Hierarchical Surface Pattern on Ni-Free Ti-Based Bulk Metallic Glass to Control Cell Interactions.

Ni-free Ti-based bulk metallic glasses (BMGs) are exciting materials for biomedical applications because of their outstanding biocompatibility and advantageous mechanical properties. The glassy nature of BMGs allows them to be shaped and patterned via thermoplastic forming (TPF). This work demonstrates the versatility of the TPF technique to create micro- and nano-patterns and hierarchical structures on Ti40Zr10Cu34Pd14Sn2 BMG. Particularly, a hierarchical structure fabricated by a two-step TPF process integrates 400 nm hexagonal close-packed protrusions on 2.5 µm square protuberances while preserving the advantageous mechanical properties from the as-cast material state. The correlations between thermal history, structure, and mechanical properties are explored. Regarding biocompatibility, Ti40Zr10Cu34Pd14Sn2 BMGs with four surface topographies (flat, micro-patterned, nano-patterned, and hierarchical-structured surfaces) are investigated using Saos-2 cell lines. Alamar Blue assay and live/dead analysis show that all tested surfaces have good cell proliferation and viability. Patterned surfaces are observed to promote the formation of longer filopodia on the edge of the cytoskeleton, leading to star-shaped and dendritic cell morphologies compared with the flat surface. In addition to potential implant applications, TPF-patterned Ti-BMGs enable a high level of order and design flexibility on the surface topography, expanding the available toolbox for studying cell behavior on rigid and ordered surfaces.

Assessing Fire-Damage in Historical Papers and Alleviating Damage with Soft Cellulose Nanofibers.

The conservation of historical paper objects with high cultural value is an important societal task. Papers that have been severely damaged by fire, heat, and extinguishing water, are a particularly challenging case, because of the complexity and severity of damage patterns. In-depth analysis of fire-damaged papers, by means of examples from the catastrophic fire in a 17th-century German library, shows the changes, which proceeded from the margin to the center, to go beyond surface charring and formation of hydrophobic carbon-rich layers. The charred paper exhibits structural changes in the nano- and micro-range, with increased porosity and water sorption. In less charred areas, cellulose is affected by both chain cleavage and cross-linking. Based on these results and conclusions with regard to adhesion of auxiliaries, a stabilization method is developed, which coats the damaged paper with a thin layer of cellulose nanofibers. It enables the reliable preservation of the paper and-most importantly-retrieval of the contained historical information: the nanofibers form a flexible, transparent film on the surface and adhere strongly to the damaged matrix, greatly reducing its fragility, giving it stability, and enabling digitization and further handling.

Probing the charge transfer and electron-hole asymmetry in graphene-graphene quantum dot heterostructure.

In recent years, graphene-based van der Waals (vdW) heterostructures have come into prominence showcasing interesting charge transfer dynamics which is significant for optoelectronic applications. These novel structures are highly tunable depending on several factors such as the combination of the two-dimensional materials, the number of layers and band alignment exhibiting interfacial charge transfer dynamics. Here, we report on a novel graphene based 0D-2D vdW heterostructure between graphene and amine-functionalized graphene quantum dots (GQD) to investigate the interfacial charge transfer and doping possibilities. Using a combination ofab initiosimulations and Kelvin probe force microscopy (KPFM) measurements, we confirm that the incorporation of functional GQDs leads to a charge transfer induced p-type doping in graphene. A shift of the Dirac point by 0.05 eV with respect to the Fermi level (EF) in the graphene from the heterostructure was deduced from the calculated density of states. KPFM measurements revealed an increment in the surface potential of the GQD in the 0D-2D heterostructure by 29 mV with respect to graphene. Furthermore, we conducted power dependent Raman spectroscopy for both graphene and the heterostructure samples. An optical doping-induced gating effect resulted in a stiffening of theGband for electrons and holes in both samples (graphene and the heterostructure), suggesting a breakdown of the adiabatic Born-Oppenheimer approximation. Moreover, charge imbalance and renormalization of the electron-hole dispersion under the additional influence of the doped functional GQDs is pointing to an asymmetry in conduction and carrier mobility.

