Deposition of Aerosol Nanoparticles on Flat Substrate Surfaces

The deposition process in a homogeneous electric field, and the subsequent microscopic arrangement of charged, metallic aerosol nanoparticles in the size range of 30 nm on flat substrate surfaces is described. The first aspect of the investigation is the transfer of the particles from a three-dimensional distribution in the gas phase into their arrangement on the substrate surface, in dependence on particle-particle interactions and on Brownian motion. The theoretical results obtained with a trajectory model are compared with experimental results obtained by scanning electron microscope investigation of the deposition patterns. The second aspect of the investigation is the nanostructured arrangement of nanoparticles by means of inhomogeneous electric microfields. We demonstrate a parallel process for the transfer of charge patterns on oxidized silicon surfaces followed by the deposition of monodisperse singly charged nanoparticles, which allows the creation of particle arrangements reaching from 100 nm resolution up to structures in the upper micrometer range. The charge patterns are transferred using a polydimethylsiloxane (PDMS)-stamp, which is covered with a metal layer.     

Nanostructured Deposition of Nanoparticles from the Gas Phase

For many applications, nanoparticles from the gas phase are of interest due to their physical properties. Especially for electronic or optoelectronic applications, the transfer from their random distribution in the gas phase onto flat substrate surfaces has to be controlled because the particles are needed in exactly defined areas on the substrate. We demonstrate a parallel process for the transfer of charge patterns on oxidized silicon surfaces followed by the deposition of monodisperse singly charged nanoparticles, which allows the creation of particle arrangements reaching from 100 nm resolution up to structures in the upper micrometer range. The charge patterns are transferred using a polydimethylsiloxane (PDMS) stamp, which is covered with a metal layer. By applying different voltages to the stamp, negative or positive charges can be transferred. Thus, nanoparticles of different polarities can be guided to certain places.     

The surface cracking behavior in air plasma sprayed thermal barrier coating system incorporating interface roughness effect

The objective of this work is to understand the effect of interface roughness on the strain energy release rate and surface cracking behavior in air plasma sprayed thermal barrier coating system. This is achieved by a parameter investigation of the interfacial shapes, in which the extended finite element method (XFEM) and periodic boundary condition are used. Predictions for the stress field and driving force of multiple surface cracks in the film/substrate system are presented. It is seen that the interface roughness has significant effects on the strain energy release rate, the interfacial stress distribution, and the crack propagation patterns. One can see the completely different distributions of stress and strain energy release rate in the regions of convex and concave asperities of the substrate. Variation of the interface asperity is responsible for the oscillatory characteristics of strain energy release rate, which can cause the local arrest of surface cracks. It is concluded that artificially created rough interface can enhance the durability of film/substrate system with multiple cracks.     

Tribological behavior of micro/nano-patterned surfaces in contact with AFM colloidal probe

In effort to investigate the influence of the micro/nano-patterning or surface texturing on the nanotribological properties of patterned surfaces, the patterned polydimethylsiloxane (PDMS) surfaces with pillars were fabricated by replica molding technique. The surface morphologies of patterned PDMS surfaces with varying pillar sizes and spacing between pillars were characterized by atomic force microscope (AFM) and scanning electron microscope (SEM). The AFM/FFM was used to acquire the friction force images of micro/nano-patterned surfaces using a colloidal probe. A difference in friction force produced a contrast on the friction force images when the colloidal probe slid over different regions of the patterned polymer surfaces. The average friction force of patterned surface was related to the spacing between the pillars and their size. It decreased with the decreasing of spacing between the pillars and the increasing of pillar size. A reduction in friction force was attributed to the reduced area of contact between patterned surface and colloidal probe. Additionally, the average friction force increased with increasing applied load and sliding velocity.     

