Characterisation of electronic and structural properties of thin silicon dioxide films by scanned probe microscopy

This paper concerns the application of scanned probe microscopy to the study of thin silicon dioxide films. We show how the formation of 7 nm diameter silicon carbide particles on a silicon surface during high temperature processing affects the quality of subsequently grown oxide. To measure the local dielectric properties of thin oxides we have developed a new type of probe measurement which allows high resolution surface imaging, based on an atomic force microscope, combined with local electrical measurements. The spatial resolution of the electrical measurements was shown to be < 40 nm. Applying the technique to 500 nm capacitors fabricated on device quality oxide it was shown that some capacitors broke down during imaging while others remained stable at electric fields up to 30 MVcm^?1. This higher breakdown strength may have substantial impact on future electronic device reliablity and performance.     

On the stiction of MEMS materials

Stiction is a serious problem in microelectromechanical systems (MEMS) due to their large surface area-to-volume ratio. Stiction is closely related to surface forces, which greatly depend on the materials used, surface topography and surface treatment process. In this paper, we investigate surface energies and stiction of commonly used MEMS materials by contact angle measurements and atomic force microscopy (AFM). Dispersive and polar components of surface energies are calculated by Owens–Wendt–Rabel–Kaelble method. Silicon and silicon-related materials have higher polar surface energies than SU-8 and poly-methylmethacrylate (PMMA), thereby have larger surface energies and enhanced tendency for stiction. The nano-scale adhesion forces between Si₃N₄ tip and surfaces obtained by AFM further verified that silicon wafer with native oxide has 3–4 times higher adhesion force than SU-8 and PMMA. It has been shown that the materials with higher surface energy have higher sticton/adhesion forces. The topography of surface influences the contact angle and stiction, and is also discussed in the paper.     

Improvement of surface electrical conductivity in poly carbonate composite by nitrogen ion implantation

This study is to investigate the nitrogen ion implantation process in PC (Polycarbonate) composite for improving surface electrical conductivity. The suggested process is applied for the thin wall shape polymer which is composed of low carbon black and carbon fiber in order to increase electric conductivity. The acceleration voltage which is relatively low 3∼50 keV in ion implantation process is used to obtain the thin conductive surface layer around 2 micrometer. The surface electrical conductivity of PC composite is realized up to below 10⁶ Ω/cm² by controlling ion dose without degrading mechanical properties. This technology can be adopted to make conductive plastic product which is applicable for static electricity prevention and electromagnetic wave masking. In order to evaluate the effect of surface modification of PC by nitrogen ion implantation, its surface resistance, tensile strength, tensile elongation, and half-life have been measured. The properties of PC/CF and PC/CB increased surface resistance and tensile strength. Also, the properties of PC/CF and PC/CB significantly decreased tensile elongation and half-life.     

Ion implantation and surface modification in tribology

Ion implantation is a vacuum process by which virtually any element can be injected into the surface regions of a solid target. Current interest in materials technology and recent developments in ion implantation machines have resulted in ion-induced surface property changes in a variety of different fields including tribology. Large changes in friction coefficient (up to ± 60%) have been recorded on steel surfaces implanted with such ions as Pb⁺ and Sn⁺. Implantation of boron, nitrogen and molybdenum reduces wear by more than a factor of 10, from measurements with a pin-and-disc machine. An outline is given of the scope and application of ion implantation and the results evaluated in the context of the testing methods used. Examples are given of some present and future applications of ion implantation to tribology.     

Rheology of Thin Organic Films

This paper deals with the effects of contact pressure and temperature on the shear strength of thin organic films. The experimental method involves depositing the material as thin films (ca. 3 nm to 500 nm) on smooth glass surfaces. The film is sheared by sliding over it indenters of fired glass. By varying the indenter radius from 4 μm to 2.5 mm and the load from 10 mg to 20 g, the contact pressure may be varied from 10⁷ Pa (1.4 × 10³ P.s.i.) to 8 × 10⁹ Pa (12 × 10⁵ p.s.i.). The temperature dependence of the shear strength is also studied. Two types of organic materials have been investigated. These range from simple low molecular weight compounds such as stearates, to more complex high molecular weight polymers, for example P.M.M.A.

The shear strength of these films has been compared with the bulk shear properties and consideration has been given to the molecular processes occurring during shear.     

Microtribology,squeeze, and friction of the colloidal layer

Lubricant films containing colloidal overbased calcium salts have particular effects on detergency and on the wear process. The mechanical properties of such boundary films are very dependent on the process conditions, and are essentially a result of physico-chemical transformations of the colloid. Three types of films were compared: a film obtained by the drying of the base solvent, a film due to the compaction of the colloid between two steel surfaces, and a friction film obtained with this type of lubricant. Adsorption, compaction, and shear transformations induce a solid film. The pressure effect on the frictional behaviour of these colloidal films has been investigated using a surface force apparatus for low contact pressure (10⁴ to 10⁶ Pa), and using tribometers supporting heavy loads for the analysis of the high pressure domain. Above a critical pressure, evaluated at 10⁶ Pa, the colloidal film does not flow, but forms a compacted mattress sliding on the surface plane and squeezing a molecular layer of lubricant.     

