Bio-inspired dual surface modification to improve tribological properties at small-scale

In miniaturized devices like micro/nano-electro-mechanical systems (MEMS/NEMS), the critical forces, namely adhesion and friction restrict the smooth operation of the elements that are in relative motion. MEMS/NEMS are traditionally made of silicon, whose tribological properties are not good. In this paper, we present an investigation on the approach of dual surface modification of silicon surfaces and their tribological properties at micro-scale. The dual surface modification is a combination of topographical and chemical modifications. As the topographical modification, micro-patterns with varying shapes of pillars and channels were fabricated on Si(1 0 0) wafer surfaces using photolithography method. Chemical modification included the coating of micro-patterns with diamond-like carbon (DLC) and Z-DOL (perfluoropolyether, PFPE) thin films. The surfaces with combined modification were evaluated for their micro-friction behavior in comparison with those of bare Si(1 0 0) flat surfaces and the topographically/chemically modified silicon surfaces. Results showed that the surfaces with dual modification exhibited superior tribological properties. These results indicate that a combination of topographical and chemical modification is very effective in enhancing tribological properties at small-scale. The combined surface treatments such as the ones investigated in the current work could be useful for tribological applications in small-scale devices such as MEMS/NEMS. The motivation for undertaking the dual modification approach comes from an earlier observation made on the significant influence of the surface characteristics of lotus leaf on its micro-friction behavior.     

Preparation and tribological tests of thin fluoroorganic films

Adhesion, friction and consequent wear of sliding surfaces are the basic problems that limit the performance and reliability of microelectromechanical devices. Lubrication of these nano- and microscale contacts is different from traditional lubricants. Self-assembled monolayers (SAMs) chemically bonded to the substrate are considered to be the best solution of lubrication. The majority of these monolayers are hydrophobic providing low friction, adhesion and wear.Chemical vapor deposition was used to grow a fluorosilane film on silicon Si(1 0 0) and a condensed monolayer of 3-mercaptopropyltrimethoxysilane (MPTMS) on Au(1 1 1). The films were characterized by means of a contact angle analyzer for hydrophobicity, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) for identification of thin fluoroorganic monolayers deposited on silica surfaces and condensed monolayer MPTMS. Adhesion and friction measurements were performed using atomic force microscopy (AFM) and compared with measurements performed using a microtribometer operating in millinewton (mN) normal load range. Nanotribological measurements indicated that silica and MPTMS modified by fluorosilanes have the lowest friction coefficient and indicated a decrease friction coefficient with increasing fluoric alkyl chain length.     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

Tribological properties of chemically bonded polyimide films on silicon with polyglycidyl methacrylate brush as adhesive layer

Polyimide thin films, which possess good stability and film uniformity, are successfully fabricated on single crystal silicon wafers coated with a thin polymer brush by suface-initiated polymerization (SIP) as an adhesive layer. The growth kinetic of polyglycidyl methacrylate (PGMA) brush was studied by the means of ellipsometry. The nano-scale morphology and chemical composition of PGMA brush and polyimide film were studied with atomic force microscopy (AFM), Fourier transform infrared spectrum (FT-IR), and X-ray photoelectron spectroscopy (XPS). The tribological behaviors of the thin films sliding against AISI-52100 steel ball were examined on a static-dynamic friction precision measurement apparatus and UMT-2MT tribometer. The worn surface of the polyimide thin films was investigated with scanning electron microscopy (SEM). The results indicated that the chemically bonded polyimide films exhibited better friction reduction and antiwear behavior compared to the polymide films on bare silicon surface. At a load of 0.5 N and sliding speed of 20 mm s⁻¹, the durability life of the polyimide thin films is over 25,000 sliding cycles and the friction coefficient is about 0.08.     

Control of tribological properties of diamond-like carbon films with femtosecond-laser-induced nanostructuring

This paper reports tribological properties of diamond-like carbon (DLC) films nanostructured by femtosecond (fs) laser ablation. The nanostructure was formed in an area of more than 15 mm × 15 mm on the DLC surface, using a precise target-scan system developed for the fs-laser processing. The frictional properties of the DLC film are greatly improved by coating a MoS₂ layer on the nanostructured surface, while the friction coefficient can be increased by surface texturing of the nanostructured zone in a net-like patterning. The results demonstrate that the tribological properties of a DLC surface can be controlled using fs-laser-induced nanostructuring.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Microtribological study of perfluoropolyether with different functional groups coated on hydrogen terminated Si

Friction and wear properties of different perfluoropolyether (PFPE) films with and without hydrogen termination on Si (Si-H) were studied using a ball-on-disk tribometer. The physical and chemical properties of the films were evaluated using contact angle measurement, atomic force microscopy and X-ray photoelectron spectroscopy. Coating of PFPEs onto bare Si has lowered the coefficient of friction (from 0.6 for Si to ∼0.05 with PFPE) and enhanced the wear durability (20,000 times) in comparison with those for bare Si which failed immediately. The introduction of hydrogen termination onto Si prior to PFPE coating has further increased the wear durability of PFPE with different functional groups several times (>5 times) under a normal load of 30 mN and a sliding speed of 0.052 m/s.     

