Surface characteristics and tribology study of metal oxide thin films

Abstract

Microcrystalline high quality undoped ZnO thin films were deposited on Si(100) and Corning 1737F glass substrates by a dc magnetron sputtering system. Surface and mechanical properties of ZnO thin films deposited under different deposition conditions (thickness, deposition rate and plasma composition) were investigated. Atomic force microscopy, nanoindentation techniques and scratch tests have been carried out. The lateral grain radius was between 50 and 160 nm. Surface roughness was found to vary from 1·3 to 10·3. In order to measure the real hardness of ZnO thin films grown on Si(100) and glass Continuous Stiffness Measurement technique was used. The hardness was found to be between 11 and 13 GPa for the polycrystalline ZnO almost five times larger than for the corresponding single crystalline material, while scratch tests verified a film structure, thickness, and surface morphology dependency on the mechanical properties for these metal oxide thin films.     

应用L-MBE方法制备ZnO薄膜的结构和光学特性

用激光分子束外延(Laser Molecular Beam Epitaxy,L-MBE)设备在p型Si(111)衬底上制备了不同衬底温度和不同氧压的ZnO薄膜,用X射线衍射仪(XRD)和原子力显微镜(AFM)分别对薄膜的结构和形貌进行了分析,用He-Cd激光(325nm)激发的光致发光测试系统对薄膜进行了荧光光谱分析。研究发现,在衬底温度为400℃,氧压1Pa左右所制备的ZnO薄膜表面比较均匀致密,晶粒生长较充分,有较高的结晶质量和发光强度。ZnO薄膜的近带边发射与薄膜的结晶质量和化学配比均有关系。     

Multifractal analysis of Mg-doped ZnO thin films deposited by sol–gel spin coating method

A multifractal analysis has been performed on the 3D (three-dimensional) surface microtexture of magnesium-doped zinc oxide (ZnO:Mg) thin films with doping concentration of 0, 2, 4, and 5%. Thin films were deposited onto the glass substrates via the sol–gel spin coating method. The effect of magnesium doping, on the crystal structure, morphology, and band gap for ZnO:Mg thin films has been analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV–Vis spectroscopy. It has been observed that the surface of ZnO thin films is multifractal in nature. However, multifractality and complexity observed to decrease with increasing content of Mg in ZnO thin films due to formation of islands on the surface in accordance with Volmer–Weber growth mechanism. The investigations revealed that crystallinity, microtexture, morphology, and optical properties of the thin films can be tuned by controlling the Mg content within the ZnO lattice. In particular, their optical band gap energies were 3.27, 3.31, 3.34, and 3.33 eV at 0, 2, 4, and 5%, respectively. The prepared thin films of ZnO:Mg with tuned characteristics would have promising applications in optoelectronic devices.     

Al、Sn掺杂对于ZnO薄膜微结构及光学特性的影响

采用真空电子束蒸发金属薄膜及后续热氧化技术在石英衬底上分别制备出了ZnO、Al∶ZnO以及Sn∶ZnO薄膜。通过X射线衍射仪(XRD),紫外-可见分光光度计和原子力显微镜(AFM)等分析仪器对比研究了Al、Sn掺杂对ZnO薄膜结晶质量、光学性质及表面形貌的影响。测试结果表明,Al、Sn掺杂可以使薄膜结晶质量得到提高,薄膜应力部分释放,薄膜表面的粗糙度也相应增加,掺杂对薄膜光学带隙的影响在一定程度取决于金属薄膜的氧化程度,氧化充分可以使光学带隙变宽,反之则变窄。     

Study on the c-axis preferred orientation of ZnO film on various metal electrodes

ZnO thin film was deposited on various metal electrodes by reactive sputtering, and c-axis preferred orientation of the film has been studied. ZnO, which has high piezoelectricity, is promising for oscillators or filter devices such as surface acoustic wave (SAW) device, gas sensor, and film bulk acoustic resonator (FBAR). But, for the application of ZnO film for these devices, the film should be grown with c-axis normal to the electrode. In this study, Pt, Al, and Au were deposited on Si wafer, and the surface roughness and crystal structure of the ZnO film on the electrode were investigated using AFM, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Columnar structures of ZnO films were grown with c-axis normal to all electrodes, and among them Pt electrode showed the highest preferred orientation of ZnO film.     

Influence of substrate orientation on the morphologyand orientation of LaNiO3 thin films

LaNiO₃ thin films were successfully prepared by a chemical method from citrate precursors. The LNO precursor solution was spin‐coated onto Si (100) and Si (111) substrates. To obtain epitaxial or highly oriented films, the deposited layers were slowly heated in a gradient thermal field, with a heating rate of 1° min^?1, and annealed at 700°C. The influence of different substrate orientations on the thin film morphology was investigated using atomic force microscopy and X‐ray diffraction analysis. Well‐crystallized films with grains aligned along a certain direction were obtained on both substrates. Films deposited on both substrates were very smooth, but with a different grain size and shape depending on the crystal orientation. Films deposited on Si (100) grew in the (110) direction and had elongated grains, whereas those on Si (111) grew in the (211) direction and had a quasi‐square grain shape.     

