Wet chemical surface functionalization of oxide-free silicon

Silicon is by far the most important semiconductor material in the microelectronic industry mostly due to the high quality of the Si/SiO₂ interface. Consequently, applications requiring chemical functionalization of Si substrates have focused on molecular grafting of SiO₂ surfaces. Unfortunately, there are practical problems affecting homogeneity and stability of many organic layers grafted on SiO₂, such as silanes and phosphonates, related to polymerization and hydrolysis of Si–O–Si and Si–O–P bonds. These issues have stimulated efforts in grafting functional molecules on oxide-free Si surfaces, mostly with wet chemical processes. This review focuses therefore directly on wet chemical surface functionalization of oxide-free Si surfaces, starting from H-terminated Si surfaces. The main preparation methods of oxide-free H-terminated Si and their stability are first summarized. Functionalization is then classified into indirect substitution of H-termination by functional organic molecules, such as hydrosilylation, and direct substitution by other atoms (e.g. halogens) or small functional groups (e.g. OH, NH₂) that can be used for further reaction. An emphasis is placed on a recently discovered method to produce a nanopattern of functional groups on otherwise oxide-free, H-terminated and atomically flat Si(1 1 1) surfaces. Such model surfaces are particularly interesting because they make it possible to derive fundamental knowledge of surface chemical reactions.     

Optimal surface functionalization of silicon quantum dots

Surface functionalization is a critical step for Si nanocrystals being used as biological probes and sensors. Using density-functional tight-binding calculations, we systematically investigate the optical properties of silicon quantum dots (SiQDs) with various termination groups, including H, CH(3), NH(2), SH, and OH. Our calculations reveal that capping SiQDs with alkyl group (-Si-C-) induces minimal changes in the optical spectra, while covering the surface with NH(2), SH, and OH results in evident changes compared to hydrogenated SiQDs. The structural deformations and electronic property changes due to surface passivation were shown to be responsible for the above-described features. Interestingly, we find that the optical properties of SiQDs can be controlled by varying the S coverage on the surface. This tuning effect may have important implications in device fabrications.     

DNA-binding small-ligand-immobilized surface plasmon resonance biosensor for detecting thymine-related single-nucleotide polymorphisms

A surface plasmon resonance (SPR) biosensor that carries DNA-binding small ligands has been developed for the detection of single-nucleotide polymorphisms (SNPs). 3,5-Diaminopyrazine derivatives, with a hydrogen-bonding profile fully complementary to the thymine base, were utilized as recognition elements on the sensor surface, and a target single-stranded DNA sequence was hybridized with a DNA probe containing an abasic site to place this site opposite a nucleobase to be detected. In a continuous flow of sample solutions buffered to pH 6.4 (0.25 M NaCl), the 3,5-diaminopyrazine-based SPR sensor can detect an orphan nucleobase in the duplex with a clear selectivity for thymine over cytosine, guanine, and adenine (5'-GTT GGA GCT GXG GGC GTA GGC-3'/3'-CAA CCT CGA CNC CCG CAT CCG-5'; X=abasic site, N=target nucleobase G, C, A, or T). The SPR response was linear in the concentration range 10-100 nM. Allele discrimination is possible based on the combination of different binding surfaces in a flow cell of the SPR system, which is demonstrated for the analysis of the thymine/cytosine mutation present in 63-meric polymerase chain reaction (PCR) amplification products (Ha-ras gene, codon 12, antisense strand). Comparison with a bulk assay based on 3,5-diaminopyrazine/DNA binding shows that the immobilization of 3,5-diaminopyrazine derivatives on the SPR sensor allows more sensitive detection of the target DNA sequence, and binding selectivity can be tuned by controlling the salt concentration of sample solutions. These features of the DNA-binding small-molecule-immobilized SPR sensor are discussed as a basis for the design of SPR biosensors for SNP genotyping.     

