Growth of Fe-BDC Metal-Organic Frameworks onto Functionalized Si (111) Surfaces.

The realization of metal-organic framework (MOF) layers onto solid surfaces is a prerequisite for their integration into devices. This work reports the direct growth of Fe3+ /benzene di-carboxylate MOFs onto functionalized silicon surfaces, compatible with a wide range of MOF synthesis conditions. The co-nucleation and growth of different crystalline phases are evidenced, whose coverage depends on the surface chemistry and/or the solution composition. Three structural phases - the cubic MIL-101(Fe), a hexagonal phase with a structure close to MOF-235 and a MIL-53(Fe) with a monoclinic symmetry - are identified through characteristic crystal shapes and their structural parameters inferred from X-Ray Diffraction. In addition to the oriented growth of 3D crystallites, the formation of two-dimensional MIL-101 nano-crystallites or thin layers/islands exhibiting extended monocrystalline domains with (111) texture is also demonstrated through high-resolution atomic force microscopy. Post-synthesis treatments reveal a weak adhesion of the hexagonal phase, indicating a different surface anchoring.

ToF-SIMS Li Depth Profiling of Pure and Methylated Amorphous Silicon Electrodes After Their Partial Lithiation.

Pure (a-Si:H) and methylated [a-Si0.95(CH3)0.05:H] amorphous silicon thin films were analyzed by time-of-flight secondary ion mass spectrometry after partial lithiation. Depth profiling gives insights into the lithiation mechanism of the material, enabling us to study the detailed biphasic process in the first lithiation process. Lithiation induces swelling and roughening of the active layer. In both a-Si:H and a-Si0.95(CH3)0.05:H, no measurable Li diffusion was observed after stopping current-induced lithiation. After applying the same lithiation charges, distinct Li profiles were observed for these two materials. Unlike a-Si:H, the Li concentration drops slowly from the heavily lithiated region to the non-lithiated region in a-Si0.95(CH3)0.05:H. This apparent progressive transition between the lithiated and lithium-free regions is attributed to the presence of nanovoids inside the material. When their concentration is high enough, these nanovoids constitute favorable quasi-percolating paths for lithium during the first lithiation. A specific model was developed to simulate the Li depth profiles, fully supporting this hypothesis.

Controlled oxidation, biofunctionalization, and patterning of alkyl monolayers on silicon and silicon nitride surfaces using plasma treatment.

A new method is presented for the fast and reproducible functionalization of silicon and silicon nitride surfaces coated with covalently attached alkyl monolayers. After formation of a methyl-terminated 1-hexadecyl monolayer on H-terminated Si(100) and Si(111) surfaces, short plasma treatments (1-3 s) are sufficient to create oxidized functionalities without damaging the underlying oxide-free silicon. The new functional groups can, e.g., be derivatized using the reaction of surface aldehyde groups with primary amines to form imine bonds. In this way, plasma-treated monolayers on silicon or silicon nitride surfaces were successfully coated with nanoparticles, or proteins such as avidin. In addition, we demonstrate the possibility of micropatterning, using a soft contact mask during the plasma treatment. Using water contact angle measurements, ellipsometry, XPS, IRRAS, AFM, and reflectometry, proof of principle is demonstrated of a yet unexplored way to form patterned alkyl monolayers on oxide-free silicon surfaces.

Transition between two dendritic growth mechanisms in electrodeposition.

We report in this paper the observation of a transition between two different dendritic growth mechanisms in the electrodeposition of a metal from a binary electrolyte. Our results, in particular concerning the dendritic growth velocities, enable us to explain this behavior in terms of models previously proposed in the literature.

Effect of lithiation potential and cycling on chemical and morphological evolution of Si thin film electrode studied by ToF-SIMS.

Si thin films obtained by plasma enhanced chemical vapor deposition (PECVD) were used to investigate chemical and morphological modifications induced by lithiation potential and cycling. These modifications were thoughtfully analyzed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profiling, which allows to distinguish the surface and bulk processes related to the formation of the solid electrolyte interphase (SEI) layer, and Li-Si alloying, respectively. The main results are a volume expansion/shrinkage and a dynamic behavior of the SEI layer during the single lithiation/delithiation process and multicycling. Trapping of lithium and other ions corresponding to products of electrolyte decomposition are the major reasons of electrode modifications. It is shown that the SEI layer contributes to 60% of the total volume variation of Si electrodes (100 nm). The apparent diffusion coefficient of lithium (DLi) calculated from the Fick's second law directly from Li-ion ToF-SIMS profiles is of the order of ∼5.9 × 10(-15) cm(2).s(-1). This quite low value can be explained by Li trapping in the bulk of electrode material, at the interfaces, continuous growth of the SEI layer and increase of SiO2 quantity. These modifications can result in limitation the ionic transport of Li.

Monodisperse hydrogel microspheres by forced droplet formation in aqueous two-phase systems.

This paper presents a method to form micron-sized droplets in an aqueous two-phase system (ATPS) and to subsequently polymerize the droplets to produce hydrogel beads. Owing to the low interfacial tension in ATPS, droplets do not easily form spontaneously. We enforce the formation of drops by perturbing an otherwise stable jet that forms at the junction where the two aqueous streams meet. This is done by actuating a piezo-electric bending disc integrated in our device. The influence of forcing amplitude and frequency on jet breakup is described and related to the size of monodisperse droplets with a diameter in the range between 30 and 60 µm. Rapid on-chip polymerization of derivatized dextran inside the droplets created monodisperse hydrogel particles. This work shows how droplet-based microfluidics can be used in all-aqueous, surfactant-free, organic-solvent-free biocompatible two-phase environment.

