Transient deflection response in microcantilever array integrated with polydimethylsiloxane (PDMS) microfluidics

We report the integration of a nanomechanical sensor consisting of 16 silicon microcantilevers with polydimethylsiloxane (PDMS) microfluidics. For microcantilevers positioned near the bottom of a microfluidic flow channel, a transient differential analyte concentration for the top versus bottom surface of each microcantilever is created when an analyte-bearing fluid is introduced into the flow channel (which is initially filled with a non-analyte containing solution). We use this effect to characterize a bare (nonfunctionalized) microcantilever array in which the microcantilevers are simultaneously read out with our recently developed high sensitivity in-plane photonic transduction method. We first examine the case of non-specific binding of bovine serum albumin (BSA) to silicon. The average maximum transient microcantilever deflection in the array is -1.6 nm, which corresponds to a differential surface stress of only -0.23 mN m(-1). This is in excellent agreement with the maximum differential surface stress calculated based on a modified rate equation in conjunction with finite element simulation. Following BSA adsorption, buffer solutions with different pH are introduced to further study microcantilever array transient response. Deflections of 20-100 nm are observed (2-14 mN m(-1) differential surface stress). At a flow rate of 5 μL min(-1), the average measured temporal width (FWHM) of the transient response is 5.3 s for BSA non-specific binding and 0.74 s for pH changes.     

FTIR-ATR evaluation of organic contaminant cleaning methods for SiO2 surfaces.

The effectiveness of cleaning organic contaminants from silicon dioxide (SiO2) surfaces was studied by conducting highly sensitive measurements using Fourier Transform Infrared Attenuated Total reflectance (FTIR-ATR) with a Si prism as the waveguide. To serve as an example, the surface of the prism was oxidized to an order of a few nanometers. The oxidized Si surface film was allowed to stand in the atmosphere and then wet-cleaned in a repeated manner; subsequently its thickness was measured by ellipsometry. Although, various wet-cleaning methods were tested, they only showed values of 0.1-0.2 nm larger than, but not equal to, the original thickness immediately after oxidation. FTIR-ATR measurements of the spectral change after exposure to air revealed that organic species, such as C-CH3 and -(CH2)n-, increased with time. Wet-cleaning the sample failed to remove the C-CH3 species, which indicates that they corresponded to the film thickness increment from the original.     

Development of a classical force field for the oxidized Si surface: application to hydrophilic wafer bonding

We have developed a classical two- and three-body interaction potential to simulate the hydroxylated, natively oxidized Si surface in contact with water solutions, based on the combination and extension of the Stillinger-Weber potential and of a potential originally developed to simulate SiO(2) polymorphs. The potential parameters are chosen to reproduce the structure, charge distribution, tensile surface stress, and interactions with single water molecules of a natively oxidized Si surface model previously obtained by means of accurate density functional theory simulations. We have applied the potential to the case of hydrophilic silicon wafer bonding at room temperature, revealing maximum room temperature work of adhesion values for natively oxidized and amorphous silica surfaces of 97 and 90 mJm(2), respectively, at a water adsorption coverage of approximately 1 ML. The difference arises from the stronger interaction of the natively oxidized surface with liquid water, resulting in a higher heat of immersion (203 vs 166 mJm(2)), and may be explained in terms of the more pronounced water structuring close to the surface in alternating layers of larger and smaller densities with respect to the liquid bulk. The computed force-displacement bonding curves may be a useful input for cohesive zone models where both the topographic details of the surfaces and the dependence of the attractive force on the initial surface separation and wetting can be taken into account.     

