Probing the viscoelastic response of glassy polymer films using atomic force microscopy

The mechanical properties of glassy films and glass surfaces have been studied using an atomic force microscope (AFM) through various imaging modes and measuring methods. In this paper, we discuss the viscoelastic response of a glassy surface probed using an AFM. We analyzed the force-distance curves measured on a glassy film or a glassy surface at temperatures near the glass transition temperature, Tg, using a Burgers model. We found that the material's characteristics of reversible anelastic response and viscous creep can be extracted from a force-distance curve. Anelastic response shifts the repulsive force-distance curve while viscous creep strongly affects the slope of the repulsive force-distance curve. When coupled with capillary force, due to the condensation of a thin layer of liquid film at the tip-surface joint, the anelasticity and viscous creep can alter the curve significantly in the attractive region.     

Nonsolvents cause swelling at the interface with poly(methyl methacrylate) films

Density profiles of a perdeuterated poly(methyl methacrylate) (dPMMA) film spin-coated on a substrate in water, hexane, and methanol, which are "nonsolvents" for dPMMA, were examined along the direction normal to the interface by specular neutron reflectivity (NR). The interfaces of dPMMA with the liquids were diffuse in comparison with the pristine interface with air; the interfacial width with water was thicker than that with hexane. Interestingly, in water, the dPMMA film was composed of a swollen layer and the interior region, which also contained water, in addition to the diffused layer. The interface of dPMMA with hexane was sharper than that with water. Although there were slight indications of a swollen layer for the dPMMA in hexane, the solvent molecules did not penetrate significantly into the film. On the other hand, in methanol, the whole region of the dPMMA film was strikingly swollen. To conserve mass, the swelling of the film by the nonsolvents is accompanied by an increase in the film thickness. The change in the film thickness estimated by NR was in excellent accord with the results of direct observations using atomic force microscopy (AFM). The modulus of dPMMA in the vicinity of the interfaces with liquids was also examined on the basis of force-distance curves measured by AFM. The modulus decreased closer to the outermost region of the film. The extent to which the modulus decreased in the interfacial region was consistent with the amount of liquid sorbed into the film.     

A chemo-mechanical tweezer for single-molecular characterization of soft materials

A new atomic force microscopy (AFM)-based chemo-mechanical tweezer has been developed that can measure mechanical properties of individual macromolecules in supramolecular assembly and reveal positions of azide-containing polymers. A key feature of the new technology is the use of an AFM tip densely modified with 4-dibenzocyclooctynols (chemo-mechanical tweezer) that can react with multiple azide containing macromolecules of micelles to give triazole "clicked" compounds, which during retracting phases of AFM imaging are removed from the macromolecular assembly thereby providing a surface topographical image and positions of azide-containing polymers. The force-distance curves gave mechanical properties of removal of individual molecules from a supramolecular assembly. The new chemo-mechanical tweezer will make it possible to characterize molecular details of macromolecular assemblies thereby offering new avenues to tailor properties of such assemblies.     

基底界面效应对聚苯乙烯薄膜分子运动行为的影响

本文研究了Si／Si02、Si／Si—H基底与聚苯乙烯（Ps）之间的界面相互作用对Ps薄膜的玻璃化转变及相关力学性能的影响．结果显示,无论何种基底,Ps薄膜的玻璃化转变温度（L）都随其厚度降低而降低．但相同厚度（〈110nm）下,以Si／Si-H为基底时Ps薄膜的瓦比以Si／Si02为基底的PS薄膜高．Si／Si02表面Ps薄膜疋开始下降的临界厚度为110nm,远高于以Si／Si—H为基底时的40nm．对Ps薄膜的膨胀系数和弹性模量进行研究,也得到相似的临界厚度．另外,与Si／Si02基底相比,在Si／Si-H上的Ps薄膜具有更低的膨胀系数以及较高弹性模量．可能原因是Si／Si-H与Ps具有较强的相互作用,限制了该界面分子的运动能力,导致基底／PS界面效应对薄膜分子运动的影响力增强,造成该薄膜瓦的厚度依赖性下降,并呈现出相对较硬的力学特征．     

Analyzing refractive index profiles of confined fluids by interferometry part II: Multilayer and asymmetric systems

Methods for determining the substrate properties and the optical thickness of thin films or any variation in the refractive index of a fluid or film near a surface for unknown 5-layer symmetric and 3-layer asymmetric interferometers are presented. Both systems can be fully resolved without any known layer properties and without contact or confining the films. The method was tested using realistic simulated interferometer data, and was found to consistently yield accurate values for all desired properties. The method was experimentally validated through analysis of an asymmetric three layer interferometer system of linear polyethyleneimine (LPEI) adsorbed onto mica substrates of differing thickness and identical refractive index. The results were in excellent agreement with the dry polymer film properties measured using conventional SFA contact measurements. More complicated systems were also evaluated for feasibility, and any additional parameter specifications required for analysis were determined. The utility of this method is broad, as a single experiment in a laboratory setting can independently provide non-contact film properties and the effects of confinement on the film structure, which can be correlated to a simultaneously measured interaction force profile.     

