Nano/Microtribological Properties of Ultrathin Functionalized Imidazolium Wear-Resistant Ionic Liquid Films on Single Crystal Silicon

Ionic liquids (ILs) are considered as a new kind of lubricant for micro/nanoelectromechanical system (M/NEMS) due to their excellent thermal and electrical conductivity. However, so far, only few reports have investigated the tribological behavior of molecular thin films of various ILs. Evaluating the nanoscale tribological performance of ILs when applied as a few nanometers-thick film on a substrate is a critical step for their application in MEMS/NEMS devices. To this end, four kinds of ionic liquid carrying methyl, hydroxyl, nitrile, and carboxyl group were synthesized and these molecular thin films were prepared on single crystal silicon wafer by dip-coating method. Film thickness was determined by ellipsometric method. The chemical composition and morphology were characterized by the means of multi-technique X-ray photoelectron spectrometric analysis, and atomic force microscopic (AFM) analysis, respectively. The nano- and microtribological properties of the ionic liquid films were investigated. The morphologies of wear tracks of IL films were examined using a 3D non-contact interferometric microscope. The influence of temperature on friction and adhesion behavior at nanoscale, and the effect of sliding frequency and load on friction coefficient, load bearing capacity, and anti-wear durability at microscale were studied. Corresponding tribological mechanisms of IL films were investigated by AFM and ball-on-plane microtribotester. Friction reduction, adhesion resistance, and durability of IL films were dependent on their cation chemical structures, wettability, and ambient environment.     

Suppression of spurious vibration of cantilever in atomic force microscopy by enhancement of bending rigidity of cantilever chip substrate

To improve the precision of dynamic atomic force microscopy (AFM) using cantilever vibration spectra, a simple but effective method for suppressing spurious response (SR) was developed. The dominant origin of SR was identified to be the bending vibration of the cantilever substrate, by the analysis of the frequency of SR. Although a rigid cover pressing the whole surface of the substrate suppressed SR, the utility was insufficient. Then, a method of enhancing the bending rigidity of the substrate by gluing a rigid plate (clamping plate, CP) to the substrate was developed. This chip can be used with an ordinary cantilever holder, so that the reproducibility of SR suppression when attaching and detaching the cantilever chip to the holder was improved. To verify its utility, the evaluation of a microdevice electrode was performed by ultrasonic atomic force microscopy. The delamination at a submicron depth was visualized and the detailed variation of the delamination was evaluated for the first time using clear resonance spectra. The CP method will particularly contribute to improving dynamic-mode AFM, in which resonance spectra with a low quality factor are used, such as noncontact mode AFM in liquid or contact resonance mode AFM. The effect of the CP can be achieved by fabricating a substrate with a thick plate beforehand.     

Improving tapping mode atomic force microscopy with piezoelectric cantilevers

This article summarizes improvements to the speed, simplicity and versatility of tapping mode atomic force microscopy (AFM). Improvements are enabled by a piezoelectric microcantilever with a sharp silicon tip and a thin, low-stress zinc oxide (ZnO) film to both actuate and sense deflection. First, we demonstrate self-sensing tapping mode without laser detection. Similar previous work has been limited by unoptimized probe tips, cantilever thicknesses, and stress in the piezoelectric films. Tests indicate self-sensing amplitude resolution is as good or better than optical detection, with double the sensitivity, using the same type of cantilever. Second, we demonstrate self-oscillating tapping mode AFM. The cantilever's integrated piezoelectric film serves as the frequency-determining component of an oscillator circuit. The circuit oscillates the cantilever near its resonant frequency by applying positive feedback to the film. We present images and force-distance curves using both self-sensing and self-oscillating techniques. Finally, high-speed tapping mode imaging in liquid, where electric components of the cantilever require insulation, is demonstrated. Three cantilever coating schemes are tested. The insulated microactuator is used to simultaneously vibrate and actuate the cantilever over topographical features. Preliminary images in water and saline are presented, including one taken at 75.5 μm/s—a threefold improvement in bandwidth versus conventional piezotube actuators.     