Improving titanium dioxide dispersion in water through surface functionalization by a dicarboxylic acid

In this work, we show evidence of improving the dispersion of titanium dioxide particles in water. This is observed in the titanium dioxide-water colloid by the shear-thinning flow behavior in rheological measurements induced by the functionalization of a glutaric acid layer on the surface of titanium dioxide particles. The characterization of the layer was achieved by using infrared spectroscopy and ^13?C nuclear magnetic resonance. Rheological measurements corroborated that functionalization of TiO₂ particles decreases the rheological properties such as viscosity measurements at a constant shear rate in two orders of magnitude compared with the pure TiO₂ in suspensions. We present the results as a novel strategy to limit the formation of agglomerates in these colloidal suspensions, and this will be of great use in applications in the paints field and printing technologies.     

Dual silane surface functionalization for the selective attachment of human neuronal cells to porous silicon

Porous silicon (pSi) surfaces were chemically micropatterned through a combination of photolithography and surface silanization reactions. This patterning technique produces discretely defined regions on a pSi surface functionalized with a specific chemical functionality, and the surrounding surface displays a completely different functionality. The generated chemical patterns were characterized by a combination of IR microscopy and the conjugation of two different fluorescent organic dyes. Finally, the chemically patterned pSi surface was used to direct the attachment of neuronal cells to the surface. This patterning strategy will be useful for the development of high-throughput platforms for investigating cell behavior.     

Synthesis, surface functionalization, and properties of freestanding silicon nanocrystals

Freestanding silicon nanoparticles (FS-nc-Si) have intriguing chemical and optical properties. The present contribution outlines known synthetic methodologies and protocols for surface functionalization. Recent advancements in tailoring the photoluminescence properties of FS-nc-Si and future research directions will be briefly discussed.     

Control of Alq3 wetting layer thickness via substrate surface functionalization

The effects of substrate surface energy and vapor deposition rate on the initial growth of porous columnar tris(8-hydroxyquinoline)aluminum (Alq3) nanostructures were investigated. Alq3 nanostructures thermally evaporated onto as-supplied Si substrates bearing an oxide were observed to form a solid wetting layer, likely caused by an interfacial energy mismatch between the substrate and Alq3. Wetting layer thickness control is important for potential optoelectronic applications. A dramatic decrease in wetting layer thickness was achieved by depositing Alq3 onto alkyltrichlorosilane-derivatized Si/oxide substrates. Similar effects were noted with increasing deposition rates. These two effects enable tailoring of the wetting layer thickness.     

Chemical modification of a porous silicon surface induced by nitrogen dioxide adsorption

The effect of gaseous and liquid nitrogen dioxide on the composition and electronic properties of porous silicon (PS) is investigated by means of optical spectroscopy and electron paramagnetic resonance. It is detected that the interaction process is weak and strong forms of chemisorption on the PS surface, and the process may be regarded as an actual chemical reaction between PS and NO(2). It is found that NO(2) adsorption consists in forming different surface nitrogen-containing molecular groups and dangling bonds of Si atoms (P(b)-centers) as well as in oxidizing and hydrating the PS surface. Also observed are the formation of ionic complexes of P(b)-centers with NO(2) molecules and the generation of free charge carriers (holes) in the volume of silicon nanocrystals forming PS.     

Silicon surface modification with a mixed silanes layer to immobilize proteins for biosensor with imaging ellipsometry

One kind of surface modification method on silicon wafer was presented in this paper. A mixed silanes layer was used to modify silicon surface and rendered the surface medium hydrophobic. The mixed silanes layer contained two kinds of compounds, aminopropyltriethoxysilane (APTES) and methyltriethoxysilane (MTES). A few of APTES molecules in the layer was used to immobilize covalently human immunoglobulin G (IgG) on the silicon surface. The human IgG molecules immobilized covalently on the modified surface could retain their structures well and bind more antibody molecules than that on silicon surface modified with only APTES. This kind of surface modification method effectively improved the sensitivity of the biosensor with imaging ellipsometry.     