Protein-repellent silicon nitride surfaces: UV-induced formation of oligoethylene oxide monolayers.

The grafting of polymers and oligomers of ethylene oxide onto surfaces is widely used to prevent nonspecific adsorption of biological material on sensors and membrane surfaces. In this report, we show for the first time the robust covalent attachment of short oligoethylene oxide-terminated alkenes (CH(3)O(CH(2)CH(2)O)(3)(CH(2))(11)-(CH═CH(2)) [EO(3)] and CH(3)O(CH(2)CH(2)O)(6)(CH(2))(11)-(CH═CH(2)) [EO(6)]) from the reaction of alkenes onto silicon-rich silicon nitride surfaces at room temperature using UV light. Reflectometry is used to monitor in situ the nonspecific adsorption of bovine serum albumin (BSA) and fibrinogen (FIB) onto oligoethylene oxide coated silicon-rich silicon nitride surfaces (EO(n)-Si(x)N(4), x > 3) in comparison with plasma-oxidized silicon-rich silicon nitride surfaces (SiO(y)-Si(x)N(4)) and hexadecane-coated Si(x)N(4) surfaces (C(16)-Si(x)N(4)). A significant reduction in protein adsorption on EO(n)-Si(x)N(4) surfaces was achieved, adsorption onto EO(3)-Si(x)N(4) and EO(6)-Si(x)N(4) were 0.22 mg m(-2) and 0.08 mg m(-2), respectively. The performance of the obtained EO(3) and EO(6) layers is comparable to those of similar, highly protein-repellent monolayers formed on gold and silver surfaces. EO(6)-Si(x)N(4) surfaces prevented significantly the adsorption of BSA (0.08 mg m(-2)). Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray reflectivity and static water contact angle measurements were employed to characterize the modified surfaces. In addition, the stability of EO(6)-Si(x)N(4) surfaces in phosphate-buffered saline solution (PBS) and alkaline condition (pH 10) was studied. Prolonged exposure of the surfaces to PBS solution for 1 week or alkaline condition for 2 h resulted in only minor degradation of the ethylene oxide moieties and no oxidation of the Si(x)N(4) substrates was observed. Highly stable antifouling coatings on Si(x)N(4) surfaces significantly broaden the application potential of silicon nitride-coated microdevices, and in particular of microfabricated filtration membranes.

Covalently attached organic monolayers on SiC and SixN4 surfaces: formation using UV light at room temperature.

We describe the formation of alkyl monolayers on silicon carbide (SiC) and silicon-rich silicon nitride (SixN4) surfaces, using UV irradiation in the presence of alkenes. Both the surface preparation and the monolayer attachment were carried out under ambient conditions. The stable coatings obtained in this way were studied by water contact angle measurements, infrared reflection absorption spectroscopy, X-ray reflectivity, and X-ray photoelectron spectroscopy. Besides unfunctionalized 1-alkenes, methyl undec-10-enoate, and 2,2,2-trifluoroethyl undec-10-enoate were also grafted onto both substrates. The resulting ester-terminated surfaces could then be further reacted after hydrolysis using amide chemistry to easily allow the attachment of amine-containing compounds.

Covalent attachment of organic monolayers to silicon carbide surfaces.

This work presents the first alkyl monolayers covalently bound on HF-treated silicon carbide surfaces (SiC) through thermal reaction with 1-alkenes. Treatment of SiC with diluted aqueous HF solutions removes the native oxide layer (SiO2) and provides a reactive hydroxyl-covered surface. Very hydrophobic methyl-terminated surfaces (water contact angle theta = 107 degrees ) are obtained on flat SiC, whereas attachment of omega-functionalized 1-alkenes also yields well-defined functionalized surfaces. Infrared reflection absorption spectroscopy, ellipsometry, and X-ray photoelectron spectroscopy measurements are used to characterize the monolayers and show their covalent attachment. The resulting surfaces are shown to be extremely stable under harsh acidic conditions (e.g., no change in theta after 4 h in 2 M HCl at 90 degrees C), while their stability in alkaline conditions (pH = 11, 60 degrees C) also supersedes that of analogous monolayers such as those on Au, Si, and SiO2. These results are very promising for applications involving functionalized silicon carbide.

Covalent biofunctionalization of silicon nitride surfaces.

Covalently attached organic monolayers on etched silicon nitride (SixN4; x >/= 3) surfaces were prepared by reaction of SixN4-coated wafers with neat or solutions of 1-alkenes and 1-alkynes in refluxing mesitylene. The surface modification was monitored by measurement of the static water contact angle, XPS, IRRAS, AFM, and ToF-SIMS, and evidence for the formation of Si-C bonds is presented. The etching can be achieved by dilute HF solutions and yields both Si-H and N-H moieties. The resulting etched SixN4 surfaces are functionalized by terminal carboxylic acid groups in either of two ways: (a) via attachment of a 10-undecenoic acid 2,2,2-trifluoroethyl ester (trifluoro ethanol ester) and subsequent thermal acid hydrolysis; (b) through attachment of a photocleavable ester, and subsequent photochemical cleavage, as this would allow photopatterned functionalized SixN4. The carboxylic acids are successfully used for the attachment of oligopeptides (aspartame) and complete proteins using EDC/NHS chemistry. Finally, an amino-terminated organic monolayer can be formed by reaction of HF-treated SixN4 surfaces with a N-(omega-undecylenyl)phthalimide, which yields an amino-terminated surface upon deprotection with hydrazine.