脉冲激光沉积薄膜的残余应力测量

为了测量脉冲激光沉积法制备的小面积薄膜的残余应力,并解决Stoney公式在特定情况下误差较大的问题,本文提出了一种基于悬臂梁结构和数值计算的薄膜残余应力测量方法。该方法以初始曲率为零的原子力显微镜探针作为衬底梁,在衬底梁上使用脉冲激光沉积方法沉积被测薄膜,并记录衬底梁在薄膜沉积前后的翘曲形貌变化,再结合薄膜厚度、衬底梁几何尺寸、所涉及材料的杨氏模量与泊松比等其他参数,借助数值计算对实验数据进行分析,得出被测薄膜的残余应力。使用该方法测出:基于脉冲激光沉积法在高温环境下制备的二氧化钒薄膜的残余应力为-340 MPa,与文献报道的结果相符。本文提出的基于悬臂梁结构和数值计算的薄膜残余应力测量方法具有适用范围广、准确度好、实验成本低的优点。     

Preparation of TiO2 nanowire gas nanosensor by AFM anode oxidation

Applications of atomic force microscopy (AFM) to the fabrication of chemical nanosensors are presented in this paper. Using AFM cantilever as cathode, the surface of Ti thin film is oxidized to form a few tens of nanometers wide oxidized metal semiconductor wire, which works as a nanowire-based hydrogen sensor. The reaction mechanism is proposed. The AFM observations of fabrication of a TiO₂ nanowire are carried out. The sensitive characteristic of such TiO₂ nanowires to hydrogen is investigated.     

Tribological properties of ultra-thin ionic liquid films on single-crystal silicon wafers with functionalized surfaces

Two kinds of room temperature ionic liquid (RTIL) films carrying vinyl and hydroxyl functional groups were prepared on single-crystal Si wafers by spin coating. The tribological properties of the RTIL films sliding against AISI-52100 steel ball and Si₃N₄ ball in a ball-on-plate configuration were investigated on a dynamic–static friction coefficient measurement apparatus, using perfluoropolyether (PFPE) film as a comparison. The tribological behaviors of the ionic liquid films sliding against the same counterparts at extended test durations were also evaluated using a universal UMT-2MT test rig. The morphologies of the wear tracks of the RTIL films and the counterparts were examined using a scanning electron microscope equipped with an energy-dispersive X-ray analyzer attachment. It was found that the tribological performances of the ionic liquid films were closely related to the chemical structures of the RTILs and the chemical characteristics of the substrate surfaces. The films of vinyl group functionalized ionic liquids on hydroxylated substrate and vinyl group modified substrate exhibited very good friction-reduction and wear-resistant properties. It was assumed that there were enough strong forces between the films and substrate in these cases, and the ionic liquid molecules maintained good flexibility simultaneously. The films on hydrogen-terminated and methyl-terminated substrate showed poor tribological performance, which could be related to the relatively weak forces between the films and substrates. Moreover, the films on hydroxylated substrate showed lower friction at higher sliding velocities, which was assumed to be governed by the more rapid adsorption of the ionic liquid molecules on the steel ball at a higher sliding velocity. In addition, the ionic liquid films also had excellent tribological properties as they slid against silicon nitride ball. Therefore, it was supposed that the ionic liquid films could be used as a kind of universal lubricant for various combinations of the frictional pair.     

Retrofitting an atomic force microscope with photothermal excitation for a clean cantilever response in low Q environments

It is well known that the low-Q regime in dynamic atomic force microscopy is afflicted by instrumental artifacts (known as "the forest of peaks") caused by piezoacoustic excitation of the cantilever. In this article, we unveil additional issues associated with piezoacoustic excitation that become apparent and problematic at low Q values. We present the design of a photothermal excitation system that resolves these issues, and demonstrate its performance on force spectroscopy at the interface of gold and an ionic liquid with an overdamped cantilever (Q < 0.5). Finally, challenges in the interpretation of low-Q dynamic AFM measurements are discussed.     

Preparation of TiO2 nanowire gas nanosensor by AFM anode oxidation

Applications of atomic force microscopy (AFM) to the fabrication of chemical nanosensors are presented in this paper. Using AFM cantilever as cathode, the surface of Ti thin film is oxidized to form a few tens of nanometers wide oxidized metal semiconductor wire, which works as a nanowire-based hydrogen sensor. The reaction mechanism is proposed. The AFM observations of fabrication of a TiO2 nanowire are carried out. The sensitive characteristic of such TiO2 nanowires to hydrogen is investigated.     

An In Situ Method for Simultaneous Friction Measurements and Imaging of Interfacial Tribochemical Film Growth in Lubricated Contacts

Tribological investigations of macroscopic lubricated sliding contacts are critical for a wide range of industrial applications including automotive engines, gears, bearings, and any other contacting surfaces in relative motion. However, the inability of existing techniques to access buried sliding interfaces with high spatial resolution inhibits the development of fundamental insights into the tribological processes at play. Here we demonstrate a novel and general in situ method, based on atomic force microscopy (AFM), in which micrometer-scale spherical probes are attached to a standard microfabricated AFM cantilever which is then slid over a substrate while immersed in a liquid lubricant. In this case, steel colloidal probes and steel substrates were used, and the contact was immersed in a commercial polyalphaolefin oil with zinc dialkyl dithiophosphate (ZDDP) additive at both room temperature and 100 °C, but the method can be used for a broad range of material combinations, lubricants, and temperatures. We demonstrate that the in situ measurements of friction force and the morphological evolution of the tribochemical films on the substrate can be simultaneously achieved with nanometer-level spatial resolution. In addition, we demonstrate that the sliding zone is readily accessible for further characterization with higher spatial resolution using standard AFM probes with nanometer-scale tip radii. Ex situ characterization of the micrometer-scale probe and the sample is also feasible, which is demonstrated by acquiring high-resolution AFM topographic imaging of the final state of the probe.     

