Controlled assembly of DNA nanostructures on silanized silicon and mica surfaces for future molecular devices

In order to establish key technology for future molecular devices, we have explored the assembly behaviour of λ-deoxyribonucleic acid (DNA) molecules adsorbed on silanized mica and silanized oxide silicon surfaces by using atomic force microscopy (AFM). AFM experiments show that λ-DNA molecules can be hardly adsorbed on untreated mica and oxidized silicon surfaces, but can be strongly adsorbed onto aminosilanized mica and oxidized silicon surfaces. Importantly, DNA molecules can be assembled into linear DNA alignment, and can also self-assemble into various network structures on the silanized surfaces. Our experimental observations have demonstrated the feasibility of assembling DNA-based nanostructures by varying surface chemistry of substrates, and offer useful clues in constructing DNA-based nanodevices for nanoelectronics and biomolecular computation as well as quantum computation.     

Wide temperature range operation of micrometer-scale silicon electro-optic modulators

We demonstrate high bit rate electro-optic modulation in a resonant micrometer-scale silicon modulator over an ambient temperature range of 15 K. We show that low bit error rates can be achieved by varying the bias current through the device to thermally counteract the ambient temperature changes. Robustness in the presence of thermal variations can enable a wide variety of applications for dense on chip electronic photonic integration.     

Resonant electronic energy transfer from excitons confined in silicon nanocrystals to oxygen molecules

We demonstrate efficient resonant energy transfer from excitons confined in silicon nanocrystals to molecular oxygen (MO). Quenching of photoluminescence (PL) of silicon nanocrystals by MO physisorbed on their surface is found to be most efficient when the energy of excitons coincides with triplet-singlet splitting energy of oxygen molecules. The dependence of PL quenching efficiency on nanocrystal surface termination is consistent with short-range resonant electron exchange mechanism of energy transfer. A highly developed surface of silicon nanocrystal assemblies and a long radiative lifetime of excitons are favorable for achieving a high efficiency of this process.     

Au标蛋白自组装表面增强拉曼光谱的研究

采用免疫Au标技术,用尺寸大约在13 nm的Au胶体颗粒标记了人血清蛋白(Human IgG),然后将Au标蛋白复合体固定在通过三氨基三乙氧基硅烷和戊二醛自组装单膜的Si片上。这种方法在基底表面上不仅牢固地固定了单层Au纳米颗粒标记的蛋白分子复合体而且提高了复合体的表面覆盖度,保持了生物分子的结构。利用原子力显微镜(AFM)观察了Au标蛋白的自组装表面。实验结果表明Au标蛋白在Si片表面聚积形成一定的Au标蛋白分子的复合体“岛状”单层,并且在这些岛状单层上获得了很明显的标记蛋白的表面增强拉曼散射(SERS)信号。文章在Si表面自组装了Au标蛋白分子,获得了较好的蛋白分子的SERS信号,提供了一种研究蛋白分子的SERS活性基底。     

Formation of dicarboxylic acid-terminated monolayers on silicon wafer surface

Dicarboxylic acid-terminated monolayers on hydroxylated silicon wafer were prepared via the chemisorption of 3-glycidoxypropyldimethylethoxysilane (GPDMES) molecules and subsequent reaction of the epoxy groups with iminodiacetic acid (IDA). The structure and surface composition of the monolayers were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, reflectance FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Moreover, we found that the dicarboxylic acid-terminated monolayers on silicon wafer exhibit well-defined contact angle titration curve from which the surface acid dissociation constants were determined. The results were compared with the pK_a values reported in the literature for IDA in aqueous solution. Small difference in the surface pK_a values was attributed to variations of the microenvironment of the acid moieties. These experimental findings provide fundamental knowledge at the molecular level for the preparation of bioactive surfaces of controlled reactivity on silicon substrates.     