Two-dimensional talc as a van der Waals material for solid lubrication at the nanoscale.

Talc is a van der Waals and naturally abundant mineral with the chemical formula Mg3Si4O10(OH)2. Two-dimensional (2D) talc could be an alternative to hBN as van der Waals dielectric in 2D heterostructures. Furthermore, due to its good mechanical and frictional properties, 2D talc could be integrated into various hybrid microelectromechanical systems, or used as a functional filler in polymers. However, properties of talcas one of the main representatives of the phyllosilicate (sheet silicates) group are almost completely unexplored when ultrathin crystalline films and monolayers are considered. We investigate 2D talc flakes down to single layer thickness and reveal their efficiency for solid lubrication at the nanoscale. We demonstrate by atomic force microscopy based methods and contact angle measurements that several nanometer thick talc flakes have all properties necessary for efficient lubrication: a low adhesion, hydrophobic nature, and a low friction coefficient of 0.10 ± 0.02. Compared to the silicon-dioxide substrate, 2D talc flakes reduce friction by more than a factor of five, adhesion by around 20%, and energy dissipation by around 7%. Considering our findings, together with the natural abundance of talc, we put forward that 2D talc can be a cost-effective solid lubricant in micro- and nano-mechanical devices.

Synthesis and Assembly of Zinc Oxide Microcrystals by a Low-Temperature Dissolution-Reprecipitation Process: Lessons Learned About Twin Formation in Heterogeneous Reactions.

Cobalt-doped zinc oxide single crystals with the shape of hexagonal platelets were synthesized by thermohydrolysis of zinc acetate, cobalt acetate, and hexamethylenetetramine (HMTA) in mixtures of ethanol and water. The mineralization proceeds by a low-temperature dissolution-reprecipitation process from the liquid phase by the formation of basic cobalt zinc salts as intermediates. The crystal shape as well as twin formation of the resulting oxide phase can be influenced by careful choice of the solvent mixture and the amount of doping. An understanding of the course of the reaction was achieved by comprehensive employment of analytical techniques (i.e., SEM, XRD, IR) including an in-depth HRTEM study of precipitates from various reaction stages. In addition, EPR as well as UV/Vis spectroscopic measurements provide information about the insertion of the cobalt dopant into the zincite lattice. The Langmuir-Blodgett (LB) technique is shown to be suitable for depositing coatings of the platelets on glass substrates functionalized with polyelectrolyte multilayers and hence is applied for the formation of monolayers containing domains with ordered tessellation. No major differences are found between deposits on substrates with anionic or cationic surface modification. The adherence to the substrates is sufficient to determine the absolute orientation of the deposited polar single crystals by piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) studies.

From Permeation to Cluster Arrays: Graphene on Ir(111) Exposed to Carbon Vapor.

Our scanning tunneling microscopy and X-ray photoelectron spectroscopy experiments along with first-principles calculations uncover the rich phenomenology and enable a coherent understanding of carbon vapor interaction with graphene on Ir(111). At high temperatures, carbon vapor not only permeates to the metal surface but also densifies the graphene cover. Thereby, in addition to underlayer graphene growth, upon cool down also severe wrinkling of the densified graphene cover is observed. In contrast, at low temperatures the adsorbed carbon largely remains on top and self-organizes into a regular array of fullerene-like, thermally highly stable clusters that are covalently bonded to the underlying graphene sheet. Thus, a new type of predominantly sp2-hybridized nanostructured and ultrathin carbon material emerges, which may be useful to encage or stably bind metal in finely dispersed form.

Combining adhesive contact mechanics with a viscoelastic material model to probe local material properties by AFM.