Evaluation of bacterial adhesion on Si-doped diamond-like carbon films

Diamond-like carbon (DLC) films as biomaterial for medical devices have been attracting great interest due to their excellent properties such as hardness, low friction and chemical inertness. It has been demonstrated that the properties of DLC films can be further improved by the addition of silicon into DLC films, such as thermal stability, compressive stress, etc. However no research work on anti-bacterial properties of silicon-doped diamond-like carbon films has been reported. In this paper the surface physical and chemical properties of Si-doped diamond-like carbon films with various Si contents on 316 stainless steel substrate prepared by a magnetron sputtering technique were investigated, including surface topography, surface chemistry, the sp³/sp² ratio, contact angle, surface free energy, etc. Bacterial adhesion to Si-doped DLC films was evaluated with Pseudomonas aeruginosa, Staphylococcus epidermidis and Staphylococcus aureus which frequently cause medical device-associated infections. The experimental results showed that bacterial adhesion decreased with increasing the silicon content in the films. All the Si-doped DLC films performed much better than stainless steel 316L on reducing bacterial attachment.     

Friction,adhesion and wear durability of an ultra-thin perfluoropolyether-coated 3-glycidoxypropyltrimethoxy silane self-assembled monolayer on a Si surface

The tribological properties, such as coefficient of friction, adhesion and wear durability of an ultra-thin (<10?nm) dual-layer film on a silicon surface were investigated. The dual-layer film was prepared by dip-coating perfluoropolyether (PFPE), a liquid polymer lubricant, as the top layer onto a 3-glycidoxypropyltrimethoxy silane self-assembled monolayer (epoxy SAM)-coated Si substrate. PFPE contains hydroxyl groups at both ends of its backbone chain, while the SAM surface contains epoxy groups, which terminate at the surface. A combination of tests involving contact angle measurements, ellipsometry, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) was used to study the physical and chemical properties of the film. The coefficient of friction and wear durability of the film were investigated using a ball-on-disk tribometer (4?mm diameter Si₃N₄ ball as the counterface at a nominal contact pressure of ～330?MPa). AFM was used to investigate the adhesion forces between a sharp Si₃N₄ tip and the film. This dual-layer film had a very low coefficient of friction, adhesion and wear when compared to epoxy SAM-coated Si only or bare Si surface. The reasons for the improved tribological performance are explained in terms of the lubrication characteristics of PFPE molecules, low surface energy of PFPE, covalent bonding between PFPE and epoxy SAM coupled with reduced mobile PFPE. The low adhesion forces coupled with high wear durability show that the film has applications as a wear resistant and anti-stiction film for microcomponents made from Si.     

掺硅类金刚石薄膜摩擦过程的分子动力学模拟

掺硅类金刚石(Si-DLC) 薄膜表现出优异的摩擦学性能, 在潮湿空气和高温中显示出极低的摩擦系数和很好的耐磨性, 但是许多实验表明Si-DLC膜的摩擦性能受其硅含量的影响很大. 因此, 本文采用分子动力学模拟的方法分别研究干摩擦和油润滑两种情况下不同硅含量的Si-DLC膜的摩擦过程. 滑移结果表明干摩擦时DLC膜和掺硅DLC膜之间生成了一层转移膜, 而油润滑时则为边界膜. 因此干摩擦时的摩擦力明显大于油润滑时的摩擦力. 少量添加硅确实能降低DLC膜的摩擦力, 但是硅含量大于20%后对DLC膜的摩擦行为几乎无影响. 干摩擦时硅含量对转移膜内键的数量影响很大, 转移膜内CC键和CSi键都先增加后减少, 滑移结束时几乎不含CSi键.     

Defect effect on tribological behavior of diamond-like carbon films deposited with hydrogen diluted benzene gas in aqueous environment

This study examined the friction and wear behavior of diamond-like carbon (DLC) films deposited from a radio frequency glow discharge using a hydrogen diluted benzene gas mixture. The DLC films were deposited on Si (1 0 0) and polished stainless steel substrates by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) at hydrogen to benzene ratios, or the hydrogen dilution ratio, ranging from 0 to 2.0. The wear test was carried out in both ambient and aqueous environments using a homemade ball-on-disk type wear rig. The stability of the DLC coating in an aqueous environment was improved by diluting the benzene precursor gas with hydrogen, suggesting that hydrogen dilution during the deposition of DLC films suppressed the initiation of defects in the film and improved the adhesion of the coating to the interface.     