Enhanced broadband light absorption in silicon film by large-size lumpy silver particles

Broadband light absorption enhancement in crystalline silicon thin-film solar cells by rear-located 400 nm lumpy silver particles has been studied, based on the theoretical simulations of 3D finite-difference time-domain method. By simulations, we have investigated the light scattering properties of 400 nm lumpy Ag particles and put it to silicon thin-film solar cells. In addition, the varying rear-located Ag particles coverage and two surface situations of silicon films, which could influence on the light absorption of solar devices, have also been comprehensively considered. The results have shown that rear-located 400 nm lumpy Ag particles would enhance the absorption in silicon films in a broadband range. And it has been proved that 20 % coverage density of rear-located Ag particles is optimal for improving the light absorption of smooth silicon thin-film solar devices. When we create rough surface on one or both sides of silicon films, the absorbed light would further increase, and the theoretical maximum enhancement is 15.1 % compared with the smooth silicon thin-film solar cell without Ag particles.     

Enhanced instability in thin liquid films by improved compatibility

We investigated experimentally the morphological evolution of thin polydimethylsiloxane films sandwiched between a silicon wafer and different bounding liquids with interfacial tensions varying by 2 orders of magnitude. It is shown that increasing the compatibility between film and bounding liquid by adding a few surfactant molecules results in a faster instability of shorter characteristic wavelength. Inversely, based on the characteristic parameters describing the instability we determined extremely small interfacial tensions with a remarkable accuracy.     

STM characterisation of organic molecules on H-terminated Si(111)

We present the first high resolution STM images of organic molecules on the technological important hydrogen terminated silicon surface. Ordered layers of PTCDA and PTCDI were prepared on this surface by organic molecular beam epitaxy. The submolecular contrast of these molecules on Si(111)/H obtained in the high resolution images agrees with the corresponding images on HOPG and MoS₂ substrates.     

The special features of adsorption and the kinetics of decomposition of monosilane molecules on the epitaxial surface of silicon

Analytic equations relating the rate of the incorporation of silicon atoms into a growing crystal to the characteristic frequency of the pyrolysis of silane molecules on the surface of silicon were obtained over the temperature range corresponding to the epitaxial growth of silicon films. As distinct from the earlier works, it was assumed that adsorbed silicon atoms and monosilane molecules formed double bonds with the surface. The data of technological experiments for the most extensively used pyrolysis models obtained thus far were used to determine the region of the characteristic frequencies of the decomposition of hydride molecule radicals adsorbed on the surface of a silicon plate over the temperature range 450–700°C. The temperature dependence of the frequency of monosilane molecule decomposition was shown to be to a great extent determined by the form of the temperature dependence of the $ \tilde v_{SiH_2 }^0 $ \tilde v_{SiH_2 }^0 preexponential factor. It was also found that the characteristic frequency of the decomposition of silane molecules was sensitive to the stage of pyrolysis at which hydrogen atoms released from silane molecules were captured by the surface. Decomposition occurred at the highest rate if hydrogen molecules were adsorbed at the stage of the adsorption of monosilane. The lowest rate of decomposition was observed if hydrogen molecules were adsorbed at the stage of the decomposition of radicals already captured by the surface. The temperature dependence of the coefficient of adsorption of monosilane molecules was characterized by a negative activation energy of the process for almost all the most important system models over the temperature range of growth. At elevated growth temperatures, the adsorption of monosilane molecules by the surface of silicon proceeded via an intermediate state characterized by the difference of desorption and chemisorption energies on the order of 0.28 eV.     

Influence of successive electron and laser irradiation on the photoluminescence of porous silicon

The influence of electron irradiation on the light-emitting properties of p-and n-type porous silicon prepared by electrochemical etching is investigated. The dose and energy dependences of the electron-stimulated quenching of the photoluminescence (PL) are determined. It is shown that electron treatment of a porous silicon surface followed by prolonged storage in air can be used to stabilize the PL. The excitation of photoluminescence by a UV laser acting on sections of porous silicon samples subjected to preliminary electron treatment is discovered for the first time. The influence of the electron energy and the power of the laser beam on this process is investigated. The results presented are attributed to variation in the number of radiative recombination centers as a result of the dissociation and restoration of hydrogen-containing groups on the pore surface. Zh. Tekh. Fiz. 68, 58–63 (March 1998)     

Surface characterization of porous silicon after pore opening processes inducing chemical modifications

In this paper, we present a study on the porous silicon surface with the aim of filling porous silicon layers with organics. We discuss on two processes used to remove the outer parasitic layer created during the porous silicon formation. We demonstrate that these etching processes influences the surface properties, in particular wetting ability. By XPS and infrared absorption spectroscopy studies, we show that a SF₆ plasma treatment does not modify irreversibly the chemistry of porous silicon surface, nor the surface morphology. We also point out that NaOH etching does bring significant morphological modifications and influences the hydrophilicity of the porous silicon surface. This last treatment increases the polar groups (SiO) concentration on the pore surface and therefore allows a better filling of a porous silicon layer with organics, like dibromo-EDOT which can be thermally converted into PEDOT.     

