The Beneficial Effect of High-Temperature Oxidation on the Tribological Behaviour of V and VN Coatings

This paper investigates the influence of the applied load and sliding velocity on the microfrictional properties of native oxide-covered Si(100) and Si(100) coated with octadecyltrichlorosilane (OTS) and perfluorodecyltrichlorosilane (FDTS) self-assembled monolayers (SAMs) using a precision microtribometer. Microfriction was investigated as a function of the applied load and sliding velocity. As has been confirmed in earlier studies, in the microtribological regime, OTS and FDTS significantly reduce the friction force in comparison to the bare native oxide-covered (hydrophilic) silicon surface. The friction versus applied load curve of the substrate material as well as the SAMs-covered surfaces can be described by a model based on contact mechanics. For the native oxide surface, microfriction is reduced with increasing sliding speed. The friction force of the OTS- and FDTS-covered surfaces increases with load and is proportional to the natural logarithm of sliding speed. The increase with sliding velocity gets larger for higher normal loads. It can be shown that this increase is proportional to the contact area of the counter sample with the SAMs.     

Microtribology of silicon,oxide, and carbide surfaces

This paper presents an overview of the microtribological properties of silicon oxide, sapphire, and titanium carbide surfaces as well as a self‐assembled monolayer with respect to their application in microsystems. Testing was performed with a reciprocating microtribometer with normal loads in the micronewton to millinewton range. Silicon and titanium carbide balls were used as counterbodies. For silicon oxide, sapphire and a perfluorodecyltrichlorosilane self‐assembled monolayer (FDTS), the microfriction corresponds to the water contact angle when the smoother titanium carbide ball or the relatively rougher silicon ball was used as a counterbody. Microfriction measurements performed on tribopairs of the same material, but having different roughnesses, showed that the friction of the rougher tribopairs is lower than that of the smoother ones. Interestingly, in the microforce regime, reduction in friction was significant and almost as much as when hydrophobic self‐assembled monolayers are applied on smooth surfaces. This investigation showed that comparative microtribological investigations between different material systems can be very challenging due to the fact that comparable roughness values on samples and countersamples are difficult to realize. Copyright © 2006 John Wiley & Sons, Ltd.     

Friction and fracture properties of polysilicon coated with self-assembled monolayers

The increasing use of small micromechanical devices and advanced sensors has led to concern about the failure modes and reliability of these structures. The enormous promise will not materialize without substantial progress in overcoming the stiction, friction and wear associated with such devices and understanding the mechanical behavior of MEMS materials and structures. Self-assembled monolayers (SAMs) are release and anti-stiction coatings for MEMS. In this paper, the anti-stiction properties of octadecyltrichlorosilane (OTS) SAM were calculated. The microtribological properties of OTS SAM were investigated with a ball-on-flat microtribometer. The influence of OTS SAM on the mechanical properties of micromachined polysilicon films for MEMS was investigated with an accurate evaluation using the microtensile test device. It was concluded that the OTS SAM has good anti-stiction properties and low friction coefficients. The hydrophobic property of OTS is the main factor leading to an increase in the average fracture strength of micromachined polysilicon up to 32.46%. Thus, the operational stability and lifetime of MEMS can be raised when coated with self-assembled monolayers.     

环境湿度下硅材料表面的粘滑行为及其抑制

通过自行开发的微摩擦测试仪,分别研究了小载荷湿度环境下光洁硅片、物理形貌修饰表面和OTS膜修饰表面的微摩擦行为。实验结果表明,OTS膜表面和凹坑形貌修饰表面在高湿度环境下可以有效地抑制粘滑现象的发生。通过对湿度环境下液桥作用机制的研究,初步认为摩擦力来自于工作间隙的固固、固液和液液3个接触面间相互作用,并且高湿度下是否出现粘滑现象取决于这3种界面间力的竞争关系。     

Multi-asperity Nanotribology of Self-Assembled Monolayers Grafted on Silicon Wafers Displaying Various Crystallographic Orientations and Nanostructures

Micro/nanotribological study of self-assembled monolayers (SAMs) derived from n-alkyltrichlorosilanes deposited on silicon wafers displaying various crystallographic orientations—Si (100), Si (111) and Si (110)—has been conducted using a ball-on-disc nanotribometer. The parameters that have been varied are (i) the alkyl chain length, (ii) the tribological parameters (i.e. the normal load, the sliding velocity, the sliding distance and the relative humidity level) and (iii) some surface characteristics of the silicon substrates (i.e. crystallographic orientation, roughness, and thickness of the amorphous native oxide). Experimental results show that the key parameter controlling the tribological behaviour is not the alkyl chain length as generally reported for adsorbed and grafted monolayers, but rather the film’s homogeneity—i.e. the degree of packing and the surface coverage of the monolayer—in connection with the crystallographic orientation of the substrate.     