Hydrostatic ionic liquid-lubricated fluid film bearing for a rotational electron-beam lithography system

Rotational electron-beam mastering (REBM) systems have been studied with the aim of achieving the high data density necessary to facilitate the fabrication of next-generation optical data media, such as holographic storage. This study reports the design and testing of an ionic liquid (IL)-lubricated hydrostatic spindle system comprising an IL bearing, IL supply pump, and ionic magnetic fluid seal; and its outgassing performance under high-vacuum conditions. An inner vacuum chamber pressure of approximately 10⁻⁴ Pa was maintained during rotation of the spindle system. The outgassed products, as measured by a quadrupole mass spectrometer, were primarily generated from the air components in the lubricant IL. The non-repeatable runout in the radial direction, which is an important parameter of REBM accuracy, was 100 nm for a rotational speed of less than 130 min⁻¹. The proposed method can be used for a 100-nm scale REBM device.     

Characterization of nitride thin films by electron backscatter diffraction

Thin films incorporating GaN, InGaN and AlGaN are presently arousing considerable excitement because of their suitability for UV and visible light‐emitting diodes and laser diodes. However, because of the lattice mismatch between presently used substrates and epitaxial nitride thin films, the films are of variable quality. In this paper we describe our preliminary studies of nitride thin films using electron backscattered diffraction (EBSD). We show that the EBSD technique may be used to reveal the relative orientation of an epitaxial thin film with respect to its substrate (a 90° rotation between a GaN epitaxial thin film and its sapphire substrate is observed) and to determine its tilt (a GaN thin film was found to be tilted by 13 ± 1° towards [101 0]_GaN), where the tilt is due to the inclination of the sapphire substrate (cut off‐axis by 10° from (0001)_sapphire towards (101 0)_sapphire). We compare EBSD patterns obtained from As‐doped GaN films grown by plasma‐assisted molecular beam epitaxy (PA‐MBE) with low and high As₄ flux, respectively. Higher As₄ flux results in sharper, better defined patterns, this observation is consistent with the improved surface morphology observed in AFM studies. Finally, we show that more detail can be discerned in EBSD patterns from GaN thin films when samples are cooled.     

A large-sample atomic force microscope observing in both air and liquid

A large-sample atomic force microscope (AFM) that allows high resolution observation in both air and liquid has been developed. With a unique beam tracking method, laser beam is capable of reflecting off the same spot on the AFM cantilever throughout raster scan over the entire scan area, either operating in air or in liquid environment. Incorporating the stand-alone AFM probe unit with an automated large sample stage, wide-scan-range imaging can be realized with high resolution and slight distortion. In addition, an image stitching method is utilized to build a broad merged image with range up to millimeters while keeping nanometer order resolution. By using a large-volume liquid bath, large and massive sample can be observed in liquid with this AFM system. Several typical experiments have been carried out to demonstrate the imaging ability and stability of this AFM. Topographic structures of gold pattern on a glass substrate are scanned at two different places on the same specimen surface. The porosity of a sheet of filter paper is then characterized in both air and water. Finally, larger-area AFM image of anodic aluminum oxide template in oxalic acid is on spot obtained by merging several individually scanned images together. Experiments show that this AFM system can offer high resolution and wide range AFM images even for large samples with remarkable capabilities in various environments.     

High-throughput analysis of thin-film stresses using arrays of micromachined cantilever beams

We report on a technique for making high-throughput residual stress measurements on thin films by means of micromachined cantilever beams and an array of parallel laser beams. In this technique, the film of interest is deposited onto a silicon substrate with micromachined cantilever beams. The residual stress in the film causes the beams to bend. The curvature of the beams, which is proportional to the residual stress in the film, is measured by scanning an array of parallel laser beams generated with a diffraction grating along the length of the beams. The reflections of the laser beams are captured using a digital camera. A heating stage enables measurement of the residual stress as a function of temperature. As the curvature of each beam is determined by the local stress in the film, the film stress can be mapped across the substrate. This feature makes the technique a useful tool for the combinatorial analysis of phase transformations in thin films, especially when combined with the use of films with lateral composition gradients. As an illustration, we apply the technique to evaluate the thermomechanical behavior of Fe-Pd binary alloys as a function of composition.     