Relations between electronic properties of clean surfaces and activated adsorption

Surface reconstruction and steps alter the electron affinity and ionization potential of surfaces by a few tenth of an eV. In an simple potential model these variations are related to the changes in the activation energy for chemisorption. Without introducing fitted parameters the model describes semiquantitatively the influence of surface re-construction, step density and doping on the oxygen sticking coefficient on silicon and gallium arsenide. Possible applications of the model to stepped metal surfaces and to the influence of steps on catalysis in general are discussed as well.     

Anchoring of alkyl chain molecules on oxide surface using silicon alkoxide

Chemical states of the interfaces between octadecyl-triethoxy-silane (ODTS) molecules and sapphire surface were measured by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) using synchrotron soft X-rays. The nearly self-assembled monolayer of ODTS was formed on the sapphire surface. For XPS and NEXAFS measurements, it was elucidated that the chemical bond between silicon alkoxide in ODTS and the surface was formed, and the alkane chain of ODTS locates upper side on the surface. As a result, it was elucidated that the silicon alkoxide is a good anchor for the immobilization of organic molecules on oxides.     

Effects of wettability and interfacial nanobubbles on flow through structured nanochannels: an investigation of molecular dynamics

Solid–fluid boundary conditions are strongly influenced by a number of factors, including the intrinsic properties of the solid/fluid materials, surface roughness, wettability, and the presence of interfacial nanobubbles (INBs). The interconnected nature of these factors means that they should be considered jointly. This paper employs molecular dynamics (MD) simulation in a series of studies aimed at elucidating the influence of wettability in boundary behaviour and the accumulation of interfacial gas. Specifically, we examined the relationship between effective slip length, the morphology of nanobubbles, and wettability. Two methods were employed for the promotion of hydrophobicity between two structured substrates with similar intrinsic contact angles. We also compared anisotropic and isotropic atomic arrangements in the form of graphite and Si(100), respectively. A physical method was employed to deal with variations in surface roughness, whereas a chemical method was used to adjust the wall–fluid interaction energy (?_wf). We first compared the characteristic properties of wettability, including contact angle and fluid density within the cavity. We then investigated the means by which variations in solid–fluid interfacial wettability affect interfacial gas molecules. Our results reveal that the morphology of INB on a patterned substrate is determined by wettability as well as the methods employed for the promotion of hydrophobicity. The present study also illustrates the means by which the multiple effects of the atomic arrangement of solids, surface roughness, wettability and INB influence effective slip length.     

Self-assembled and electrochemically deposited mono/multilayers for molecular electronics applications

For the development of molecular electronics, it is desirable to investigate characteristics of organic molecules with electronic device functionalities. In near future, such molecular devices could be integrated with silicon to prepare hybrid nanoelectronic devices. In this paper, we review work done in our laboratory on study of characteristics of some functional molecules. For these studies molecular mono and multilayers have been deposited on silicon surface by self-assembly and electrochemical deposition techniques. Both commercially available and specially designed and synthesized molecules have been utilized for these investigations. We demonstrate dielectric layers, memory, switching, rectifier and negative differential resistance devices based on molecular mono and multilayers.     

Tuning the geometry of shape-restricted DNA molecules on the functionalized Si(1 1 1)

Designing a well-defined and stable interface between biomolecules and semiconductor surfaces is of great importance for current and future biosensing and bioelectronic applications. The well-characterized chemistry, stability, and easily tunable electronic properties of silicon substrate make it a practical platform for this type of interface. It has been established in our previous work that a robust, covalent attachment between thiol-DNA molecules of a pre-designed geometrical shape and a modified silicon surface can be achieved. This work focuses on using this binding model and altering the distance between the DNA molecules and silicon surface by strategically placing thiol linkers within the pre-determined geometric design of the rectangularly shaped DNA. The statistical analysis of the height profiles of DNA molecules attached to the surface, as determined by AFM, provides specific insight into how the construction of the DNA molecules affects the binding distance. A comparison between two thiol-DNA molecules with different numbers of thiol groups placed either within the rectangular shape or anchored to the free loop of the same geometric design suggest that the average distance of these molecules to the functionalized silicon surface can be changed by approximately 0.5 nm.     