Assessing Nanotribological Performance and Surface Energies of Inconel-ZrN,Cr-ZrN,Nb-ZrN,and ZrN Thin Films

The nanotribological performance for three groups of metal-ZrN, including Inconel-ZrN, Cr-ZrN, Nb-ZrN, and polycrystalline ZrN thin films has been investigated and results were correlated with surface energy evaluations. Metal-ZrN and ZrN thin films were deposited using direct current (DC) unbalanced magnetron sputtering and their elemental composition was investigated using X-ray photoelectron spectroscopy (XPS). Both nanomechanical and nanotribological properties were evaluated using a triboscope interfaced with an atomic force microscope (AFM) and the surface energies were calculated from the contact angle measurements. The present research reports for the first time on the nanowear behavior, surface roughness, and friction coefficients correlated with surface energies of metal-ZrN and ZrN thin films.

All metal-ZrN thin films showed improved nanotribological performance compared to the polycrystalline ZrN. Results indicate that several of the Inconel-ZrN thin film compositions have both superior nanotribological behavior and good wettability and thus have high potential use for wear resistant applications.     

表面分析仪器在超疏水表面研究中的应用

超疏水表面制备与研究是近年来材料科学的重要研究方向,超疏水表面的研究离不开表面分析测试仪器。本文简要介绍了超疏水材料的表面特性、理论模型及其制备方法,重点介绍了扫描电子显微镜、X射线光电子能谱、原子力显微镜和表面接触角测试等几种常用表面分析方法的基本原理及其在超疏水表面研究中的具体应用。     

Differences between nanoscale structural and electrical properties of AZO:N and AZO used in polymer light‐emitting diodes

Conducting atomic force microscopy and scanning surface potential microscopy were adopted to investigate the nanoscale surface electrical properties of N‐doped aluminum zinc oxide (AZO:N) films that were prepared by pulsed laser deposition (PLD) at various substrate temperatures. Experimental results demonstrated that when the substrate temperature is 150°C and the N₂O background pressure is 150 mTorr, the N‐dopant concentration on the surface is optimal. In addition, the root‐mean‐square roughness value of the film surface, the low contact current (<400 nA) conducting region as a percentage of the total area, and the mean work function value are 1.43 nm, 96.9%, and 4.88 eV, respectively, all of which are better than those of the optimal AZO film made by PLD. This result indicates that N‐doped AZO films are better for use as window materials in polymer light‐emitting diodes. Microsc. Res. Tech., 2010. © 2009 Wiley‐Liss, Inc.     

Design criteria for superlubricity in carbon films and related microstructures

Carbon offers the kind of flexibility that one needs in the design and production of chemically unique microstructures with properties ranging from superlubricity to super-hardness and/or -softness. This flexibility can be exploited for numerous tribological applications, ranging in sizes from nano-scale electromechanical systems to meso-scale engine parts and components. Recently, carbon was used in our laboratory to produce nearly frictionless carbon (NFC) films having friction coefficients as low as 0.001 and wear rates of 10⁻¹¹–10⁻¹⁰ mm³/N m even under dry sliding conditions and at very high contact pressures. Using advanced fabrication and chemical vapor deposition methods, our research team has pioneered the development of other unique microstructures possessing exceptional physical, chemical, mechanical, electrical, and tribological properties. The combination of such exceptional properties in one material is rather rare, but urgently needed by the industry to meet the increasingly multifunctional needs of advanced mechanical systems and devices. This paper provides an overview of recent progress in the study and understanding of the tribological properties of carbon-based coatings. The design and surface engineering aspects of such coatings are discussed and the principles of superlubricity in these films are presented. Examples of current and future applications for two- and three-dimensional carbon-based structures are also provided.     

Carbon Nanotube Reinforced Polyimide Thin-film for High Wear Durability

In this paper, the influence of single walled carbon nano tubes (SWCNTs) addition on the tribological properties of the polyimide (PI) films on silicon substrate was studied. PI films, with and without SWCNTs, were spin coated onto the Si surface. Coefficient of friction and wear durability were characterized using a ball-on-disk tribometer by employing a 4 mm diameter Si₃N₄ ball sliding against the film, at a contact pressure of ∼370 MPa, and a sliding velocity of 0.042 ms⁻¹. Water contact angle, AFM topography, and nano-indentation tests were conducted to study the physical and mechanical properties of the films. SWCNTs marginally increased the water contact angle of PI film. The addition of SWCNTs to PI has increased the hardness and elastic modulus of pristine PI films by 60–70%. The coefficient of friction of PI films increased slightly (∼20%) after the addition of SWCNTs, whereas, there was at least two-fold increase in the wear life of the film based on the film failure condition of coefficient of friction higher than 0.3. However, the film did not show any sign of wear even after 100,000 cycles of rotation indicating its robustness. This increase in the wear durability due to the addition of the SWCNTs is believed to be because of the improvement in the load-bearing capacity of the composite film and sliding induced microstructural changes of the composite film.     