The role of the organic layer functionalization in the formation of silicon/organic layer/metal junctions with coinage metals

The design of silicon/alkyl layer/metal junctions for the formation of optimal top metal contacts requires knowledge of the mechanistic and energetic aspects of the interactions of metal atoms with the modified surface. This involves (a) the interaction of the metal with the terminal groups of the organic layer, (b) the diffusion of metal atoms through the organic layer and (c) the reactions of metal atoms with the silicon surface atoms. The diffusion through the monolayer and the metal catalyzed breakage of Si-C bonds must be avoided to obtain high quality junctions. In this work, we performed a comprehensive density functional theory investigation to identify the reaction pathways of all these processes. In the absence of a reactive terminal group, gold atoms may penetrate through a compact alkyl monolayer on Si(111) with no energy barrier. However, the presence of thiol terminal groups introduces a high energy barrier which blocks the diffusion of metals into the monolayer. The diffusion barriers increase in the order Ag < Au < Cu and correlate with the stability of metal-thiolate complexes whereas the barriers for the formation of metal silicides increase in the order Cu < Au < Ag in correlation with the increasing metallic radii. The reactivity of gold clusters with functionalized Si(111) surfaces was also investigated. Metal silicide formation can only be avoided by a compact monolayer terminated by a reactive functional group. The mechanistic and energetic picture obtained in this work contributes to understanding of the factors that influence the quality of top metal contacts during the formation of silicon/organic layer/metal junctions.     

Preparation of mesoporous silicon dioxide with high specific surface area

The influence of the reactant ratio on the specific surface area, total pore volume, and mean pore diameter of mesoporous silicon dioxide prepared by the sol-gel method was examined. The optimal reactant ratio for preparing the material with a high specific surface area was determimed.     

Catalyst-free functionalization for versatile modification of nonoxidized silicon structures

Here, we report on a simple, catalyst-free route for obtaining highly versatile subsequent functionalization on Si nanowires and Si(111) substrates. The versatility of this approach allows subsequent functionalization not only for organic species but also for inorganic (nanomaterial) species. The method has the advantage of controlling the density of reactive cross-linkers without affecting the stability of the Si samples and without having metallic (or catalyst) residues on the surface. This method also allows formation of monolayers with a variety of termination groups and is expected to open up a wide range of opportunities for producing stable molecule-based (opto)electronic and (bio)sensing devices. Immobilization of inorganic nanomaterial on the Si samples offers advanced opportunities in molecular switches, (bio)sensors, molecular scale memory, and Si-based nanoelectronic devices.     

Enzyme-encapsulated silica monolayers for rapid functionalization of a gold surface

We report a simple and rapid method for the deposition of amorphous silica onto a gold surface. The method is based on the ability of lysozyme to mediate the formation of silica nanoparticles. A monolayer of lysozyme is deposited via non-specific binding to gold. The lysozyme then mediates the self-assembled formation of a silica monolayer. The silica formation described herein occurs on a surface plasmon resonance (SPR) gold surface and is characterized by SPR spectroscopy. The silica layer significantly increases the surface area compared to the gold substrate and is directly compatible with a detection system. The maximum surface concentration of lysozyme was found to be a monolayer of 2.6 ng/mm(2) which allowed the deposition of a silica layer of a further 2 ng/mm(2). For additional surface functionalization, the silica was also demonstrated to be a suitable matrix for immobilization of biomolecules. The encapsulation of organophosphate hydrolase (OPH) was demonstrated as a model system. The silica forms at ambient conditions in a reaction that allows the encapsulation of enzymes directly during silica formation. OPH was successfully encapsulated within the silica particles and a detection limit for the substrate, paraoxon, using the surface-encapsulated enzyme was found to be 20 microM.     

Chemically modified silicon dioxide surfaces Reaction of n-alkyldimethylsilanols and n-oxaalkyldimethylsilanols with the hydrated surface of silicon dioxide — the question of the limiting surface concentration

Firstly, a model is proposed for the surface of highly dispersed silicon dioxides (Aerosil, Cabosil). In the first part, the investigation of the uncatalysed reaction of the surface hydroxyls on Cabosil with alkyl and oxa-alkyldimethylsilanols is described. The reaction mechanism is discussed on the basis of kinetic measurements. The reaction attains a limiting surface concentration of 3.1 μmol m⁻² of alkyldimethylsiloxy groups, a value which is independent of the chain length of the non-branched alkyl substituent, as well as of the reaction temperature between 200 and 340°C. By repeating the reaction, the surface concentration can be further increased. However, the limiting value attained after about three repeated treatments at 300°C depends on the chain length of the alkyl substituent, 4.0 μmol m⁻² for trimethylsiloxy groups and 3.5 for the other alkyldimethylsiloxy groups with longer alkyl or oxa-alkyl substituents. An interpretation of the results is proposed in the light of the suggested model.     