柔性基周期性厚度梯度薄膜的应变效应

可控的表面微结构在柔性电子、仿生器件和能源材料等方面均具有重要的应用价值.本文采用编织铜网作为掩模板,利用磁控溅射技术在柔性聚二甲基硅氧烷(PDMS)基底上制备具有周期分布的厚度梯度金属银薄膜,研究了薄膜在单轴压缩/拉伸过程中的形貌演化规律.实验发现,在单轴机械载荷作用下,银薄膜表面将形成相互垂直的条纹褶皱和多重裂纹.膜厚的梯度变化调制了薄膜的面内应力分布,导致褶皱在膜厚较小处率先形成,并逐渐扩展到膜厚较大区域,而裂纹则基本限定在膜厚较小区域.基于应力理论和有限元计算,对周期性厚度梯度薄膜的褶皱和裂纹的形貌特征、演化行为和物理机制进行了深入分析.该研究将有助于加深对非均匀薄膜体系的应变效应的理解,并有望通过梯度薄膜的结构设计在柔性电子等领域获得应用.     

Effect of periodic surface cracks on the interfacial fracture of thermal barrier coating system

Periodic surface cracks and interfacial debonding in thermal barrier coating (TBC) system may be induced during cooling process. The objective of this work is to investigate the effect of periodic surface cracks on the interfacial fracture of TBC system. The finite element method (FEM) incorporating cohesive zone model is used in analysis. It is found that surface crack spacing has significant effect on the initiation and propagation of short interface crack. Three different regions are identified for describing the effect of surface crack spacing. In Region I the interface crack driving force is dramatically reduced due to high surface crack density. In this case, the initiation of interfacial delamination can be delayed. Region II applies as the surface crack spacing is moderate. Analysis of this transition zone brings to the definition of normalized critical surface crack spacing. Region III arises for sufficient large surface crack spacing. In this case, the interface crack driving force reaches a steady state, where the effects of adjacent surface cracks are relatively insignificant and can be ignored. It can be concluded that an appropriately high surface crack density can enhance the durability of TBC system.     

The interaction and the surface crack of single-crystal silicon induced by a millisecond laser

When the silicon material is irradiated by laser, it absorbs the laser energy leading to the temperature rise and the thermal stress. The damage effect includes melting, vaporation and thermal stress damage. Once the thermal stress exceeds the stress strength the crack will initiate. The silicon surface cracks induced by a millisecond laser are investigated. The experimental results show that three types of cracks are generated including cleavage crack, radial crack and circumferential crack. The cleavage crack is located within the laser spot. The radial crack and circumferential crack are located outside the laser spot. A two-dimensional spatial axisymmetric model of silicon irradiated by a 1064 nm millisecond laser is established. To assess what stresses generate and explain the generation mechanism of the different cracks, the thermal stress fields during laser irradiation and the cooling process are obtained using finite element method. The radial stress and hoop stress within the laser spot are tensile stress after the laser irradiation. The temperature in the center is the highest but the thermal stress in the center is not always highest during the laser irradiation. The cleavage cracks are induced by the tensile stress after the laser irradiation. The radial crack and the circumferential crack are generated during the laser irradiation.     

Effect of micro-dimple patterns on capillary pull-off force and friction force of silicon surface

A microtribometer is used to measure and compare pull-off forces and friction forces exerted on (a) micro-dimpled silicon surfaces, (b) bare silicon surfaces, and (c) octadecyltrichlorosilane (OTS) treated silicon surfaces at different relative humidity (RH) levels separately. It is found that above a critical RH level, the capillary pull-off force increases abruptly and that the micro-dimple textured surface has a lower critical RH value as well as a higher pull-off force value than the other two surfaces. A micro topography parameter, namely sidewall area ratio, is found to play a major role in controlling the capillary pull-off force. Furthermore, micro-dimpled silicon surface is also proved to be not sensitive to variation in RH level, and can realize a stable and decreased friction coefficient compared with un-textured silicon surfaces. The reservoir-like function of micro dimples is considered to weaken or avoid the breakage effect of liquid bridges at different RH levels, thereby maintaining a stable frictional behaviour.     