Dynamic variations in adhesion of self-assembled monolayers on nanoasperities probed by atomic force microscopy

Octadecyltriethoxysilane (OTE) self- assembled monolayers (SAMs) and their effects on friction and adhesion have been investigated on various combinations of functionalized and unfunctionalized silicon oxide surfaces including the oxidized surface of crystalline Si(100), silica nanoparticle films, and oxidized Si atomic force microscopy (AFM) tips. Force-distance spectroscopy was utilized to probe and compare the properties of the OTE SAMs on silica asperities with nanoscale curvature against these same monolayers on surfaces with sub-1 nm roughness (flat surfaces). It was found that adhesion between SAMs and silicon oxide surfaces can vary significantly when assembly takes place on surfaces with nanoscopic curvature as compared to flat surfaces. Observations indicate that the SAM structure present during force measurements is dynamic in nature, which yields different adhesion values when measured with variations of both tip-sample contact time and tip-approach/retract rates. These results point the need in reporting a number of measurement parameters when probing adhesion by SAM functionalized tips.     

Self-assembled monolayer protective films for hybrid sliding contacts

Abstract

Silicon nitride as an energy efficient material is replacing conventional steels for new generation engineering components such as bearings, cutting tools, electronics and engine parts in automotive, aerospace and wind industries. Compared with steel bearings, silicon nitride bearings can be operated at much higher temperatures and speeds with >60% weight reduction and up to 80% friction reduction. These are all due to its unique material properties, including high wear and corrosion resistance, low density and heat generation. Current lubrication solutions for hybrid contacts, where silicon nitride balls and steel races are used, are mostly relying on the protection film formed on the metal surfaces. Self-assembled monolayers (SAMs) have been found very useful in modifying surfaces, especially for microelectromechanical system and nanoscale applications, e.g. atomic force microscopy tips, etc. This study aims to investigate the feasibility of forming a SAM protection film on industrial grade bearing material silicon nitride to reduce the friction for the oil lubricated hybrid contacts. Four silanes with different functional head groups, including octadecyltrichlorosilane (OTS), octyltrichlorosilane, chlorodimethyloctadecylsilane and octadecyltrimethoxysilane, were initially investigated to form SAMs on industrial grade silicon nitride surfaces. The effects of concentration and immersion time of the silanes on the formation of SAMs on the silicon nitride surface were evaluated using contact angle measurements. The preliminary results show that the wetting properties of the silicon nitride surface can be effectively modified by the formation of SAMs from the silane solutions. OTS can form an order and compact SAM on the silicon nitride surfaces within 2 min at the concentration of 2··5 mM in decane solution, while the other three alkylsilanes can also effectively modify silicon nitride surfaces given sufficient immersion time, e.g. over 1 h. Tribological tests were subsequently carried out on a ball on disc rig where a steel ball and a silicon nitride disc were used. The effect of the formation of alkylsilane SAMs on the friction between the sliding contacts has been evaluated in two different methods. The first method was to test preformed SAM films under dry conditions, and the second was to premix one of the surfactants with Shell Vitrea ISO 32 mineral base oil and then spray the mixture to the contacts during the ball on disc testing. The test results show that an average of over 40 and 30% friction reduction was achieved for the hybrid contact when lubricated with the base oil mixed with OTS (>2··5 mM) and octadecyltrimethoxysilane (5 mM) respectively compared with that of the sliding contact lubricated by the base oil only. Since OTS may produce corrosive byproducts during SAM formation, octadecyltrimethoxysilane may be a more suitable additive for the hybrid contacts.     