Interface diffusion and chemical reaction of PZT layer/Si (111) sample during the annealing treatment in air

The interface diffusion and chemical reaction between a PZT (PbZrxTi1-xO3) layer and a Si(111) substrate during the annealing treatment in air have been studied by using XPS (X-Ray Photoelectron Spectroscopy) and AES (Auger Electron Spectroscopy). The results indicate that the Ti element in the PZT precursor reacted with residual carbon and silicon, diffused from the Si substrate, to form TiCx, TiSix species in the PZT layer during the thermal treatment. A great interface diffusion and chemical reaction took place on the interface of PZT Si also. The silicon atoms diffused from silicon substrate onto the surface of PZT layer. The oxygen atoms, which came from air, diffused into silicon substrate also and reacted with Si atoms to form a SiO2 interlayer between the PZT layer and the Si (111) substrate. The thickness of SiO2 interlayer was proportional to the square root of treatment time. The formation of the SiO2 interlayer was governed by the diffusion of oxygen in the PZT layer at low annealing tempera     

Effect of boron on the surface tension of molten silicon and its temperature coefficient

The influence of boron concentration (C(B)/mass%) on the surface tension of molten silicon has been investigated with the sessile drop method under oxygen partial pressure P(O(2))=1.62x10(-25)-2.63x10(-22) MPa, and the results can be summarized as follows. The surface tension increases with C(B) in the range below 2.09 mass%, and the maximum increase rate of the surface tension is about 30 mN m(-1)(mass% C(B))(-1). The temperature coefficient of the surface tension, ( partial differential sigma/ partial differential T)C(B), was found to increase with the boron concentration in molten silicon. At the interface between molten silicon and the BN substrate, a discontinuous Si(3)N(4) layer was reckoned to form and the layer might prevent BN from dissolving into the molten silicon. Since dissolved boron from the BN substrate into the molten silicon is below 0.054 mass% and the associated increase in surface tension is below 1.5 mN m(-1), the contamination from the BN substrate on the surface tension can be ignored. The relation between the surface tension and C(B) indicates negative adsorption of boron and can be well described by combining the Gibbs adsorption isotherm with the Langmuir isotherm.     

X-ray photoelectron spectroscopic analysis of Si nanoclusters in SiO2 matrix

We investigated silicon nanoclusters Si(nc) in a SiO2 matrix prepared by the plasma-enhanced chemical vapor deposition technique, using X-ray photoelectron spectroscopy (XPS) with external voltage stimuli in both static and pulsed modes. This method enables us to induce an additional charging shift of 0.8 eV between the Si2p peaks of the oxide and the underlying silicon, both in static and time-resolved modes, for a silicon sample containing a 6 nm oxide layer. In the case of the sample containing silicon nanoclusters, both Si2p peaks of Si(nc) and host SiO2 undergo a charging shift that is 1 order of magnitude larger (>15 eV), with no measurable difference between them (i.e., no differential charging between the silicon nanoclusters and the oxide matrix could be detected). By use of a measured Auger parameter, we estimate the relaxation energy of the Si(nc) in the SiO2 matrix as -0.4 eV, which yields a -0.6 eV shift in the binding energy of the Si(nc) with respect to that of bulk Si in the opposite direction of the expected quantum size effect. This must be related to the residual differential charging between the silicon nanoclusters and the oxide host. Therefore, differential charging is still the biggest obstacle for extracting size-dependent binding energy shifts with XPS when one uses the oxide peak as the reference.     

Anisotropic polymerization of a long-chain diacetylene derivative Langmuir-Blodgett film on a step-bunched SiO2/Si surface

Alternating facet/terrace nanostructures were fabricated on a SiO2 surface by step-bunching and thermal oxidation of a vicinal Si(111) substrate, and their influence upon the polymerization direction of a long-chain diacetylene derivative monolayer film was investigated by angle-dependent polarized near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was found that the peak intensity of the C 1s-pi transition was stronger when the electric vector plane of the incident X-ray was parallel to the direction of the periodic facet/terrace structures rather than perpendicular to them. On the contrary, a polymer film fabricated on a flat SiO2 surface showed no in-plane anisotropy of the peak intensity. These results indicate that the diacetylene groups in the diacetylene derivative monolayer are preferentially photopolymerized in the direction not across but along the periodic one-dimensional structures on the step-bunched and thermally oxidized SiO2/Si(111) surface.     