Towards a statistical theory of solid dry friction

Wearless dry friction of an elastic block of weight N, driven by an external force F over a rigid substrate, is investigated. The slider and substrate surfaces are both microscopically rough, interacting via a repulsive potential that depends on the local overlap. The model reproduces Amontons’s laws which state that the friction force is proportional to the normal loading force N and independent of the nominal surface area. In this model, the dynamic friction force decays for large velocities and approaches a finite static friction for small velocities if the surface profiles are self-affine on small length scales.     

Sub-15 femtosecond laser-induced nanostructures emerging on Si(100) surfaces immersed in water: analysis of structural phases

Nanoscale periodic rifts and subwavelength ripples as well as randomly nanoporous surface structures were generated on Si(100) surfaces immersed in water by tightly focused high-repetition rate sub-15 femtosecond sub-nanojoule pulsed Ti:sapphire laser light. Subsequent to laser processing, silicon oxide nanoparticles, which originated from a reaction of ablated silicon with water and aggregated on the exposed areas, were etched off by hydrofluoric acid. The structural phases of the three types of silicon nanostructures were investigated by transmission electron microscopy diffraction images recorded on focused ion beam sections. On nanorift patterns, which were produced at radiant exposure extremely close to the ablation threshold, only the ideal Si-I phase at its original bulk orientation was observed. Electron diffraction micrographs of periodic ripples, which were generated at slightly higher radiant exposure, revealed a compression of Si-I in the vertical direction by 6 %, which is attributed to recoil pressure acting during ablation. However, transitions to the high-pressure phase Si-II, which implies compression in the same direction at pressures in excess of 10 GPa, to the metastable phases Si-III or Si-IV that arise from Si-II on pressure relief or to other high-pressure phases (Si-V–Si-XII) were not observed. The nanoporous surfaces featured Si-I material with grains of resolidified silicon occurring at lattice orientations different from the bulk. Characteristic orientational relationships as well as small-angle grain boundaries reflected the rapid crystal growth on the substrate.     

Tribological behaviors of self-assembled 3-aminopropyltriethoxysilane films on silicon

3-Aminopropyltriethoxysilane (APTES) thin films were prepared on the hydroxylated silicon substrate by a self-assembling process from formulated solution. Chemical compositions of the films were detected by X-ray photoelectron spectrometry (XPS). The thickness of the films was determined with an ellipsometer, while the morphologies of the original and worn surfaces of the samples were analyzed by means of atomic force microscopy (AFM) and scanning electron microscopy (SEM), respectively. The tribological properties of APTES thin films sliding against GCr15 steel ball were evaluated on a UMT-2MT reciprocating friction and wear tester. It was found that the macroscopic friction coefficients for coating times more than 1 h ranged from 0.177 to 0.3 whereas the value for short coating time was as high as 0.8. It was also found that the tribological behaviors of APTES films were sensitive to normal load and sliding velocity. SEM observation of the morphologies of worn surfaces indicates that the wear of silicon is characteristic of brittle fracture and severe abrasion. Differently, abrasion and micro-crack dominate the wear of APTES–SAM. The superior friction reduction and wear resistance of APTES films compared to the silicon substrate are attributed to good adhesion of the films to the substrate.     

Hydrophobic surfaces of spin-assisted layer-by-layer assembled polyelectrolyte multilayers doped with copper nanoparticles and modified by fluoroalkylsilane

Polyelectrolyte multilayers (PEMs) fabricated by spin-assisted layer-by-layer assembly technique were used as nanoreactors for in situ synthesis of Cu nanoparticles, allowing generation of Cu nanoparticles doped composite, denoted as Cu-nanoparticles PEMs. Thus chemical reaction within the PEMs was initiated by a series of reaction cycles in which Cu²⁺ was absorbed into the polymer-coated silicon substrate and reduced in NaBH₄ solution. The surface of Cu-nanoparticles PEMs was modified by heptadecafluorodecyl-trimethoxysilane (FAS-17) with low surface energy, generating a hydrophobic film. The adhesion and nano-friction behavior of the hydrophobic film was investigated using an atomic force microscope, while its macro-tribological behavior sliding against stainless steel under dry- and distilled-water-lubricated conditions was investigated using a UMT-2 test rig. It was found that Cu-nanoparticles PEMs modified with FAS-17 has a lower friction and higher adhesion than that without modification. Moreover, the hydrophobic film possesses lower friction coefficient under water-lubrication and higher friction coefficient under dry-sliding than the hydrophilic film under the same conditions, which could be mainly due to the difference in the surface energy. The titled hydrophobic films with low adhesion and friction would have potential application in micro/nano-electro-mechanical systems.     

