ZIF-8 thin films by a vapor-phase process: limits to growth.

Metal-organic frameworks are a class of porous materials that show promising properties in the field of microelectronics. To reach industrial use of these materials, gas phase techniques are often preferred and were recently introduced. However, the thicknesses achieved are not sufficient, limiting further development. In this work, an improved gas phase process allowing ZIF-8 layer formation of several hundreds of nm using cyclic ligand/water exposures is described. Then, by a combination of in-depth surface analyses and molecular dynamics simulations, the presence and role of hydroxyl defects in the ZIF-8 layer to reach this thickness are established. At the same time, this study unveils an inherent limit of the method: thickness growth is consubstantial with defect repairing upon the crystallites ripening; such defect repairing eventually leads to the decrease of the pore window below the diffusion radius of the incoming linker, thus apparently capping the maximum MOF thickness observable for this type of material topology through this growth method.

Sub-10 nm spatial resolution for electrical properties measurements using bimodal excitation in electric force microscopy.

We demonstrate that under ambient and humidity-controlled conditions, operation of bimodal excitation single-scan electric force microscopy with no electrical feedback loop increases the spatial resolution of surface electrical property measurements down to the 5 nm limit. This technical improvement is featured on epitaxial graphene layers on SiC, which is used as a model sample. The experimental conditions developed to achieve such resolution are discussed and linked to the stable imaging achieved using the proposed method. The application of the herein reported method is achieved without the need to apply DC bias voltages, which benefits specimens that are highly sensitive to polarization. Besides, it allows the simultaneous parallel acquisition of surface electrical properties (such as contact potential difference) at the same scanning rate as in amplitude modulation atomic force microscopy (AFM) topography measurements. This makes it attractive for applications in high scanning speed AFM experiments in various fields for material screening and metrology of semiconductor systems.

Combining surface-sensitive microscopies for analysis of biological tissues after neural device implantation.

In order to address the complexity of chemical analysis of biological systems, time-of-flight secondary ion mass spectrometry (ToF-SIMS), x-ray photoelectron spectroscopy (XPS), and x-ray photoemission electron microscopy (XPEEM) were used for combined surface imaging of a biological tissue formed around a surface neural device after implantation on a nonhuman primate brain. Results show patterns on biological tissue based on extracellular matrix (ECM) and phospholipid membrane (PM) molecular fragments, which were contrasted through principal component analysis of ToF-SIMS negative spectrum. This chemical differentiation may indicate severe inflammation on tissue with an early case of necrosis. Quantification of the elemental composition and the chemical bonding states on both ECM-rich and PM-rich features was possible through XPS analysis from survey and high-resolution spectra, respectively. Variable amounts of carbon (68%-80.5%), nitrogen (10%-2.4%), and oxygen (20.8%-16.5%) were detected on the surface of the biological tissue. Chlorine, phosphorous sodium, and sulfur were also identified in lower extends. Besides that, analysis of the C 1s high-resolution spectra for the same two regions (ECM and PM ones) showed that a compromise between C-C (41.8 at. %) and C-N/C-O (35.6 at. %) amounts may indicate a strong presence of amino acids and proteoglycans on the ECM fragment-rich region, while the great amount of C-C (70.1 at. %) on the PM fragment-rich region is attributed to the large chains of fatty acids connected to phospholipid molecules. The micrometer-scale imaging of these chemical states on tissue was accomplished through XPEEM analysis. The C-C presence was found uniformly distributed across the entire analyzed area, while C-N/C-O and C=O were in two distinct regions. The combination of ToF-SIMS, XPS, and XPEEM is shown here as a powerful, noninvasive approach to map out elemental and chemical properties of biological tissues, i.e., identification of chemically distinct regions, followed by quantification of the surface chemical composition in each distinct region.

Characterization of Collagen/Lipid Nanoparticle-Curcumin Cryostructurates for Wound Healing Applications.

Curcumin-loaded collagen cryostructurates have been devised for wound healing applications. Curcumin displays strong antioxidant, antiseptic, and anti-inflammatory properties, while collagen is acknowledged for promoting cell adhesion, migration and differentiation. However, when curcumin is loaded directly into collagen hydrogels, it forms large molecular aggregates and clogs the matrix pores. A double-encapsulation strategy is therefore developed by loading curcumin into lipid nanoparticles (LNP), and embedding these particles inside collagen scaffolds. The resulting collagen/LNP cryostructurates have an optimal fibrous structure with ≈100 µm average pore size for sustaining cell migration. Results show that collagen is structurally unaltered and that nanoparticles are homogeneously distributed amidst collagen fibers. Hydrogels soaked in saline buffer release about 20 to 30% of their nanoparticles content within 24 h, while achieved 100% release after 25 days. When exposed to NIH 3T3 fibroblasts, these hydrogels provide a satisfactory scaffold for cell interaction as early as 4 h after seeding, with no cytotoxic counter effect. These positive features make the collagen/lipid cryostructurates a promising material for further use in wound healing.

