, and the formation of protruding covalent S-S bonds on the surface. Alternatively, local heating MoS2 in N2 produces n-character.

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.

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.

Sub-10 nm Resolution Patterning of Pockets for Enzyme Immobilization with Independent Density and Quasi-3D Topography Control.

The ability to precisely control the localization of enzymes on a surface is critical for several applications including biosensing, bionanoreactors, and single molecule studies. Despite recent advances, fabrication of enzyme patterns with resolution at the single enzyme level is limited by the lack of lithography methods that combine high resolution, compatibility with soft, polymeric structures, ease of fabrication, and high throughput. Here, a method to generate enzyme nanopatterns (using thermolysin as a model system) on a polymer surface is demonstrated using thermochemical scanning probe lithography (tc-SPL). Electrostatic immobilization of negatively charged sulfonated enzymes occurs selectively at positively charged amine nanopatterns produced by thermal deprotection of amines along the side-chain of a methacrylate-based copolymer film via tc-SPL. This process occurs simultaneously with local thermal quasi-3D topographical patterning of the same polymer, offering lateral sub-10 nm resolution, and vertical 1 nm resolution, as well as high throughput (5.2 × 104 µm2/h). The obtained single-enzyme resolution patterns are characterized by atomic force microscopy (AFM) and fluorescence microscopy. The enzyme density, the surface passivation, and the quasi-3D arbitrary geometry of these patterned pockets are directly controlled during the tc-SPL process in a single step without the need of markers or masks. Other unique features of this patterning approach include the combined single-enzyme resolution over mm2 areas and the possibility of fabricating enzymes nanogradients.

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.

Å-Indentation for non-destructive elastic moduli measurements of supported ultra-hard ultra-thin films and nanostructures.

During conventional nanoindentation measurements, the indentation depths are usually larger than 1-10 nm, which hinders the ability to study ultra-thin films (<10 nm) and supported atomically thin two-dimensional (2D) materials. Here, we discuss the development of modulated Å-indentation to achieve sub-Å indentations depths during force-indentation measurements while also imaging materials with nanoscale resolution. Modulated nanoindentation (MoNI) was originally invented to measure the radial elasticity of multi-walled nanotubes. Now, by using extremely small amplitude oscillations (<<1 Å) at high frequency, and stiff cantilevers, we show how modulated nano/Å-indentation (MoNI/ÅI) enables non-destructive measurements of the contact stiffness and indentation modulus of ultra-thin ultra-stiff films, including CVD diamond films (~1000 GPa stiffness), as well as the transverse modulus of 2D materials. Our analysis demonstrates that in presence of a standard laboratory noise floor, the signal to noise ratio of MoNI/ÅI implemented with a commercial atomic force microscope (AFM) is such that a dynamic range of 80 dB -- achievable with commercial Lock-in amplifiers -- is sufficient to observe superior indentation curves, having indentation depths as small as 0.3 Å, resolution in indentation <0.05 Å, and in normal load <0.5 nN. Being implemented on a standard AFM, this method has the potential for a broad applicability.

Author Correction: Ultrahard carbon film from epitaxial two-layer graphene.

In the version of this Article originally published, the second affiliation for Walter A. de Heer had not been included; it should be 'TICNN, Tianjin University, Tianjin, China'. This has now been added and the numbering of subsequent affiliations amended accordingly in all versions of the Article.

Friction and work function oscillatory behavior for an even and odd number of layers in polycrystalline MoS2.

A large effort is underway to investigate the properties of two-dimensional (2D) materials for their potential to become building blocks in a variety of integrated nanodevices. In particular, the ability to understand the relationship between friction, adhesion, electric charges and defects in 2D materials is of key importance for their assembly and use in nano-electro-mechanical and energy harvesting systems. Here, we report on a new oscillatory behavior of nanoscopic friction in continuous polycrystalline MoS2 films for an odd and even number of atomic layers, where odd layers show higher friction and lower work function. Friction force microscopy combined with Kelvin probe force microscopy and X-ray photoelectron spectroscopy demonstrates that an enhanced adsorption of charges and OH molecules is at the origin of the observed increase in friction for 1 and 3 polycrystalline MoS2 layers. In polycrystalline films with an odd number of layers, each crystalline nano-grain carries a dipole due to the MoS2 piezoelectricity, therefore charged molecules adsorb at the grain boundaries all over the surface of the continuous MoS2 film. Their displacement during the sliding of a nano-size tip gives rise to the observed enhanced dissipation and larger nanoscale friction for odd layer-numbers. Similarly, charged adsorbed molecules are responsible for the work function decrease in odd layer-number.

Ultrahard carbon film from epitaxial two-layer graphene.

Atomically thin graphene exhibits fascinating mechanical properties, although its hardness and transverse stiffness are inferior to those of diamond. So far, there has been no practical demonstration of the transformation of multilayer graphene into diamond-like ultrahard structures. Here we show that at room temperature and after nano-indentation, two-layer graphene on SiC(0001) exhibits a transverse stiffness and hardness comparable to diamond, is resistant to perforation with a diamond indenter and shows a reversible drop in electrical conductivity upon indentation. Density functional theory calculations suggest that, upon compression, the two-layer graphene film transforms into a diamond-like film, producing both elastic deformations and sp 2 to sp 3 chemical changes. Experiments and calculations show that this reversible phase change is not observed for a single buffer layer on SiC or graphene films thicker than three to five layers. Indeed, calculations show that whereas in two-layer graphene layer-stacking configuration controls the conformation of the diamond-like film, in a multilayer film it hinders the phase transformation.

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.

Van der Waals Force Isolation of Monolayer MoS2.

Monolayer MoS2 can effectively screen the vdW interaction of underlying substrates with external systems by >90% because of the substantial increase in the separation between the substrate and external systems due to the presence of the monolayer. This substantial screening of vdW interactions by MoS2 monolayer is different from what reported at graphene.