Forces de surface et contact : les derniers nanomètres

Surface and contact forces: the last nanometres. We describe the use of surface force measurements to characterize contact properties of oxide surfaces. This technique is highly sensitive and permits us to evidence various phenomena related to surface interactions and surface mechanical response. Examples will be presented, dealing with adhesion (adhesion energy, interaction range for oxide powders and metal–oxide interfaces) and the mechanical response of adsorbed organic layers (elasticity modulus, toughness).     

Structure of superconducting thin films of YBa2Cu3O7−x grown on SrTiO3 and cubic zirconia

Thin films of the superconductive oxide YBa₂Cu₃O_7?x have been made by electron-beam coevaporation of the metals in an oxygen atmosphere onto single-crystal {001}-oriented SrTiO₃ and yttria-stabilized zirconia (YSZ) substrates. The oxide films were superconducting in the as-deposited state (T_c = 81–83K, J_c = 10⁶ A/cm² at 4.2K). Bright-field imaging, selectedarea diffraction (SAD), and high-resolution imaging in the transmission electron microscope were used to characterize the microstructure of these films. All of the films were polycrystalline. On SrTiO₃ the films were oriented, for the most part, with {110} parallel to the substrate surface. On YSZ, two microstructures were observed: one with smaller rectangular grains oriented with (100) or (010) parallel to the substrate surface and the other with (001) parallel to the surface (i.e., c-axis up).     

Tribological behaviour of duplex treated Ti–6Al–4V: combining nitrogen PSII with a DLC coating

The chemical structure and tribological behaviour of Ti–6Al–4V plasma source ion implanted with nitrogen then DLC-coated in an acetylene plus hydrogen-glow discharge (bias voltage −10 to −30 kV) were investigated. The as-modified samples have a TiN/H:DLC multilayer architecture (coating resistivity 1.6×10⁹ to 2.4×10¹¹ Ω/cm) and exhibit higher hardness, especially at low loads or plastic penetrations in the order of deposition bias voltage −10, −20 and −30 kV. At a lower contact load (1 N) and higher sliding speed (0.05 m/s), frictional properties in most cases improved, as did wear properties. At a higher contact load (5 N) and lower sliding speed (0.04 m/s), friction showed almost no improvement, and wear properties deteriorated. When the material of the counterbody was then changed from AISI 52100 to Ti–6Al–4V modified as the disc (contact load 5 N unchanged, sliding speed decreased), the friction coefficient decreased (but showed no improvement compared with the unmodified sample), while wear properties deteriorated further, and wear was changed from just the disc to both disc and ball, abrasive and adhesive dominated. Transfer films, mainly made up of wear debris transferred from the disc wear surfaces, were formed on the wear scars of the counterbodies. The deterioration of wear properties of the modified samples at the higher contact load is considered to be caused by the “thin ice” effect.     

岛状纳米多孔金制备及其SERS特性研究

表面增强拉曼散射（surface-enhanced Raman scattering,SERS）技术将纳米结构材料和拉曼光谱相结合,解决了传统拉曼散射技术灵敏度低的问题,为痕量物质检测提供了新的技术手段。高SERS活性基底材料是将拉曼光谱应用到痕量物质检测中的关键。采用磁控溅射技术结合脱合金工艺在硅片上制备出岛状纳米多孔金SERS基底,该基底的孔隙尺寸和金韧带宽度的比值远小于传统纳米多孔金,有效地增强了金韧带之间的电磁耦合效应,表现出更强的局域电磁场。该基底的检测极限可达约10-10 mol·L-1,且SERS光谱相对强度与浓度呈现出较好的线性关系,动态响应范围可达3个数量级。同时该基底结构均匀、性能稳定,制备工艺具有良好的可重复性。     

Evaluation of surface roughness and nanostructure of indium tin oxide (ITO) films by atomic force microscopy

Indium tin oxide was deposited on a glass (soda lime glass) by radiofrequency sputtering system at different sputtering gas (argon/oxygen 90/10%) pressures (20-34 mTorr) at room temperature. The sputtering rate was affected by the sputtering gas pressure. The optimum sputtering gas pressure was found to be 27 mTorr. The samples at different thicknesses (168, 300, 400, 425, 475, 500 and 630 nm) were deposited on the substrate. Transparency, electrical conductivity and surface roughness of the films were characterized. The samples were annealed at 350, 400 and 450 degrees C to evaluate annealing process effects on the concerned parameters and, therefore, the above-mentioned measurements were repeated again. The films exhibited reasonable optical transmittance and electrical conductivity and greatly improved after annealing. The characterization was focused on the scanning of the film surfaces before and after annealing, which has a prominent effect on the optical properties of the films. Film surfaces were scanned by scanning probe microscopy in contact atomic force mode. The most consideration was devoted to image analysis.     