A scanning probe microscopy study of nanostructured TiO2/poly(3-hexylthiophene) hybrid heterojunctions for photovoltaic applications.

The nanoscale morphology of photoactive hybrid heterojunctions plays a key role in the performances of hybrid solar cells. In this work, the heterojunctions consist of a nanocolumnar TiO2 surface covalently grafted with a monolayer of poly(3-hexylthiophene) (P3HT) functionalized with carboxylic groups (-COOH). Through a joint analysis of the photovoltaic properties at the nanoscale by photoconductive-AFM (PC-AFM) and surface photovoltage imaging, we investigated the physical mechanisms taking place locally during the photovoltaic process and the correlation to the nanoscale morphology. A down-shift of the vacuum level of the TiO2 surface upon grafting was measured by Kelvin probe force microscopy (KPFM), evidencing the formation of a dipole at the TiO2/P3HT-COOH interface. Upon in situ illumination, a positive photovoltage was observed as a result of the accumulation of photogenerated holes in the P3HT layer. A positive photocurrent was recorded in PC-AFM measurements, whose spatial mapping was interpreted consistently with the corresponding KPFM analysis, offering a correlated analysis of interest from both a theoretical and material design perspective.

A synthetic redox biofilm made from metalloprotein-prion domain chimera nanowires.

Engineering bioelectronic components and set-ups that mimic natural systems is extremely challenging. Here we report the design of a protein-only redox film inspired by the architecture of bacterial electroactive biofilms. The nanowire scaffold is formed using a chimeric protein that results from the attachment of a prion domain to a rubredoxin (Rd) that acts as an electron carrier. The prion domain self-assembles into stable fibres and provides a suitable arrangement of redox metal centres in Rd to permit electron transport. This results in highly organized films, able to transport electrons over several micrometres through a network of bionanowires. We demonstrate that our bionanowires can be used as electron-transfer mediators to build a bioelectrode for the electrocatalytic oxygen reduction by laccase. This approach opens opportunities for the engineering of protein-only electron mediators (with tunable redox potentials and optimized interactions with enzymes) and applications in the field of protein-only bioelectrodes.

Doping characteristics of iodine on as-grown chemical vapor deposited graphene on Pt.

Using laboratory X-ray photoelectron emission microscopy (XPEEM), we investigated the doping efficiency and thermal stability of iodine on as-grown graphene on Pt. After iodine adsorption of graphene in saturated vapor of I2, monolayer and bilayer graphene exhibited work function of 4.93 eV and 4.87 eV, respectively. Annealing of the doped monolayer graphene at 100 °C led to desorption of hydrocarbons, which increased the work function of monolayer graphene by ~0.2 eV. The composition of the polyiodide complexes evolved upon a step-by-step annealing at temperatures from 100 °C to 300 °C while the work-function non-monotonically changed with decreasing iodine content. The iodine dopant was stable at relatively high temperature as a significant amount of iodine remained up to the annealing temperature of 350 °C.

Work function tuning for high-performance solution-processed organic photodetectors with inverted structure.

Organic photodetectors with inverted structure are fabricated by solution process techniques. A very thin interfacing layer of polyethyleneimine leads to a homogenous interface with low work function. The devices exhibit excellent performances, in particular in terms of low dark current density, wide range linearity, high detectivity, and remarkable stability in ambient air without encapsulation.

Highly end-doped silicon nanowires for field-effect transistors on flexible substrates.

We report on the VLS (vapour-liquid-solid) fabrication and characterization of in situ axially doped silicon nanowires (SiNWs) at both ends, and on their integration into a bottom gate-top contact geometry on both rigid and flexible substrates to realize field-effect transistors (FETs). To improve contact resistance between SiNWs and source/drain electrodes, we axially tuned the level of doping at both ends of the SiNWs by sequential in situ addition of PH(3). Characterisation of SiNWs by scanning spreading resistance microscopy in the device configuration allowed us to determine precisely the different sections of the SiNWs. The transfer to flexible substrates still allowed for workable FET structures. Transistors with electron mobilities exceeding 120 cm(2) V(-1) s(-1), I(on)/I(off) ratios greater than 10(7) and ambipolar behaviour were achieved.

A hard x-ray nanoprobe for scanning and projection nanotomography.

To fabricate and qualify nanodevices, characterization tools must be developed to provide a large panel of information over spatial scales spanning from the millimeter down to the nanometer. Synchrotron x-ray-based tomography techniques are getting increasing interest since they can provide fully three-dimensional (3D) images of morphology, elemental distribution, and crystallinity of a sample. Here we show that by combining suitable scanning schemes together with high brilliance x-ray nanobeams, such multispectral 3D volumes can be obtained during a single analysis in a very efficient and nondestructive way. We also show that, unlike other techniques, hard x-ray nanotomography allows reconstructing the elemental distribution over a wide range of atomic number and offers truly depth resolution capabilities. The sensitivity, 3D resolution, and complementarity of our approach make hard x-ray nanotomography an essential characterization tool for a large panel of scientific domains.