Field induced radial crack patterns in drying laponite gel

We present a study of crack patterns in a layer of laponite gel allowed to dry in a static electric field. Crack patterns in natural and synthetic clays have been studied extensively with interesting results. Since clay platelets have a surface charge in aqueous solution, it is natural to expect the cracking patterns to be affected by an electric field. This is the first report of such an observation in a radial electric field. The nano-sized disc-like laponite particles carry a quadrupole moment due to their charge distribution. The interaction of the quadrupole moment with the field gradient in a non-uniform field of radial symmetry is probably responsible for the characteristic pattern observed. The cracks start radially from the positive electrode. The same geometry with no field does not produce the characteristic pattern, neither does a uniform field with rectangular geometry.     

Periodic overlayers and moiré patterns: theoretical studies of geometric properties

Single crystal surfaces with periodic overlayers, such as graphene on hexagonal metal substrates, are found to exhibit, apart from their intrinsic periodicity, additional long-range order expressed by approximate surface lattices with large lattice constants. This phenomenon can be described as geometrically analogous to lateral interference effects resulting in periodic moiré patterns which are characterized by two-dimensional moiré lattices. Here we discuss in detail the mathematical formalism determining such moiré patterns based on concepts of two-dimensional Fourier transformation including coincidence lattices. The formalism provides simple relations that allow one to calculate possible moiré lattice vectors in their dependence on rotation angles α and scaling factors p1,p2 for periodic (p1 × p2)Rα overlayers on substrate surfaces described by general Bravais lattices. Specific emphasis will be given to hexagonal lattices where experimental data are available.     

Stamping plasmonic nanoarrays on SERS‐supporting platforms

The dielectric property of a nanoparticle‐supporting film has recently garnered attention in the fabrication of plasmonic surfaces. A few studies have shown that the localized surface plasmon resonance (LSPR), and hence surface‐enhanced Raman scattering (SERS), strongly depends on the substrate refractive index. In order to create higher efficiency SERS‐active surfaces, it is therefore necessary to consider the substrate property along with nanoparticle morphology. However, due to certain limitations of conventional lithography, it is often not feasible to create well‐defined plasmonic nanoarrays on a substrate of interest. Here, an additive nanofabrication technique, i.e., nanotransfer printing (nTP), is implemented to integrate electron beam lithography (EBL) defined high‐aspect‐ratio nanofeatures on a variety of SERS‐supporting surfaces. With the aid of suitable surface chemistries, a wide range of plasmonic particles were successfully integrated on surfaces of three physically and chemically distinct dielectric materials, namely, polydimethyl siloxane (PDMS), SU‐8 photoresist, and glass surfaces, using silicon‐based relief pillars. These nTP‐created metal nanoparticles strongly amplify the Raman signal and complement the selection of suitable substrates for better SERS enhancement. Our experimental observations are also supported by theoretical calculations. The implementation of nTP to stamp out metal nanoparticles on a multitude conventional/unconventional substrates has novel applications in designing in‐built plasmonic microanalytical devices for SERS sensing and other related photonic studies. Copyright © 2011 John Wiley & Sons, Ltd.     