Simultaneous measurement of mechanical and surface properties in thermoresponsive, anchored hydrogel films

Hydrogel films have been used extensively in the preparation of biosensors and biomedical devices. The characteristics of the aqueous interface of the polymer layer are significant for the biosensor or device function; likewise, the changing mechanical properties of thermoresponsive polymers are an important feature that affects the polymer behavior. Atomic force microscopy was used here to characterize both the surface and the mechanical properties of polymeric hydrogel films prepared from a thermoresponsive terpolymer of N-isopropylacrylamide and acrylic acid with benzophenonemethacrylate as a photoreactive cross-linker comonomer. The force-distance curves thus obtained were analyzed to assess both the surface forces and the mechanical response that were associated with the hydrogel. These properties were investigated as a function of temperature, in water and in Tris buffer, for different degrees of polymer cross-linking. For samples in water, the distance over which the surface forces were effective was found to remain constant as the temperature was increased from 26 to 42 °C, even though the mechanical response indicated that the samples had been heated past the lower critical solution temperature, or LCST. The bulk of the polymer becomes less soluble above the LCST, although this does not seem to affect the surface properties. This may be due to the segregation of the acrylic acid-rich polymer segments near the gel surface, which is in agreement with reports for related systems.     

计算机硬盘基片CMP中表面膜特性的分析研究

目前,普遍采用化学机械抛光(Chemical-mechanical polishing,CMP)技术对计算机硬盘基片(盘片)表面进行原子级平整。CMP加工中,盘片表面膜及其特性对CMP过程及CMP性能具有关键作用。本文分别采用俄歇能谱(AES)、X射线光电子能谱(XPS)、扫描电镜(SEM)、纳米硬度计、电化学极化法等分析手段对盘片表面物理、化学及机械特性进行了研究,发现盘片CMP后表面发生了氧化,氧化膜在盘片的表层,厚度在纳米量级,氧化产物为Ni(OH)₂;氧化膜为较软的、疏松的、粗糙的多孔结构;氧化膜的存在加快了盘片表面的腐蚀磨损。结合盘片CMP试验结果,推测盘片的CMP机理为盘片表面氧化生成机械强度较低的Ni(OH)₂氧化膜及随后氧化膜的机械和化学去除,二者的不断循环实现表面的全局平面化。     

Surface chemical and mechanical properties of plasma-polymerized N-isopropylacrylamide

Surface-immobilized poly(N-isopropyl acrylamide) (pNIPAM) is currently used for a wide variety of biosensor and biomaterial applications. A thorough characterization of the surface properties of pNIPAM thin films will benefit those applications. In this work, we present analysis of a plasma-polymerized NIPAM (ppNIPAM) coating by multiple surface analytical techniques, including time-of-flight secondary-ion mass spectrometry (ToF-SIMS), contact angle measurement, atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. ToF-SIMS data show that the plasma-deposited NIPAM polymer on the substrate is cross-linked with a good retention of the monomer integrity. Contact angle results confirm the thermoresponsive nature of the film as observed by a change of surface wettability as a function of temperature. Topographic and force-distance curve measurements by AFM further demonstrate that the grafted film shrinks or swells depending on the temperature of the aqueous environment. A clear transition of the elastic modulus is observed at 31-32 degrees C. The change of the surface wettability and mechanical properties vs temperature are attributed to different conformations taken by the polymer, which is reflected on the outmost surface as distinct side chain groups orienting outward at different temperatures as measured by SFG. The results suggest that a ppNIPAM thin film on a substrate experiences similar mechanical and chemical changes to pNIPAM bulk polymers in solution. The SFG result provides evidence supporting the current theory of the lower critical solution temperature (LCST) behavior of pNIPAM.     

NANOMECHANICAL MAPPING OF CARBON BLACK REINFORCED NATURAL RUBBER BY ATOMIC FORCE MICROSCOPY

Atomic force microscopy （AFM） has the advantage of obtaining mechanical properties as well as topographic information at the same time. By analyzing force-distance curves measured over two-dimensional area using Hertzian contact mechanics, Young＇s modulus mapping was obtained with nanometer-scale resolution. Furthermore, the sample deformation by the force exerted was also estimated from the force-distance curve analyses. We could thus reconstruct a real topographic image by incorporating apparent topographic image with deformation image. We applied this method to carbon black reinforced natural rubber to obtain Young＇s modulus distribution image together with reconstructed real topographic image. Then we were able to recognize three regions; rubber matrix, carbon black （or bound rubber） and intermediate regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first to report on the quantitative evaluation of the interfacial region in real space.     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.     