全氟羧酸自组装分子润滑膜的纳米摩擦学性能的研究

采用气相沉积的方法在铝表面制备了不同碳链长度的全氟羧酸自组装膜。考察了全氟羧酸自组装膜的接触角、膜厚、粘着和微摩擦等表面性质。对相对湿度和温度等环境因素对全氟羧酸自组装膜的纳米摩擦学性能的影响进行了研究。探讨了在环境因素影响下的减摩抗粘着机制。结果表明:自组装膜具有显著的抗粘着效果;随着相对湿度的增加,针尖与样品的粘着力增加,随着温度的增加,针尖与样品粘着力降低,并趋于稳定值;全氟羧酸自组装单层膜能显著降低表面的摩擦力,起到良好的减摩效果,且随烷基链越长,减摩效果越好。     

Frictional dynamics of perfluorinated self-assembled monolayers on amorphous SiO<Subscript>2</Subscript>

Silicon micromachines in microelectromechanical systems (MEMS) are coated with self-assembled monolayers (SAMs) in order to reduce the wear and stiction that are commonplace during operation. Recently, perfluorinated SAMs have been the focus of attention because they have better processing properties than hydrocarbon SAMs. In this study, we perform molecular dynamics simulations that model adhesive contact and friction for perfluorinated alkylsilane (Si(OH)₃(CF₂)₁₀CF₃) self-assembled monolayers (SAMs), which are commonly used in MEMS devices. Amorphous silica is used as the substrate for the SAMs in the simulations. The frictional behavior is investigated as a function of applied pressure (50 MPa–1 GPa) for a shear velocity of 2 m/s and compared to recent simulation results of hydrocarbon alkylsilane SAMs. The microscopic friction coefficient for the perfluorinated SAMs is the same as was measured for the hydrocarbon SAMs, but the shear stress is slightly larger than in the case of the hydrocarbon SAMs on amorphous silica.     

Tribology of silicon-thin-film-coated SiC ceramics and the effects of high energy ion irradiation

The sliding friction coefficients and specific wear of SiC ceramics coated with a silicon thin film (Si/SiC) with and without subsequent Ar⁺ irradiation against a diamond pin were measured with a pin-on-disk tester at room temperature in laboratory air of approximately 50% relative humidity without oil lubrication for 40 h. The friction coefficient of Ar⁺-irradiated Si/SiC was about 0.05 with a normal load of 9.8 N and remained almost unchanged during the 40 h test, while that of SiC increased from 0.04 to 0.12 during the test. The silicon deposition also reduced the specific wear of SiC to less than one tenth of that of the uncoated SiC. Effectively no wear was detected in Si/SiC irradiated to doses of over2×10¹⁶ions cm⁻².     

Friction mechanisms of Silicon wafer and Silicon wafer coated with diamond-like carbon film and two monolayers

The friction behaviour of Si-wafer, diamond-like carbon (DLC) and two self-assembled monolayers (SAMs) namely dimethyldichlorosilane (DMDC) and diphenyl-dichlorosilane (DPDC) coated on Si-wafer was studied under loading conditions in milli-newton (mN) range. Experiments were performed using a ball-on-flat type reciprocating micro-tribo tester. Glass balls with various radii 0.25 mm, 0.5 mm and 1 mm were used. The applied normal load was in the range of 1.5 mN to 4.8 mN. Results showed that the friction increased with the applied normal load in the case of all the test materials. It was also observed that friction was affected by the ball size. Friction increased with the increase in the ball size in the case of Si-wafer. The SAMs also showed a similar trend, but had lower values of friction than those of Si-wafer. Interestingly, for DLC it was observed that friction decreased with the increase in the ball size. This distinct difference in the behavior of friction in DLC was attributed to the difference in the operating mechanism. It was observed that Si-wafer and DLC exhibited wear, whereas wear was absent in the SAMs. Observations showed that solid-solid adhesion was dominant in Si-wafer, while plowing in DLC. The wear in these two materials significantly influenced their friction. In the case of SAMs their friction behaviour was largely influenced by the nature of their molecular chains.     