Nanoscale aggregate structures of trisiloxane surfactants at the solid-liquid interface

The self-associating structures at the solid-liquid interface of three nonionic trisiloxane surfactants ((CH3)3SiO)2Si(CH3)(CH2)3(OCH2CH2)n OH (n = 6, 8, and 12), or BEn, are studied as a function of substrate properties by atomic force microscopy (AFM) imaging and force measurement. These trisiloxane surfactants are known as superwetters, which promote rapid spreading of dilute aqueous solutions on low-energy surfaces. This study also attempts to relate the BEn surface aggregate structures at the solid-liquid interface to their superwetting behavior. Four substrates are used in the study: muscovite mica, highly oriented pyrolytic graphite, and oxidized silicon wafer with and without a full monolayer of self-assembled n-octadecyltrichlorosilane (OTS). The concentration of BEn is fixed at 2 times the critical aggregation concentration (CAC). The BEn surfactants are only weakly attracted to hydrophilic surfaces, more on oxidized silicon than on mica. All three form ordinary planar monolayers on HOPG and OTS-covered oxidized silicon. The significance of surfactant adsorption on the AFM tip is investigated by comparing the force curves obtained by tips with and without thiol modification. The surface aggregate structures of the BEn surfactants correlate with their bulk structures and do not exhibit anomalous adsorption behavior. The adsorption behavior of the BEn superwetters is similar to that of the CmEn surfactants. Thus, our results confirm previous work showing that superwetting shares its main features with other classes of surfactants.     

利用XPS 氩离子刻蚀表征锂离子电池Si/C负极材料中含硅的活性物质

以石墨、沥青和纳米硅粉为原料制备了锂离子电池Si/C负极材料,使用SEM/ BSE 、Raman、XRD、XPS及XPS氩离子刻蚀等方法对其硅活性物质进行了具体分析。结果表明,XRD和Raman仅判断出负极材料中含有活性物质单质Si;常规XPS结果发现近一半的Si已被氧化为惰性物质SiO2;而使用XPS氩离子刻蚀方法发现负极材料中Si存在5种化学态,包括活性物质单质Si、Si2O、SiO、Si2O3,及惰性物质SiO2;定量结果表明,复合材料的硅活性物质高于96.56%,且主要结构是低价态硅氧化物,而非单质Si。XPS氩离子刻蚀的分析方法为锂离子电池负极材料中硅活性物质的研究提供了新思路。     

Electrostatic field and partial Fermi level pinning at the pentacene-SiO(2) interface

Monolayer islands of pentacene deposited on silicon substrates with thermally grown oxides were studied by electric force microscopy (EFM) and scanning Kelvin probe microscopy (SKPM) in ultrahigh vacuum (UHV) after prior 10 min exposure to atmospheric ambient. On 25-nm-thick oxides, the pentacene islands are 0.5 V higher in electrostatic potential than the silicon dioxide background because of intrinsic contact potential differences. On 2-nm-thin oxides, tunneling across the oxides allows Fermi level equilibration with pentacene associated states. The surface potential difference depends on the doping of the underlying Si substrates. The Fermi level movement at the pentacene SiO(2) interface was restricted and estimated to lie between 0.3 and 0.6 eV above the pentacene valence band maximum. It is proposed that hole traps in the pentacene or at the pentacene-oxide interface are responsible for the observations.     