Ag/TCNQ双层膜传质规律与模型的理论研究

有机分子结构的多样性以及独特的光学、电学和磁学性质已引起了人们的高度重视,功能有机薄膜的深入研究已有报道,这些研究大多涉及金属／有机复合薄膜,因此研究金属／有机物双层膜间的传质过程已成为一个重要的科研课题,这对特殊结构膜的制备、可控纳米结构的实现、膜结构的稳定性及薄膜的应用与失效分析具有重要的科学与实际意义。     

Temperature dependent nano indentation of thin polymer films with the scanning force microscope

The scanning force microscope (SFM) was used to investigate the temperature dependent micro mechanical properties of polymethylmethacrylate (PMMA) films with a thickness of 35 nm in the range of the radius of gyration. Force-distance curves were performed in the glass transition range to create permanent nanometric indentations with maximal forces up to 4 μN. Quantitative measurements of the indentation depth during and after application of the force, hysteresis energy and slope of the loading part are carried out as function of sample temperature and applied force. The glass transition of the polymer film can be clearly identified by the change of the mechanical properties of the polymer. Surprisingly, only a small change of elasticity at the glass transition is observed.     

Effect of surface roughness and softness on water capillary adhesion in apolar media

The roughness and softness of interacting surfaces are both important parameters affecting the capillary condensation of water in apolar media, yet are poorly understood at present. We studied the water capillary adhesion between a cellulose surface and a silica colloidal probe in hexane by AFM force measurements. Nanomechanical measurements show that the Young's modulus of the cellulose layer in water is significantly less (~7 MPa) than in hexane (~7 GPa). In addition, the cellulose surface in both water and hexane is rather rough (6-10 nm) and the silica probe has a comparable roughness. The adhesion force between cellulose and silica in water-saturated hexane shows a time-dependent increase up to a waiting time of 200 s and is much (2 orders of magnitude) lower than that expected for a capillary bridge spanning the whole silica probe surface. This suggests the formation of one or more smaller bridges between asperities on both surfaces, which is confirmed by a theoretical analysis. The overall growth rate of the condensate cannot be explained from diffusion mediated capillary condensation alone; thin film flow due to the presence of a wetting layer of water at both the surfaces seems to be the dominant contribution. The logarithmic time dependence of the force can also be explained from the model of the formation of multiple capillary bridges with a distribution of activation times. Finally, the force-distance curves upon retraction show oscillations. Capillary condensation between an atomically smooth mica surface and the silica particle show less significant oscillations and the adhesion force is independent of waiting time. The oscillations in the force-distance curves between cellulose and silica may stem from multiple bridge formation between the asperities present on both surfaces. The softness of the cellulose surface can bring in additional complexities during retraction of the silica particle, also resulting in oscillations in the force-distance curves.     

Voltammetry at the mercury film electrodes: Comparison of theoretical and experimental results obtained for indium in thiocyanate medium

The voltammetric behaviour of the In(III)-In(Hg) system was studied at the silver-, graphite-, and glassy carbon-based mercury film electrodes under cyclic and stripping conditions in thiocyanate media. The reversible curves obtained at high thiocyanate ion concentration showed a good agreement with theoretical predictions, particularly for the cathodic process. The anodic curves obtained at thin silver-based mercury film electrodes deviated from theoretical predictions due to the interactions between indium, dissolved in mercury, and the silver substrate of the film electrode. At low thiocyanate ion concentrations, where the current was controlled partly by the rate of the preceding chemical step and partly by diffusion, the variations in the film thickness affected the position of the curve as predicted theoretically for the reversible diffusion controlled case.     

Electrochemical impedance spectroscopy of polybithiophene films in an aqueous LiClO4 solution

Polybithiophene (PBT) films (oxidized form), electrochemically deposited on Pt from an aqueous anionic micellar medium, were characterized by EIS measurements in 0.3 M aqueous LiClO₄ at different applied potentials. The EIS data were fitted with an equivalent electrical circuit in order to characterize the PBT electrochemical properties. Our experimental results show that both the double-layer and the film capacitances as well as the charge-transfer resistance decreased with the film thickness, while the diffusive capacitance and the charge-transfer and the pore resistance increased. Increasing the applied potential enhances the double-layer and film capacitances and the charge-transfer and pore resistances, but reduces the diffusive capacitance (with a minimum around the open-circuit potential) and the film resistance.     