Tribological Properties of Self-Assembled Monolayers and Their Substrates Under Various Humid Environments

Using friction force microscopy (FFM) under controlled environments, we have systematically investigated the humidity effect on the frictional properties of two important classes of self-assembled monolayers (SAMs), i.e., N-octadecyltrimethoxysilane (OTE, CH₃(CH₂)₁₇Si(OCH₃)₃) on SiO₂(OTE/SiO₂), and N-alkanethiols on Au(111), together with their respective substrates. Experimental results show that both OTE and alkylthiol SAMs can decrease the friction force between a Si₃N₄ atomic force microscope (AFM) tip and substrates. The nearly humidity-independent friction of the two kinds of SAMs indicates that these SAMs are ideal lubricants in applications of micro-electro-mechanical systems (MEMS) under different environments. The humidity dependence—as the humidity increases, the friction first increases and then decreases—of the two substrates, SiO₂ and Au(111), can be explained by the adsorption of water. The decrease in the friction at high humidity is attributed to the low viscosity in the multilayers of water, while the increase in the friction at low humidity can be explained by the high viscosity between the water monolayer and the surfaces (AFM tip and sample), possibly due to the confinement effects. The effect of modification of the AFM tip with alkanethiol molecules on the humidity dependence of Au(111) friction has also been investigated.     

Nanofriction Mechanisms Derived from the Dependence of Friction on Load and Sliding Velocity from Air to UHV on Hydrophilic Silicon

This paper examines friction as a function of the sliding velocity and applied normal load from air to UHV in a scanning force microscope (SFM) experiment in which a sharp silicon tip slides against a flat Si(100) sample. Under ambient conditions, both surfaces are covered by a native oxide, which is hydrophilic. During pump-down in the vacuum chamber housing the SFM, the behavior of friction as a function of the applied normal load and the sliding velocity undergoes a change. By analyzing these changes it is possible to identify three distinct friction regimes with corresponding contact properties: (a) friction dominated by the additional normal forces induced by capillarity due to the presence of thick water films, (b) higher drag force from ordering effects present in thin water layers and (c) low friction due to direct solid–solid contact for the sample with the counterbody. Depending on environmental conditions and the applied normal load, all three mechanisms may be present at one time. Their individual contributions can be identified by investigating the dependence of friction on the applied normal load as well as on the sliding velocity in different pressure regimes, thus providing information about nanoscale friction mechanisms.     

Friction behaviour of chemical vapor deposited self-assembled monolayers on silicon wafer

Friction characteristics of self-assembled monolayers (SAMs) coated on Si-wafer (1 0 0) by chemical vapor deposition technique were studied experimentally at nano and micro-scales. Four self-assembled monolayers, such as dimethyldichlorosilane (DMDC), diphenyldichlorosilane (DPDC), perfluorooctyltrichlorosilane (PFOTS) and perfluorodecanoicacid (PFDA) coated on Si-wafer (1 0 0) were used as test materials. Nano-scale friction was measured using atomic force microscopy (AFM) in the range of 0–40 nN normal loads, in LFM (lateral force microscopy) mode, using a contact mode type Si₃N₄ tip. Results showed that the friction of SAMs at this scale was influenced by their physical/chemical properties, while that of Si-wafer by its inherent adhesion. Further, micro-scale friction tests were also performed with a ball-on-flat type micro-tribotester under reciprocating motion. Friction was measured in the range of 1500–4800 μN applied normal loads using glass balls of varying radii, viz., 0.25, 0.5 and 1 mm. It was observed that the performance of SAMs was more superior to Si-wafer even at micro-scale, except for PFDA. Evidences obtained using scanning electron microscope showed that Si-wafer and PFDA exhibited wear at this scale. Wear in the case of Si-wafer was due to solid–solid adhesion and that in the case of PFDA due to the influence of humidity (moisture). The micro-scale friction in both these materials was severely influenced by their wear.     

The influence of coating structure on micromachine stiction

Stiction and friction in micromachines is commonly inhibited through the use of silane coupling agents such as 1H-, 1H-, 2H-, 2H-perfluorodecyltrichlorosilane (FDTS). FDTS coatings have allowed micromachine parts processed in water to be released without debilitating capillary adhesion occurring. These coatings are frequently considered as densely-packed monolayers, well-bonded to the substrate. In this paper, it is demonstrated that FDTS coatings can exhibit complex nanoscale structures, which control whether micromachine parts release or not. Surface images obtained via atomic force microscopy reveal that FDTS coating solutions can generate micellar aggregates that deposit on substrate surfaces. Interferometric imaging of model beam structures shows that stiction is high when the droplets are present and low when only monolayers are deposited. As the aggregate thickness (tens of nanometers) is insufficient to bridge the 2 m gap under the beams, the aggregates appear to promote beam–substrate adhesion by changing the wetting characteristics of coated surfaces. Contact angle measurements and condensation figure experiments have been performed on surfaces and under coated beams to quantify the changes in interfacial properties that accompany different coating structures. These results may explain the irreproducibility that is often observed with these films.     