Viscoelastic properties are often measured using probe based techniques such as nanoindentation (NI) and atomic force microscopy (AFM). Rarely, however, are these methods verified. In this article, we present a method that combines contact mechanics with a viscoelastic model (VEM) composed of springs and dashpots. We further show how to use this model to determine viscoelastic properties from creep curves recorded by a probe based technique. We focus on using the standard linear solid model and the generalized Maxwell model of order 2. The method operates in the range of 0.01 Hz to 1 Hz. Our approach is suitable for rough surfaces by providing a defined contact area using plastic pre-deformation of the material. The very same procedure is used to evaluate AFM based measurements as well as NI measurements performed on polymer samples made from poly(methyl methacrylate) and polycarbonate. The results of these measurements are then compared to those obtained by tensile creep tests also performed on the same samples. It is found that the tensile test results differ considerably from the results obtained by AFM and NI methods. The similarity between the AFM results and NI results suggests that the proposed method is capable of yielding results comparable to NI but with the advantage of the imaging possibilities of AFM. Furthermore, all three methods allowed a clear distinction between PC and PMMA by means of their respective viscoelastic properties.

Polymorphism of dioctyl-terthiophene within thin films: The role of the first monolayer.

The origins of specific polymorphic phases within thin films are still not well understood. The polymorphism of the molecule dioctyl-terthiophene is investigated during the presence of a silicon-oxide surface during the crystallisation process. It is found that a monolayer of molecules forms two-dimensional crystals on the surface. In the case of thicker films crystalline islands are formed, a comparison of the three polymorphic phases observed within thin films and the thermodynamically more stable single crystal phases reveals distinct differences which can be related to an adaption of the molecular packing with the flat surface of the substrate.

Inverted bulk-heterojunction solar cell with cross-linked hole-blocking layer.

We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium-tin-oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor-acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process.

Shape of picoliter droplets on chemically striped patterned substrates.

We studied the shape of water droplets deposited using an inkjet nozzle on a chemically striped patterned substrate consisting of alternating hydrophobic and hydrophilic stripes. The droplet dimensions are comparable to the period of the stripes, typically covering up to 13 stripes. As such, our present results bridge the gap linking two regimes previously considered: (i) droplets on single stripes and (ii) droplets covering more than 50 stripes. In line with previous work on markedly smaller water droplets, the exact deposition position is important for the final shape of the droplets. A droplet with its center deposited on a hydrophobic stripe reaches a shape that is different than when it is deposited on a hydrophilic stripe. Experimental results of different droplet configurations on the same surface are in agreement with simulations using the lattice Boltzmann model. In addition, the simulations enable a detailed analysis of droplet free energies and the volume dependence. The latter reveals scaling properties of shape parameters in terms of droplet radius scaled to the period of the stripe pattern, which have remained unexplored until now.

Island shape anisotropy in organic thin film growth induced by ion-beam irradiated rippled surfaces.

Controlling thin film growth of conjugated molecules is a key factor in organic electronics. Here, we report on the growth of the organic semiconductor para-hexaphenyl (6P) on ion bombarded, rippled TiO2(110) surfaces. These surfaces represent a one-dimensionally patterned substrate with alternating descending and ascending step trains with typical step distances below 1 nm. A clear island shape anisotropy and a discretization of the island width according to the ripple wavelength have been observed which are addressed to anisotropic detachment of molecules differently bound to the island rim at ascending and descending steps. By changing the average ripple length from ∼11 nm to ∼60 nm, the islands' length-to-width ratio could be tuned between ∼1.5 : 1 and ∼4.5 : 1. Further, strong diffusion anisotropy along and perpendicular to the ripples was found to be responsible for an increasing island density with decreasing ripple length.

X-ray based tools for the investigation of buried interfaces in organic electronic devices.