Surface stress, thickness, and mass of the first few layers of polyelectrolyte

The effects of surface stress and mass loading upon the adsorption of polyelectrolytes onto flexible silicon micromechanical cantilever sensors (MCSs) were studied in situ. A self-assembled monolayer of 2-mercaptoethylamine chloride (2-MEA) on gold was used to achieve single-side adsorption on the MCS. Such a preparation gave a positive surface potential, whereas a bare SiOx surface gave a negative surface potential. Wide scan X-ray photoelectron spectroscopy confirmed that the adsorption of polystyrenesulfonate (PSS) and polyallylamine hydrochloride (PAH) followed the general rule expected from the electrostatic interaction between the substrate and the polyelectrolyte, whereas the adsorption polyethyleneimine (PEI) did not. The adsorption of PAH on SiO(x) from a 3 mM water solution containing 1 M NaCl was associated with a deflection of the MCS toward the polyelectrolyte monolayer (tensile surface stress) owing to the hydrogen bonding between neighboring amino groups. Here, a surface stress change of 1.4 +/- 0.1 N/m was estimated. The adsorption of PSS from a 3 mM water solution containing 1 M NaCl on a 2-MEA surface induced a deflection of the MCS away from the polyelectrolyte layer (compressive stress), toward the SiO(x) side. Here, a surface stress change of 3.1 +/- 0.3 N/m was determined. The formation of a PAH layer on top of the PSS layer resulted in a deflection of the MCS toward the PAH layer. This indicated that the adjacent PSS layer was deswelling, corresponding to a surface stress change of 0.5 +/- 0.1 N/m.     

Diffusion reaction of oxygen in HfO2/SiO2/Si stacks

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.     

Redox-induced surface stress of polypyrrole-based actuators

We measure the surface stress induced by electrochemical transformations of a thin conducting polymer film. One side of a micromechanical cantilever-based sensor is covered with an electropolymerized dodecyl benzenesulfonate-doped polypyrrole (PPyDBS) film. The microcantilever serves as both the working electrode (in a conventional three-electrode cell configuration) and as the mechanical transducer for simultaneous, in situ, and real-time measurements of the current and interfacial stress changes. A compressive change in surface stress of about -2 N/m is observed when the conducting polymer is electrochemically switched between its oxidized (PPy+) and neutral (PPy0) state by cyclic voltammetry. The surface stress sensor's response during the anomalous first reductive scan is examined. The effect of long-term cycling on the mechanical transformation ability of PPy(DBS) films in both surfactant and halide-based electrolytes is also discussed. We have identified two main competing origins of surface stress acting on the PPy(DBS)/ gold-coated microcantilever: one purely mechanical due to the volume change of the conducting polymer, and a second charge-induced, owing to the interaction of anions of the supporting electrolyte with the gold surface.     

Formation of Particle Coated Fusiform Droplets via Lowering Interface Tension with Polyaluminum Sulfate

It was found that the interface tension between water and alkenyl succinic anhydride (ASA) was significantly reduced by polyaluminum sulfate (PAS), increased considerably though by TiO₂ nanoparticle. PAS with basicity of 0.75 (PAS-0.75) reduced the interface tension to a larger extent than PAS with basicity of 0.3 (PAS-0.3). By reducing interface tension with PAS-0.75, ASA-in-water emulsion bearing fusiform geometries was constructed. The emulsion stabilized by PAS-0.3 and TiO₂ nanoparticle bore spherical shapes with the exception when mass fraction of TiO₂ nanoparticle was low, in which case fused nonspherical drops were formed. Forming nonspherical emulsion crucially depends on ASA-water interface tension, where a critical interface tension was identified to be 0.6–0.7 mN/m. The fusiform geometries were transformed into spherical shapes when interface tension was higher than 0.7 mN/m. Both the lowering mechanism of the interface tension and the formation mechanism of the fusiform emulsion were proposed.      