Indirect monitoring of the dynamics at the contact interfaces of a pair of abrading titanium specimens

The novel method of using continuous tribo-electrification variations to monitor the dynamic tribological properties between metal films has been applied successfully [Y.P. Chang, A novel method of using continuous tribo-electrification variations for monitoring the tribological properties between the pure metal films, Wear, 262 (2007) 411–423]. The method was shown to produce clear and strong signals, superior to monitoring continuous friction coefficient variations. However, the above method was only shown to be suitable for the tested material pairs that were studied. In this paper, the method was improved and applied to monitoring the dynamic tribological properties between titanium oxide (TiO₂) films in the friction process. The experiment was conducted on a purposed-designed friction tester with a suitable measuring system. In order to investigate the tribological property of titanium (Ti) sliding against Ti with TiO₂ films in detail, the continuous variations of electrical contact resistance and friction coefficient were measured for monitoring the onset of film rupture between the TiO₂ films and the chemical reactions between the interfaces. Wear loss was measured by an accuracy balance and scan electron microscopy was used to observe the microstructures and material transfer. The experiments demonstrated that the novel method of using electrical contact resistance variations has great potential for monitoring the dynamic tribological properties and the chemical reactions of titanium specimens.     

Tribological properties of N+ ion implanted ultrananocrystalline diamond films

Tribological properties of ultra nanocrystalline diamond (UNCD) films have chemically been modified by N⁺ ion implantation and subsequent annealing processes. Friction coefficient is found to be 0.15 in as-prepared film comparing to 0.09 and 0.05 in N⁺ ion implanted and post-annealed films, respectively. Such a modification of friction coefficient is a characteristic of the transformation of sp³ to graphitized/amorphized sp² bonded carbon network. Transformation of sp³ to sp² carbon network causes conversion of higher surface energy state (hydrophilic) to lower (hydrophobic) one which results in ultra low friction coefficient. Graphitization/amorphization in wear track observed by micro Raman spectroscopy is found to be the prominent mechanism for the reduction in friction coefficient.     

Surface Energies of Magnetic Recording Head Components

The rate of material removal during fixed abrasive lapping is a function of friction coefficient, the surface tension of the lubricant and of the substrate, and the contact angles between the interfaces. In this study, the authors measured the surface energies of materials typically found in thin film magnetic recording heads using contact angle measurements and the Lifshitz–van der Waals acid/base approach. The different materials tested were Ni_xFe_y, Al₂O₃, and Al₂O₃-TiC. Sample preparation procedures were also considered. The chemical used to wash the surface was observed to affect the measured substrate surface energies. Surface energy values for samples washed with either acetone or hexane showed comparable results. The Ni_xFe_y gave the highest measured surface energy (46.3–48.8 mJ m⁻²) followed by Al₂O₃ (44.1–45.3 mJ m⁻²) and Al₂O₃-TiC (43.3–45.3 mJ m⁻²). In contrast, the oil-washed samples measured generally lower surface energy values. The study characterized the interaction of two lubricant types against the three materials. The oil-based lubricant spreads completely on oil-washed samples mainly because of the low surface tension of the oil (22.0 mJ m⁻²) and did not show measurable contact angles. In comparison, the water-soluble lubricant ethylene glycol, due to its higher surface tension (48.0 mJ m⁻²), formed higher contact angles ranging from 47.2 to 59.6° on the different substrates.     

金铜双金属表面增强拉曼散射基底的制备及应用

双金属材料结合了两种金属的特性从而获得远超单一金属的性能,因而在材料应用领域获得了广泛关注。如何以低成本获得高性能功能性材料是双金属推广应用的关键。以Cu30Mn70合金片材为前驱体,采用自由腐蚀和化学电镀两步法制备了金包铜纳米多孔基底(Au@NPC)。金包覆层在有效抑制铜在空气中氧化的同时,减小了韧带间孔径距离,进一步增大了紧邻韧带间的电磁耦合效应,使Au@NPC具有更强的局域电磁场增强特性,表现出优于纳米多孔铜的表面增强拉曼散射活性。金铜双金属材料可用作表面拉曼增强散射基底,具有优异的稳定性和较低的成本。