X-ray reflectivity combined with grazing incidence diffraction is a valuable tool for investigating organic multilayer structures that can be used in devices. We focus on a bilayer stack consisting of two materials (poly-(3-hexylthiophene)) (P3HT) and poly-(4-styrenesulfonic acid) (PSSA) spin cast from orthogonal solvents (water in the case of PSSA and chloroform or toluene for P3HT). X-ray reflectivity is used to determine the thickness of all layers as well as the roughness of the organic-organic hetero-interface and the P3HT surface. The surface roughness is found to be consistent with the results of atomic force microscopy measurements. For the roughness of P3HT/PSSA interface, we observe a strong dependence on the solvent used for P3HT deposition. The solvent also strongly impacts the texturing of the P3HT crystallites as revealed by grazing incidence diffraction. When applying the various PSSA/P3HT multilayers in organic thin-film transistors, we find an excellent correlation between the determined interface morphology, structure and the device performance.

Dynamics of monolayer-island transitions in 2,7-dioctyl-benzothienobenzthiophene thin films.

The order in molecular monolayers is a crucial aspect for their technological application. However, the preparation of defined monolayers by spin-coating is a challenge, since the involved processes are far from thermodynamic equilibrium. In the work reported herein, the dynamic formation of dioctyl-benzothienobenzothiophene monolayers is explored as a function of temperature by using X-ray scattering techniques and atomic force microscopy. Starting with a disordered monolayer after the spin-coating process, post-deposition self-reassembly at room temperature transforms the initially amorphous layer into a well-ordered bilayer structure with a molecular herringbone packing, whereas at elevated temperature the formation of crystalline islands occurs. At the temperature of the liquid-crystalline crystal-smectic transition, rewetting of the surface follows resulting in a complete homogeneous monolayer. By subsequent controlled cooling to room temperature, cooling-rate-dependent kinetics is observed; at rapid cooling, a stable monolayer is preserved at room temperature, whereas slow cooling causes bilayer structures. Increasing the understanding and control of monolayer formation is of high relevance for achieving ordered functional monolayers with defined two-dimensional packing, for future applications in the field of organic electronics.

Atomic force microscopy based manipulation of graphene using dynamic plowing lithography.

Tapping mode atomic force microscopy (AFM) is employed for dynamic plowing lithography of exfoliated graphene on silicon dioxide substrates. The shape of the graphene sheet is determined by the movement of the vibrating AFM probe. There are two possibilities for lithography depending on the applied force. At moderate forces, the AFM tip only deforms the graphene and generates local strain of the order of 0.1%. For sufficiently large forces the AFM tip can hook graphene and then pull it, thus cutting the graphene along the direction of the tip motion. Electrical characterization by AFM based electric force microscopy, Kelvin probe force microscopy and conductive AFM allows us to distinguish between the truly separated islands and those still connected to the surrounding graphene.

Photoinduced edge-specific nanoparticle decoration of two-dimensional tungsten diselenide nanoribbons.

Metallic nanoparticles are widely explored for boosting light-matter coupling, optoelectronic response, and improving photocatalytic performance of two-dimensional (2D) materials. However, the target area is restricted to either top or bottom of the 2D flakes. Here, we introduce an approach for edge-specific nanoparticle decoration via light-assisted reduction of silver ions and merging of silver seeds. We observe arrays of the self-limited in size silver nanoparticles along tungsten diselenide WSe2 nanoribbon edges. The density of nanoparticles is tunable by adjusting the laser fluence. Scanning electron microscopy, atomic force microscopy, and Raman spectroscopy are used to investigate the size, distribution, and photo-response of the deposited plasmonic nanoparticles on the quasi-one-dimensional nanoribbons. We report an on-surface synthesis path for creating mixed-dimensional heterostructures and heterojunctions with potential applications in opto-electronics, plasmonics, and catalysis, offering improved light matter coupling, optoelectronics response, and photocatalytic performance of 2D materials.

Electrical monitoring of organic crystal phase transition using MoS2 field effect transistor.