Effects of Pt diffusion barrier layer on the interface reaction and electric properties of PZT film/Si (111) sample

The effects of the Pt diffusion barrier layer on the interface diffusion and reaction, crystallization, dielectric and ferroelectric properties of the PZT/Si(111) sample have been studied using XPS, AES and XRD techniques. Hie results indicate that the Pt diffusion barrier layer between the PZT layer and the Si substrate prohibits the formation of TiCx TiSix and SiO2 species in the PZT layer. The Pt barrier layer also completely interrupts the diffusion of Si from the Si substrate into the PZT layer and impedes the diffusion of oxygen from air to the Si substrate greatly. Although the Pt layer can not prevent completely the diffusion and reaction between oxygen and silicon, it can prevent the formation of a stable SiO2 interface layer on the interface of PZT/Si. The Pt layer reacts with silicon to form PtSix species on the interface of Pt/Si, which can intensify the chemical binding strength between the Pt layer and the Si substrate. To play a good role as a diffusion barrier layer, the Pt barrier layer     

Adsorption of silanes bearing nitrogenated Lewis bases on SiO2/Si (100) model surfaces

The present paper describes the one-pot procedure for the formation of self-assembled thin films of two silanes on the model oxidized silicon wafer, SiO2/Si. SiO2/Si is a model system for other surfaces, such as glass, quartz, aerosol, and silica gel. MALDI-TOF MS with and without a matrix, XPS, and AFM have confirmed the formation of self-assembled thin films of both 3-imidazolylpropyltrimethoxysilane (3-IPTS) and 4-(N-propyltriethoxysilane-imino)pyridine (4-PTSIP) on the SiO2/Si surface after 30 min. Longer adsorption times lead to the deposition of nonreacted 3-IPTS precursors and the formation of agglomerates on the 3-IPTS monolayer. The formation of 4-PTSIP self-assembled layers on SiO2/Si is also demonstrated. The present results for the flat SiO2/Si surface can lead to a better understanding of the formation of a stationary phase for affinity chromatography as well as transition-metal-supported catalysts on silica and their relationship with surface roughness and ordering. The 3-IPTS and 4-PTSIP modified SiO2/Si wafers can also be envisaged as possible built-on-silicon thin-layer chromatography (TLC) extraction devices for metal determination or N-heterocycle analytes, such as histidine and histamine, with "on-spot" MALDI-TOF MS detection.     

Total attenuated reflection infrared analysis of silicon-stabilized tri-calcium phosphate

Bioceramics based on silicon stabilized tricalcium phosphate [Si-TCP] have been investigated by attenuated total reflection infrared spectroscopy using an experimental preparation that ensures consistent high-quality spectral data. Phase normalized measurements show that changes in OH bands are primarily due to a decrease in the hydroxyapatite content; however, a band at 945 cm(-1) associated with dehydration of the apatite is visible and correlated with silicon doping. Changes in absorption bands with Si content associated with PO(4)(3-) differ for SiO(2) doping levels less than and greater than 0.2 mol of SiO(2)/mol of HA as the amount of Si-TCP phase saturates. Increased resolution allows the study of weak bands linked to Si at 668, 800, 863, and 892 cm(-1) and suggests that the loss of PO(4)(3-) coincides with the development of different silicate groups-SiO(4) at lower doping levels and a new silicon species at higher doping.     

Kinetic studies of atmospherically relevant silicon chemistry. Part III: Reactions of Si+ and SiO+ with O3, and Si+ with O2