Reversible photomechanical switching of individual engineered molecules at a metallic surface

We have observed reversible light-induced mechanical switching for individual organic molecules bound to a metal surface. Scanning tunneling microscopy (STM) was used to image the features of individual azobenzene molecules on Au(111) before and after reversibly cycling their mechanical structure between trans and cis states using light. Azobenzene molecules were engineered to increase their surface photomechanical activity by attaching varying numbers of tert-butyl (TB) ligands ("legs") to the azobenzene phenyl rings. STM images show that increasing the number of TB legs "lifts" the azobenzene molecules from the substrate, thereby increasing molecular photomechanical activity by decreasing molecule-surface coupling.     

Coadsorption of silicon and chalcogen (S, O) atoms on heated Re(10\bar 10) substrate

The coadsorption of silicon and Group VI elements on the Re $(10\bar 10)$ surface is investigated by the 1 high-resolution Auger spectroscopy. It is demonstrated that, upon deposition of silicon on the surface oxide or surface sulfide, a part of silicon atoms deposited interacts with chalcogen atoms to be desorbed in the form of SiO or SiS molecules. The rest of silicon atoms occupy the becoming free adsorption sites, thus forming surface silicide. The silicon atoms incorporated into the surface silicide loose their reactivity and coexist on the surface together with adsorbed chalcogen atoms.     

Kinetics of the decomposition of disilane molecules on a silicon growth surface in vacuum chemical epitaxy

In the framework of the kinetic approach based on data of technological experiments, the range of characteristic rates of decomposition of disilane radical molecules adsorbed on the surface during the growth of a silicon layer is determined. The relationship between the rate of incorporation of silicon atoms into a growing crystal and the characteristic rate of pyrolysis of hydride molecules on the growing surface is established. The temperature dependences of the decomposition rate of disilane molecules exhibit an unusual activationless behavior in the growth temperature range. The form of the observed dependences is determined by the pyrolysis model, conditions of transferred of hydrogen from an adsorbed molecule onto the surface of the growing layer, being a function of the gas pressure and temperature in the reactor. It is demonstrated that the basic features of the behavior of the decomposition rate of disilane molecules are controlled by the specifics of the interaction of the silicon dihydride molecular beam with the growth surface under conditions of low and high degrees of bonding of hydrogen to free surface bonds. The temperature dependences are qualitatively described by a relation composed of two activation curves with different activation energies at low and high temperatures and preexponential factors depending on the surface coverage by hydrogen atoms.     

Organization of cyanobiphenyl liquid crystal molecules in prewetting films spreading on silicon wafers

We observe prewetting films of 8CB (4'-n-octyl-4-cyanobiphenyl) spreading at room temperature on silicon wafers by ellipsometry and x-ray reflectivity. Ellipsometry indicates the formation of a nondense monolayer spreading in front of a 45-A-thick film. X-ray reflectivity, performed using a ribbon geometry for the liquid crystal (LC) reservoir, allows us to determine the organization of the 8CB molecules in the homogenous film. It consists of a trilayer stacking with a smecticlike bilayer standing above a polar monolayer with tilted molecules. We show that the thickness of the bilayer is equal to the smectic periodicity in the bulk material and that the tilt angle of the molecules in contact with the solid surface is close to 60 degrees, in good agreement with second-harmonic generation studies reported by other groups. Such organization can be precisely determined using x-ray reflectivity because it induces a modulation of the electron density along the normal to the surface. Furthermore, a study of the ellispometric profile of a drop heated in the nematic phase, where we observe a complete spreading of the LC, shows the complex structuration of the LC close to the solid interface. In particular, the spreading behavior of the trilayer compared to the subsequent smecticlike bilayers indicates the existence of specific interaction between the trilayer and silicon wafer.