Growth and characterization of ferromagnetic MnAs films on different semiconductor substrates

MnAs thin films were grown by metalorganic vapour-phase epitaxy (MOVPE) on GaAs(0 0 1), Si(0 0 1) and oxidised silicon substrates. All films are crystalline and contain only the ferromagnetic α-MnAs phase. X-ray diffraction (XRD) and atomic force microscopy (AFM) measurements show that films on GaAs(0 0 1) have strong preferential orientation, developing elongated grains parallel to [1 –1 0] GaAs while films on bare and oxidised Si are polycrystalline with irregular-shaped, randomly oriented grains. Magneto-optic Kerr effect (MOKE) measurements show good magnetic properties for films on GaAs, such as strong in-plane anisotropy and squareness of the hysteresis loop in the easy direction. A Curie temperature of 340 K, remarkably higher than the bulk material (315 K), was found for a 65 nm thick film on GaAs. Films grown on bare and oxidised silicon wafers had lower Curie temperature and were magnetically isotropic.     

Influence of crystalline diamond nanoparticles on diamond-like carbon friction behavior

Crystalline diamond (CD) particles have been incorporated in diamond-like carbon (DLC) film structure in order to improve DLC electrochemical corrosion resistance. This paper shows the investigation of CD-DLC friction behavior according to the CD average sizes and concentration. The films were growth over 304 stainless steel using plasma enhanced chemical vapor deposition. The response surface methodology was used to develop a mathematical modeling of friction for these films, using the experimental results, in order to identify parameters that control friction and construct tribological maps according to the CD average sizes. The presence of bigger CD particles (250 and 500 nm) increased the film roughness. Films with CD particles of 4 nm presented the most homogeneous friction map, with minor variation in friction coefficient with the increase/decrease of load and sliding speed even when the CD concentration increase. This result suggests that in CD-DLC films containing CD particles of 4 nm average size, the nanoparticles are better incorporated in DLC structure due to its average size (4 nm) that is near than DLC grain size and could occupy the nanospaces between DLC grains.     

A low temperature surface preparation method for STM nano-lithography on Si(1 0 0)

Registration markers are crucial in connecting scanning tunneling microscope (STM) lithographed nano- and atomic-scale devices to the outside world. In this paper we revisit an ultra high vacuum annealing method with a low thermal budget that is fully compatible with etched registration markers and results in clean 2 × 1 reconstructed Si(1 0 0) surfaces required for STM lithography. Surface contamination is prevented by chemically stripping and reforming a protective silicon oxide layer before transferring the sample to the vacuum system. This allows for annealing temperatures of only 900 °C, where normally carbon contaminants result in the formation of SiC clusters on the surface at annealing temperatures below 950 °C. Reactive ion etched marker structures with an etch depth of 60 nm and a typical lateral dimension of only 150 nm survive a 900 °C flash anneal.     

Influence of high temperature annealing on the structure, hardness and tribological properties of diamond-like carbon and TiAlSiCN nanocomposite coatings

Diamond-like carbon (DLC) and TiAlSiCN nanocomposite coatings were synthesized and annealed at different temperatures in a vacuum environment. The microstructure, hardness and tribological properties of as-deposited and annealed DLC-TiAlSiCN nanocomposite coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, nano-indentation and friction tests. The TEM results reveal that the as-deposited DLC-TiAlSiCN coating has a unique nanocomposite structure consisting of TiCN nanocrystals embedded in an amorphous matrix consisting of a-Si₃N₄, a-SiC, a-CN and DLC, and the structure changed little after annealing at 800 °C. However, XPS and Raman results show that an obvious graphitization of the DLC phase occurred during the annealing process and it worsened with annealing temperature. Because of the graphitization, the hardness of the DLC-TiAlSiCN coating after annealing at 800 °C decreased from 45 to 36 GPa. In addition, the DLC-TiAlSiCN coating after annealing at 800 °C has a similar friction coefficient to the as-deposited coating.     

The study of ion mixed amorphous carbon films on single crystal silicon by C ion implantation

Amorphous-carbon (a-C) films were deposited on a single-crystal silicon substrate by vacuum vapor deposition system and these amorphous carbon films were implanted with 110 keV C⁺ at fluences of 1 × 10¹⁷ ions/cm². The effect of ion mixing on the surface morphology, friction behavior and adhesion strengths of amorphous carbon films was examined making use of atomic force microscopy (AFM), ball-on-disk reciprocating friction tester, nano-indentation system and scanning electron microscope (SEM). The changes in chemical composition and structure were investigated by using X-ray photoelectron spectroscopy (XPS). The results show that the anti-wear life and adhesion of amorphous carbon films on the Si substrates were significantly increased by C ion implantation. The SiC chemical bonding across the interface plays a key role in the increase of adhesion strength and the anti-wear life of amorphous carbon film. The friction and wear mechanisms of amorphous carbon film under dry friction condition were also discussed.     