A study of phase transformations in the surface layer of titanium dioxide

The capabilities of the diffuse reflectance spectroscopy in a study of the state of the surface layer of anatase in anatase-rutile phase transformations in successive thermal treatments of anatase in the temperature range 200–900°C and in analysis of titanium dioxide of P25 brand (Degussa) containing anatase and rutile in a 80: 20 ratio, respectively, are demonstrated for the example of dispersed titanium oxide.     

Photoelectron spectroscopy studies of the functionalization of a silicon surface with a phosphorylcholine-terminated polymer grafted onto (3-aminopropyl)trimethoxysilane

The structure of a biomimetic phosphorylcholine (PC)-functionalized poly(trimethylene carbonate) (PC-PTMC-PC), linked to a silicon substrate through an aminolysis reaction at 120 degrees C with (3-aminopropyl)trimethoxysilane (APTMS), was studied using photoelectron spectroscopy. Two chemical states were found for the unreacted APTMS amine, a neutral state and a protonated state, where the protonated amine on average was situated closer to the silicon substrate than the neutral amine. The experiments also indicated the presence of a third chemical state, where amines interact with unreacted silanol groups. The PTMC chains of the grafted films were found to consist of only 2-3 repeat units, with the grafted chains enriched in the zwitterionic end group, suggesting that these groups are attracted to the surface. This was further supported by the experiments showing that the PC groups were situated deeper within the film.     

A surface plasmon resonance biosensor for detecting Pseudomonas aeruginosa cells with self-assembled chitosan-alginate multilayers

A self-assembled multilayer (SAMu) including the alginate layer was prepared for detecting Pseudomonas aeruginosa cells in a solution and its potential was evaluated with a BIAcore system. After layer-by-layer formation, the refractive units (RU) values monitored with the biosensor increased by the interaction between the layers. The responses by the binding of P. aeruginosa cells to the alginate-immobilized SAMu were visualized immediately upon injection of the cell suspension. The RU values after injection of the cells were measured with approximately 1152, 656 and 173 for 1 × 10⁹, 1 × 10⁸ and 1 × 10⁷ CFU/ml. This result suggests that the alginate-immobilized SAMu will have useful application for detecting P. aeruginosa cells in a biosensor analysis.     

Thermochemistry of hydride and phenyl groups on the surface of amorphous silicon dioxide

The thermodynamic properties of hydride and phenyl groups on the surface of amorphous silicon dioxide are investigated in the presented work. The characteristics of the surface silane centers (SiH) are determined from the data obtained by infrared spectroscopy and caloric measurements. The conversions of hydrogen and benzene with the surface are described by thermodynamic calculations at reactions take place in the gaseous phase.To model the reaction between hydrogen and the surface the thermodynamic data for (OH)_4−nSi_n (n=0-4) in the gaseous phase are used. The surface groups and the model molecules are comparable because the thermodynamic characteristics depend only from the local environment.The thermodynamic properties of (OH)₃SiC₆H₅ in the gaseous phase are determined to describe the reaction between benzene and the surface. The predications of these calculations are confirmed by the spectroscopic results. The properties of the surface phenyl groups (SiC₆H₅) are concluded from these data.     

Mass-sensitive micro- and nanosensors for detecting the vapors of explosives and associated substances

The main analytical characteristics of mass-sensitive micro- and nanosensors for detecting the vapors of explosives and associated substances are compared. The limits of detection, sensitivity, sensor setting time (response speed) and recovery time after the action of an analyte, and the selectivity of cantilever sensors, quartz crystal microbalances, surface acoustic wave sensors, and flexural plate wave sensors are considered. The effectiveness of the use of the nanosized structures of mass-sensitive sensors, and bio- and nanostructured specific coatings is analyzed.