Hybrid van der Waals heterostructures made of 2D materials and organic molecules exploit the high sensitivity of 2D materials to all interfacial modifications and the inherent versatility of the organic compounds. In this study, we are interested in the quinoidal zwitterion/MoS2 hybrid system in which organic crystals are grown by epitaxy on the MoS2 surface and reorganize in another polymorph after thermal annealing. By means of field-effect transistor measurements recorded in situ all along the process, atomic force microscopy and density functional theory calculations we demonstrate that the charge transfer between quinoidal zwitterions and MoS2 strongly depends on the conformation of the molecular film. Remarkably, both the field effect mobility and the current modulation depth of the transistors remain unchanged which opens up promising prospects for efficient devices based on this hybrid system. We also show that MoS2 transistors enable fast and accurate detection of structural modifications that occur during phases transitions of the organic layer. This work highlights that MoS2 transistors are remarkable tools for on-chip detection of molecular events occurring at the nanoscale, which paves the way for the investigation of other dynamical systems.

Pinaceae Pine Resins (Black Pine, Shore Pine, Rosin, and Baltic Amber) as Natural Dielectrics for Low Operating Voltage, Hysteresis-Free, Organic Field Effect Transistors.

Four pinaceae pine resins analyzed in this study: black pine, shore pine, Baltic amber, and rosin demonstrate excellent dielectric properties, outstanding film forming, and ease of processability from ethyl alcohol solutions. Their trap-free nature allows fabrication of virtually hysteresis-free organic field effect transistors operating in a low voltage window with excellent stability under bias stress. Such green constituents represent an excellent choice of materials for applications targeting biocompatibility and biodegradability of electronics and sensors, within the overall effort of sustainable electronics development and environmental friendliness.

Tuning kinetics to control droplet shapes on chemically striped patterned surfaces.

The typically elongated shape of droplets on chemically microstriped surfaces has been suggested to depend strongly on the kinetics during deposition. Here, we unequivocally establish the importance of impact kinetics by comparing the geometry of pico- to microliter droplets deposited from an inkjet nozzle with those obtained by conventional deposition from a syringe. For large Weber numbers, the strongly enhanced spreading during the impact in combination with direction-dependent pinning of the contact line gives rise to more spherical droplets with a low aspect ratio. The impact energy can be minimized by the prolonged firing of small picoliter droplets to form larger droplets or, as shown in the past, by using high-viscosity liquids. In the first case, the impact energy is absorbed by the liquid already present, therewith reducing the impact diameter and consequently forming markedly more elongated droplets.

Substrate selected polymorphism of epitaxially aligned tetraphenyl-porphyrin thin films.

Porphyrin molecules, of interest as versatile materials for organic electronics, are highly prone to formation of significantly different polymorphic phases. To elucidate the determinants for the specific polymorphic phase formed in thin films as well as for the arrangement of the molecules on a given substrate two different anisotropic substrate surfaces have been selected: KCl(100) and the oxygen reconstructed Cu(110) surface. We observe that the crystal structure of the thin films depends on the substrate, whereas the relative molecular orientations in both cases are similar. X-Ray and transmission electron diffraction of 30 nm thick tetraphenyl-porphyrin (H(2)TPP) and platinum tetraphenyl-porphyrin (PtTPP) thin films deposited on KCl(100) surfaces reveals that both kinds of molecules crystallize in a tetragonal polymorph with the (001) lattice planes, i.e. with their macrocycles, parallel to the substrate. Films deposited on the oxygen reconstructed Cu(110)-(2 × 1)O surface exhibit in contrast the triclinic polymorph even though molecules again align nearly parallel to the substrate surface as observed by LEED and X-ray diffraction. On both substrates we identify two driving forces for the epitaxial alignment of porphyrins: (i) molecules aligning with their macrocycles (nearly) parallel to the substrate surface and (ii) the porphyrin molecules forming a commensurate unit cell with the respective substrate. The polymorphic phase meeting both requirements is the most favorable to be formed on a given substrate and due to this structural flexibility in both cases well-ordered, epitaxially aligned porphyrin thin films are achieved.