Tribological behavior of diamond-like carbon film with different tribo-pairs: A size effect study

A friction force microscope (FFM) with different probes and a ball-on-disk (BOD) tribo-meter were used to investigate the tribological properties of diamond-like carbon (DLC) films. DLC films were prepared by chemical vapor deposition (CVD) method by altering the deposition parameters, and their morphologies and structural information were examined with an atomic force microscope (AFM) and the Raman spectrum. The wear traces of the DLC films after frictional tests were analyzed by an optical microscope. It is found that surface roughness and adhesion play important roles in characterizing the tribological properties of DLC films using FFM. Moreover, the debris accumulation is another significant factor affecting the frictional behavior of DLC films, especially for the sharp tip. The difference in coefficients of friction (COFs) obtained by the BOD method among different DLC films under water lubrication is much smaller than the case without water lubrication. The variation trends in COF for the flat tip and the BOD test are similar in comparison with the result obtained with the sharp tip. The wear traces after frictional tests suggest that DLC films under water lubrication are prone to be damaged more readily.     

Nanotribological properties of silicon surfaces nanopatterned by laser interference lithography

The problems caused by the adhesive force and friction force become more critical when the size of M/NEMS devices shrinks to micro/nano-scale. The nanotexture-patterned surface is an effective approach to reduce friction force on micro/nano-scale. Laser interference lithography is an attractive method to fabricate micro/nanotextures, which is maskless and allows large area periodical structures to be patterned by a couple of seconds’ exposure in a simple equipment system. We fabricate various nanogrooves with different pitch and space width on silicon wafers by laser interference lithography and chemical etching. We investigate the nanotribological properties of the patterned surfaces by AFM/FFM. We show that friction on the nano/micro-scale is related to the coverage rate of the nanogrooves, which decreases with increase in the space width and decrease in the pitch.     

Influence of sulfidation treatment on the structure and tribological properties of nitrogen-doped diamond-like carbon films

The nitrogen-doped diamond-like carbon (DLC) films were deposited on high speed steel (HSS) substrates in the direct current unbalanced magnetron sputtering system. Sulphurized layer was formed on the surface of DLC films by means of liquid sulfidation in the intermixture of urea and thiourea solution in order to improve the tribological properties of DLC films. The influence of sulfidation treatment on the structure and tribological properties of DLC films was investigated in this work. The structure and wear surface morphology of DLC films were analyzed by Raman spectroscopy, XPS and SEM, respectively. It reveals that the treated films are smooth and uniform; and sulfur atoms are bonded chemically. The treated films have broader distribution of Raman spectra in the range of 1000-1800 cm⁻¹ and higher I_D/I_G ratio than the untreated films as a result of the appearance of the crystalline graphite structure after the sulfidation treatment. It is showed that the sp² relative content increase in the treated films from the XPS measurement. The Raman results are consistent with the XPS results. The tribological properties of DLC films were investigated using a ball-on-disk rotating friction and wear tester under dry friction conditions. It is found that the sulfidation concentration plays an important part in the tribological properties of the treated DLC films. The results showed the treated films with low sulfidation concentration have a lower friction coefficient (0.1) than the treated films with high sulfidation concentration (0.26) and the untreated films (0.27) under the same friction testing conditions, which can be attributed to both the presence of sulfur-containing materials and the forming of the mechanical alloyed layer on the wear surface. Adding the dry nitrogen to the sliding surface in the testing system helps the friction coefficient of the treated films with low sulfidation concentration to decrease to 0.04 further in this work. On the basis of the experimental results, it is indicated that the liquid sulfidation technique, which is low-cost, non-polluting and convenience, would be an appropriate method for the surface treatment of DLC films.     

The effect of alloying on the structure and peculiarities of tribological behavior of vacuum-deposited diamond-like coatings

In this work, we report the results of a study of the atomic and crystalline structures, phase and chemical compositions and tribological properties of DLC coatings deposited by plasma-assisted (PA) CVD (a-C:H:Si and a-C:H:Si:Mo) and magnetron reactive sputtering (a-C:H:Cr). The a-C:H:Si:Mo coatings revealed the formation of ultra-dispersed inclusions of either molybdenum carbides or silicides, whereas no such inclusions were found in the a-C:H:Si compound. The a-C:H:Cr coatings that were deposited in an acetylene–nitrogen gas mixture exhibited a nanocomposite structure composed of chromium, its carbide and nitride phases. The tribological tests showed that the DLC coatings with silicon and silicon–molybdenum have a high friction coefficient and a low working performance, while the chromium-containing coatings have high levels of their mechanical and tribological characteristics, making them promising materials for operation under high contact pressures.