静电辅助气溶胶化学气相沉积法制备Al_2O_3薄膜

以乙酰丙酮铝为前驱体,N,N-二甲基甲酰胺为溶剂,采用静电辅助的气溶胶化学气相沉积(ESAVD)方法,在Si(100)衬底上制备了Al2O3薄膜,并采用场发射扫描电镜、能谱仪、X射线衍射仪和自动划痕仪等设备对制备的薄膜进行了表征。结果表明:采用ESAVD法制备的Al2O3薄膜平整致密而且晶粒细小,薄膜与基体之间及薄膜内部都未出现开裂现象;薄膜与基体的结合力约为5.56 N;沉积得到的薄膜为化学计量比为2∶3的氧化物薄膜;退火前的薄膜为非晶态,在1 200℃退火保温2 h后薄膜转变为-αAl2O3。     

Study of the nanoscopic deformation of an annealed nafion film by using atomic force microscopy and a patterned substrate

We demonstrated the repetitive imaging of the same area of a nafion film before and after annealing by using atomic force microscopy (AFM). In order to find the exact same area of the same sample after changing the cantilever and reattaching the sample, a micropatterned substrate was developed. A micropattern with a 250–500 μm pitch was prepared on the backside of a transparent glass substrate. This pattern includes various signs such as colored letters and numbers at the center of each lattice of the pattern. The nanostructures fabricated by AFM nanolithography on a nafion film using this new method were successfully characterized before and after annealing (over 100 °C). The AFM images clearly showed that the nanostructures on a nafion film were dramatically changed by annealing. The data indicated an evidence to understand why the nafion fuel cell does not work well at high temperatures. Our method is probably effective for the study of nanoscopic dynamics in various surface structures.     

Calibration of AFM cantilever spring constants

In this paper we present two simple, reliable and readily applicable methods for calibrating cantilevers and measuring the thickness of thin gold films. The spring constant calibration requires knowledge of the Young's modulus, density of the cantilever and resonant frequency. The thickness of thin gold layers was determined by measuring changes in the resonant frequency and Q-factor of beam shaped AFM cantilevers before and after coating.The techniques for measuring the spring constant and thin film thickness provide accuracy on the order of 10-15%.     

Finite-element vibration analysis of tapping-mode atomic force microscopy in liquid

Investigation of morphology and mechanical properties of biological specimens using atomic force microscopy (AFM) often requires its operation in liquid environment. Due to the hydrodynamic force, the vibration of AFM cantilevers in liquid shows dramatically different dynamic characteristics from that in air. A good understanding of the dynamics of AFM cantilevers vibrating in liquid is needed for the interpretation of scanning images, selection of AFM operating conditions, and evaluation of sample's mechanical properties. In this study, a finite element (FE) model is used for frequency and transient response analysis of AFM cantilevers in tapping mode (TM) operated in air or liquid. Hydrodynamic force exerted by the fluid on AFM cantilevers is approximated by additional mass and hydrodynamic damping. The additional mass and hydrodynamic damping matrices corresponding to beam elements are derived. With this model, numerical simulations are performed for an AFM cantilever to obtain the frequency and transient responses of the cantilever in air and liquid. The comparison between our simulated results and the experimentally obtained ones shows good agreement. Based on the simulations, different characteristics of cantilever dynamics in air and liquid are discussed.     

光学薄膜制备中的激光测温技术

概述激光测温技术在光学薄膜制备中的应用及其在自动化方面的新进展     

硅微构件的弹性模量和残余内应力的测试

叙述了利用硅悬臂梁和两端固定梁微构件进行硅微薄膜材料的弹性模量和残余内应力的测试方法。本方法利用简单的光学装置,通过测量悬臂梁和两端固定梁的一阶谐振频率,分别求弹性模量和残余内应力。本方法测量系统简单,试样制作方便。本试验获得（100）面<110>方向单晶硅微薄膜的弹性模量为128GPa,残余内应力为74.7MPa.     

Development of dual-probe atomic force microscopy system using optical beam deflection sensors with obliquely incident laser beams

We developed a dual-probe (DP) atomic force microscopy (AFM) system that has two independently controlled probes. The deflection of each cantilever is measured by the optical beam deflection (OBD) method. In order to keep a large space over the two probes for an objective lens with a large numerical aperture, we employed the OBD sensors with obliquely incident laser beams. In this paper, we describe the details of our developed DP-AFM system, including analysis of the sensitivity of the OBD sensor for detection of the cantilever deflection. We also describe a method to eliminate the crosstalk caused by the vertical translation of the cantilever. In addition, we demonstrate simultaneous topographic imaging of a test sample by the two probes and surface potential measurement on an α-sexithiophene (α-6T) thin film by one probe while electrical charges were injected by the other probe.