Microtribological Properties of Two-Phase Al2O3 Ceramic Studied by AFM and FFM in Air of Different Relative Humidity

Commercially available, monolithic alumina ceramic was modified using CO₂-laser irradiation by surface remelting and adding HfO₂ powder. Scanning electron microscopy revealed that the microstructure of the modified ceramic consisted of a fine lamellar eutectic Al₂O₃–HfO₂ phase embedded in the Al₂O₃ matrix. Differences in the microtribological properties of the matrix and the eutectic phase could be measured by friction force microscopy (FFM) during unlubricated sliding contact with a silicon tip at room temperature as a function of relative humidity of the surrounding air and normal load. The dependence of the friction coefficient and the pull-off force on humidity was explained by the formation of lubricating tribochemical surface layers and described by theoretical models.     

硅基微机械表面粘附及摩擦性能的AFM试验研究

在Si（100）基片上制备了十八烷基三氯硅烷（OTS）分子润滑膜，并用原子力显微镜（AFM）对比研究了施加OTS膜前后的硅表面的粘附、摩擦磨损性能。试验考虑了相对湿度和扫描速度对粘附、摩擦性能的影响。结果表明，相对于硅构件来讲，OTS膜表面粘附力较小，具有较小的摩擦因数，呈现较好的润滑性能；硅构件受湿度变化的影响比OTS膜明显。微构件的摩擦性能由于水合化学作用生成Si（OH）。润滑膜，使得其受相互间运动速度影响很大。OTS膜不仅是一种耐磨性较好的润滑膜，而且有良好的稳定性。     

磁控溅射MoS2薄膜的结构和微观摩擦磨损特性

利用磁控溅射法制取了ＭｏＳ２薄膜,通过Ｘ光电子能谱、Ｘ射线衍射和ＡＦＭ／ＦＦＭ方法对薄膜的表面形貌、成分、化学价态、结构和微观摩擦磨损性能进行了研究。实验结果表明：ＭｏＳ２薄膜表面呈蠕虫状,微观结构为（１００）面平行于基面的非晶态,表面膜由ＭｏＳ２和少量的ＭｏＯ３组成。在微观摩擦磨损过程中,ＭｏＳ２薄膜的摩擦系数较大,且而磨性能高;微摩擦过程中没有磨合阶段,不存在摩擦机理的转变。     

Microtribological behaviour of thin DLC films using different testing methods

To enhance the lifetime and reliability of microcomponents, thin microtribological films are applied to microparts. With reduction of the component size, investigation methods for tribological testing must be adapted. This paper studies the microtribological behaviour of thin diamond‐like carbon (DLC) films using different testing methods. To tie in with macroscopic results, to determine friction we used the well‐known pin‐on‐disc test with spherical surfaces of 10 mm diameter under a typical load of 3 N. For investigations of the behaviour under single asperity contact, Atomic Force Microscope (AFM) methods with applied loads of a few hundred micronewtons were used. Investigations on thin DLC films showed that the friction coefficient under single asperity contact is strongly dependent on the applied load and the resulting contact area. Especially for thin films (up to a few hundred nanometres) the friction coefficient is influenced by the substrate material. With decreasing substrate Young's modulus the friction coefficient also decreases. On the other hand, an increase in the abrasive wear resistance was observed using soft substrate materials. In this paper we show that the friction coefficient was also reduced by a simple surface structure. For investigations we used photolithography to create concentric circles in different substrates. This resulted in a behaviour like riding on rails for the pin‐on‐disc test. Depending on the tribological pairing the friction coefficient was reduced to more than 50% of the original value. Copyright © 2006 John Wiley & Sons, Ltd.     

Influence of humidity on microtribology of vertically aligned carbon nanotube film

The aim of this study is to probe the influence of water vapor environment on the microtribological properties of a forestlike vertically aligned carbon nanotube (VACNT) film, deposited on a silicon (001) substrate by chemical vapor deposition. Tribological experiments were performed using a gold tip under relative humidity varying from 0 to 100%. Very low adhesion forces and high friction coefficients of 0.6–1.3 resulted. The adhesion and friction forces were independent of humidity, due probably to the high hydrophobicity of VACNT. These tribological characteristics were compared to those of a diamond like carbon (DLC) sample.