Direct measurement of hydrophobic particle–bubble interactions in aqueous solutions by atomic force microscopy: Effect of particle hydrophobicity

Direct measurements of the interaction forces between a spherical silica particle and a small air bubble have been conducted in aqueous electrolyte solutions by using an atomic force microscope (AFM). The silica particle was hydrophobized with a silanating reagent, and the interaction forces were measured by using several particles with different surface hydrophobicities. In the measured force curves, a repulsive force was observed at large separation distances as the particle moved towards the bubble. The origin of the repulsive force was attributed to an electrostatic double-layer force because both the particle and bubble were negatively charged. After the repulsive force, an extremely long-range attractive force acted between the surfaces. These results indicate that the intervening thin water film between the particle and bubble rapidly collapsed, resulting in the particle penetrating the bubble.

The instability of the thin water film between the surfaces suggests the existence of an additional attractive force. By comparing the repulsive forces of the obtained force curves with the DLVO theory, the rupture thickness was estimated. The hydrophobicity of the particle did not significantly change the rupture thickness, whereas the pH of the solution is considered to be a critical factor.     

Instabilities and pattern miniaturization in confined and free elastic-viscous bilayers

We present an analysis of the instabilities engendered by van der Waals forces in bilayer systems composed of a soft elastic film (<10 microm) and a thin (<100 nm) viscous liquid film. We consider two configurations of such systems: (a) Confined bilayers, where the bilayer is sandwiched between two rigid substrates, and (b) free bilayers, where the viscous film is sandwiched between a rigid substrate and the elastic film. Linear stability analysis shows that the time and length scales of the instabilities can be tuned over a very wide range by changing the film thickness and the material properties such as shear modulus, surface tension, and viscosity. In particular, very short wavelengths comparable to the film thickness can be obtained in bilayers, which is in contrast to the instability wavelengths in single viscous and elastic films. It is also shown that the instabilities at the interfaces of the free bilayers are initiated via an in-phase "bending" mode rather than out-of-phase "squeezing" mode. The amplitudes of deformations at both the elastic-air and elastic-viscous interfaces become more similar as the elastic film thickness decreases and its modulus increases. These findings may have potential applications in the self-organized patterning of soft materials.     

Contact instability of thin elastic films on patterned substrates

The free surface of a soft elastic film becomes unstable and forms an isotropic labyrinth pattern when a rigid flat plate is brought into adhesive contact with the film. These patterns have a characteristic wavelength, lambda approximately 3H, where H is the film thickness. We show that these random structures can be ordered, modulated, and aligned by depositing the elastic film (cross-linked polydimethylsiloxane) on a patterned substrate and by bringing the free surface of the film in increasing adhesive contact with a flat stamp. Interestingly, the influence of the substrate "bleeds" through the film to its free surface. It becomes possible to generate complex two-dimensional ordered structures such as an array of femtoliter beakers even by using a simple one-dimensional stripe patterned substrate when the instability wavelength, lambda approximately 3H, nearly matches the substrate pattern periodicity. The free surface morphology is modulated in situ by merely varying the stamp-surface separation distance. The free surface structures originating from the elastic contact instability can also be made permanent by the UV-ozone induced oxidation and stiffening.     

Preparation and tribological studies of C60 thin film chemisorbed on a functional polymer surface

A novel self-assembled C60 film was prepared by chemical adsorption of C60 molecules onto an amino-group-containing polyethyleneimine-coated silicon substrate surface. The contact angle of distilled water on the C60 film was measured, the thickness was determined by means of ellipsometric analysis, and the morphology was observed with an atomic force microscope. The tribological properties of the films were investigated as well. It was found that the C60 thin film had a contact angle of about 72 degrees and thickness of 1.8 nm and exhibited a surface domain microstructure composed of fullerene clusters. Due to the hydrophobicity and low surface energy, the C60 film possessed good adhesive resistance and had an adhesive force of about 7.1 nN, which was about an order of magnitude lower than that of the silicon substrate surface. Moreover, the C60 film showed good friction reduction, load-carrying capacity, and antiwear ability, which were attributed to the higher mechanical stiffness and elastic modulus of C60 molecules. Besides, the friction coefficient decreased with increasing sliding velocity and normal loads, due to the rolling effect of the physisorbed C60 molecules.     

Performance and limitations of electron probe microanalysis applied to the characterization of coatings and layered structures

Electron probe microanalysis (EPMA) at low electron energies (typically 3-10 keV) has been used to study the composition of coatings with a film thickness of 0.1-1.3 microm ("bulk" analysis). The accuracy of quantification, including the most critical situation of low atomic number elements (boron-oxygen), is about 5% relative by use of pure element or arbitrary compound standards. A special procedure of data processing ("thin film" analysis) enables the simultaneous determination of film thickness and composition, provided that the substrate is known. The film thickness may be in the range of 2 nm to 5 microm. EPMA can be also applied in the mode of "non-destructive in-depth analysis", which is based on the combined evaluation of experiments at different electron energies. The quantitative characterization of layered structures and implantation zones is demonstrated.