Silicon ions are generated in the Earth's upper atmosphere by hyperthermal collisions of material ablated from incoming meteoroids with atmospheric molecules, and from charge transfer of silicon-bearing neutral species with major atmospheric ions. Reported Si(+) number density vs. height profiles show a sharp decrease below 95 km, which has been commonly attributed to the fast reaction with H(2)O. Here we report rate coefficients and branching ratios of the reactions of Si(+) and SiO(+) with O(3), measured using a flow tube with a laser ablation source and detection of ions by quadrupole mass spectrometry. The results obtained are (2σ uncertainty): k(Si(+) + O(3), 298 K) = (6.5 ± 2.1) × 10(-10) cm(3) molecule(-1) s(-1), with three product channels (branching ratios): SiO(+) + O(2) (0.52 ± 0.24), SiO + O(2)(+) (0.48 ± 0.24), and SiO(2)(+) + O (<0.1); k(SiO(+) + O(3), 298 K) = (6 ± 4) × 10(-10) cm(3) molecule(-1) s(-1), where the major products (branching ratio ≥ 0.95) are SiO(2) + O(2)(+). Reactions (1) and (2) therefore have the unusual ability to neutralise silicon directly, as well as forming molecular ions which can undergo dissociative recombination with electrons. These reactions, along with the recently reported reaction between Si(+) and O(2)((1)Δ(g)), largely explain the disappearance of Si(+) below 95 km in the atmosphere, relative to other major meteoric ions such as Fe(+) and Mg(+). The rate coefficient of the Si(+) + O(2) + He reaction was measured to be k(298 K) = (9.0±1.3) × 10(-30) cm(6) molecule(-2) s(-1), in agreement with previous measurements. The SiO(2)(+) species produced from this reaction, which could be vibrationally excited, is observed to charge transfer at a relatively slow rate with O(2), with a rate constant of k(298 K) = (1.5 ± 1.0) × 10(-13) cm(3) molecule(-1) s(-1).     

Sum frequency generation spectroscopic studies on phase transitions of phospholipid monolayers containing poly(ethylene oxide) lipids at the air-water interface

Vibrational sum frequency generation (SFG) spectroscopy was applied to study the phase transitions of the mixed monolayers of l-alpha-distearoyl phosphatidylethanolamine (DSPE) and DSPE covalently coupled with poly(ethylene oxide) at the amino head group (DSPE-EO(45), DSPE with 45 ethylene oxide monomers) at the air-water interface. The SFG spectra were measured for the mixed monolayers with the mole fractions of DSPE-EO(45) of 0, 1.3, 4.5, 9.0, 12.5, and 16.7% at the surface pressures of 5, 15, and 35 mN/m. The monolayer compression isotherms indicated that the mixed monolayers at 5, 15, are 35 mN/m are mainly in the so-called "pancake", "mushroom", and "brush" states, respectively. The SFG spectra in the OH stretching vibration region give rise to SFG bands near 3200 and 3400 cm(-1). The mean molecular amplitude of the former band due to the OH stretching of the "icelike" water molecules associated mainly with the hydrophilic poly(ethylene oxide) (PEO) chains, exhibits appreciable decrease on compression of the mixed monolayers from 5 to 15 mN/m. The result corroborates the model for the pancake-mushroom transition, which presumes the dissolution of the PEO chains from the air-water interface to the water subphase. Further compression of the mixed monolayers to 35 mN/m causes a slight decrease of the line amplitude, which can be explained by considering a squeezing out of water molecules from the hydrophilic groups of DSPE-EO(45) in the brush state, where the PEO chains strongly interact with each other to form a tight binding state of the hydrophilic groups. The relative intensities of the SFG bands due to the CH3 asymmetric and symmetric vibrations were used to estimate the tilt angles of the terminal methyl group of DSPE, indicating that the angle increases with increasing the mole fraction of DSPE-EO(45). The angles almost saturate at the mole fraction larger than 10%, the saturation angle being nearly 90 degrees at 5 mN/m, ca. 60 degrees at 15 mN/m, and ca. 47 degrees at 35 mN/ m. Then, the introduction of the hydrophilic PEO head group causes a large tilting of the alkyl groups of DEPE in the mixed monolayers.     

邻苯二酚作螯合剂合成全硅方钠石(Si-SOD)和全硅ZSM-5(Si-ZSM-5)分子筛大单晶

通过在两个合成分子筛的体系SiO₂-NaOH-EG-R和SiO₂-TPABr-NaOH-H₂O-R(R:邻苯二酚,EG:乙二醇)中加入邻苯二酚获得了具有较大尺寸和完美形貌的分子筛单晶。²⁹SiNMR,IR和UV-Vis光谱表明,在反应混和物中有硅-邻苯二酚螯合物生成,这种硅的螯合物在形成分子筛大单晶过程中起到了缓释硅源的作用。