两种纳米粒子的自组装及表面增强拉曼光谱研究

在氨基硅烷化的单晶硅片表面通过静电自组装技术组装上金和金核铂壳两种纳米粒子,通过改变基底浸泡在溶胶中的时间控制基底上纳米粒子的密度。用扫描电子显微镜(SEM)对基底表面上的形貌进行表征,结果表明纳米粒子呈亚单层二维阵列分布。以吡啶(Py)为探针分子,用波长为632.8 nm的激发光作为激发光源,研究纯金和金铂复合基底上的表面增强拉曼光谱(SERS)行为。数据显示在金纳米粒子之间引入金核铂壳纳米粒子后,Py的两个特征峰的频率没有明显变化,但谱峰的强度却变弱了,其SERS信号衰减最大可至原来的24%。这是由于引入的铂的d态电子使金的等离子体激发猝灭,从而破坏了电磁场增强,使金的SERS信号衰减。     

Periodic cracks and temperature-dependent stress in Mo/Si multilayers on Si substrates

This work examines formation of the peculiar periodic crack patterns observed in the thermally loaded Mo/Si multilayers. Using the substrate curvature measurements, the macroscopic film stress evolution during thermal cycling was investigated. Then high-speed microscopic observation of crack propagation in the annealed Mo/Si multilayers was presented providing experimental evidence of the mechanism underlying formation of the periodic crack patterns. The origin of the peculiar periodic crack patterns was determined. They were observed to form by the slow crack propagation under quasi-static conditions as a result of the interaction between the channelling crack propagation and the advance of the delamination front.     

Two-dimensional nanopatterning by PDMS relief structures of polymeric colloidal crystals

A new constructive method of fabricating a nanoparticle self-assembly on the patterned surface of a poly(dimethylsiloxane) (PDMS) relief nanostructure was demonstrated. Patterned PDMS templates with close-packed microwells were fabricated by molding against a self-assembled monolayer of polystyrene spheres. Alkanethiol-functionalized gold nanoparticles with an average particle size of 2.5 nm were selectively deposited onto a hydrophobic self-assembled monolayer printed on the substrate by the micro-contact printing (μCP) of the prepared PDMS microwell, in which the patterned gold nanoparticles consisted of close-packed hexagons with an average diameter of 370 nm. In addition, two-dimensional colloidal crystals derived from PMMA microspheres with a diameter of 380 nm and a negative surface charge were successfully formed on the hemispherical microwells by electrostatic force using positively charged PAH-coated PDMS as a template to produce multidimensional nanostructures.     

Field emission properties of a-C and a-C:H films deposited on silicon surfaces modified with nickel nanoparticles

The a-C and a-C:H films are deposited on silicon surfaces modified with and without nickel nanoparticles by using mid-frequency magnetron sputtering. The microstructures and morphologies of the films are analyzed by Raman spectroscopy and atomic force microscopy. Field emission behaviors of the deposited films with and without nickel nanoparticles modification are comparatively investigated. It is found that the hydrogen-free carbon film exhibits a high field emission current density and low turn-on electric field compared with the hydrogenated carbon film. Nickel modifying could increase the current density, whereas it has no significant effect on the turn-on electric field. The mechanism of field electron emission of a sample is discussed from the surface morphologies of the films and nickel nanoparticle roles in the interface between film and substrate.     

Patterning and modification of PDMS surface through laser micromachining of silicon masters and molding

We describe preparation of micro patterned PDMS sample surfaces and their chemical modification for the purposes of increased hydrophobicity. The process includes ablation of micrometer sized patterns on a silicon master by pulsed radiation from a Nd:YAG laser, transfer of the patterns to PDMS through molding, and chemical modification of the topmost surface layers of the polymer sample by further laser irradiation and UV/ozone treatment. The samples were characterized by XPS, FTIR, contact angle measurements, optical microscopy and SEM. The study shows the feasibility of the method to manufacture regular patterns with micron-sized cylindrical pillars and to control surface composition. In the absence of chemical modification of the surfaces due to preparation, we compare the effect of increased roughness on the contact angle with theoretically predicted values. Samples with patterned and chemically modified surfaces due to UV/ozone treatment show reduced hydrophobicity. PACS 52.38.Mf; 81.65.Cf; 81.05.Lg