Cross-sectional atomic force microscopy imaging of polycrystalline thin films

Atomic force microscopy (AFM) can be used to image cross-sections of thin-film samples. So far, however, it has mainly been used to study cross-sections of epitaxial systems or integrated circuits on crystalline substrates. In this paper, we show that AFM is a powerful tool to image fractured cross-sections of polycrystalline thin films deposited on crystalline and non-crystalline substrates, yielding unique information on the three-dimensional properties of the cross-sections, with a spatial resolution in the nm range. Original images of three different heterostructure systems are presented: Si(wafer)/SnO2/CdS/CdTe, glass/Mo/Cu(In,Ga)Se2,/CdS/ZnO, and glass/SnO2/WO3. We discuss the results by comparing AFM and scanning electron microscopy (SEM) images, and explain, for the different materials, why the AFM provides useful additional information.     

ZnO薄膜非线性光学特性的实验研究

利用金属有机化学气相沉积(MOCVD)技术在蓝宝石衬底上生长一层高质量的ZnO薄膜。为了考察沉积温度对样品的非线性特性的影响,在200~500 ℃生长了一系列ZnO薄膜。用X射线衍射谱(XRD)及扫描电镜(SEM)对样品结构进行了评价。以Nd:YAG激光器输出的1.06 μm的激光为基频光,对ZnO薄膜样品的二阶及三阶非线性光学特性进行了实验研究。实验发现,对于250 ℃沉积温度的样品有较强的非线性效应,实验测得的二阶非线性极化张量 χ ⁽²⁾_ZZZ=9.2 pm/V, 三阶有效非线性系数χ⁽³⁾=5.28×10^－20 m²/V²。     

Morphology and amine accessibility of (3-aminopropyl) triethoxysilane films on glass surfaces

3-Aminopropyl) triethoxysilane (APTES) is commonly used to functionalize glass substrates because it can form an amine-reactive film that is tightly attached to the surface. In this study, we investigated the morphology and chemical reactivity of APTES films prepared on glass substrates using common deposition techniques. Films were prepared using concentrated vapor-phase deposition, dilute vapor-phase deposition, anhydrous organic-phase deposition and aqueous-phase deposition. All films were annealed, or cured, at 150 degrees C. The morphology of the films was quantified by fluorescence and by atomic force microscopy (AFM). The optical equivalent of the AFM images was computed and then used to directly compare optical and AFM images. Reactive amine density was determined by a picric acid assay and by a method that employed N-succinimidyl 3-[2-pyridyldithio]-propionamido (SPDP) cross-linked rhodamine. Fluorescence and AFM images showed that silane films prepared from dilute vapor-phase and aqueous-phase deposition were more uniform and had fewer domains than those deposited by the other methods. The ratio of picric acid-accessible amino groups to SPDP cross-linked rhodamine-accessible groups varied with the preparation method, suggesting reactant size-dependent difference in amine accessibility. We found a larger number of accessible amino groups on films prepared by vapor-phase deposition than on those prepared from solution deposition. The dilute vapor-phase deposition technique produced relatively few domains, and it should be a good choice for bioconjugation applications. There were appreciable differences in the films produced by each method. We suggest that these differences originate from differences in film rearrangement during annealing.     

SEM and AFM studies of dip‐coated CuO nanofilms

Cupric oxide (CuO) semiconducting thin films were prepared at various copper sulfate concentrations by dip coating. The copper sulfate concentration was varied to yield films of thicknesses in the range of 445–685 nm by surface profilometer. X‐ray diffraction patterns revealed that the deposited films were polycrystalline in nature with monoclinic structure of (?111) plane. The surface morphology and topography of monoclinic‐phase CuO thin films were examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Surface roughness profile was plotted using WSxM software and the estimated surface roughness was about ～19.4 nm at 30 mM molar concentration. The nanosheets shaped grains were observed by SEM and AFM studies. The stoichiometric compound formation was observed at 30 mM copper sulfate concentration prepared film by EDX. The indirect band gap energy of CuO films was increased from 1.08 to 1.20 eV with the increase of copper sulfate concentrations. Microsc. Res. Tech., 2013. © 2012 Wiley Periodicals, Inc.     

Characterization of lead zirconate titanate--lanthanum ruthenate thin film structures prepared by chemical solution deposition

In this work, the results of compositional and microstructural analysis of lead zirconate titanate--lanthanum ruthenate thin film structures prepared by chemical solution deposition are discussed. The cross-section transmission electron microscope (TEM) micrographs of the La-Ru-O film deposited on a SiO2/Si substrate and annealed at 700 degrees C revealed RuO2 crystals embedded in a glassy silicate matrix. When the La-Ru-O film was deposited on a Pt/TiO2/SiO2/Si substrate, RuO2 and La4Ru6O19 crystallized after annealing at 700 degrees C. After firing at 550 degrees C randomly oriented lead zirconate titanate (PZT) thin films crystallized on the La-Ru-O/SiO2/Si substrate, while on La-Ru-O/Pt/TiO2/SiO2/Si substrates PZT thin films with (111) preferred orientation were obtained. No diffusion of the Ru atoms in the PZT film was found. Ferroelectric response of PZT thin films on these substrates is shown in comparison with the PZT film deposited directly on the Pt/TiO2/SiO2/Si substrate without a La-Ru-O layer.     

Dependence of surface morphology on molecular structure and its influence on the properties of OLEDs

Most organic light-emitting diodes (OLEDs) have a multilayer structure composed of organic layers such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) and an electron injection layer (EIL) sandwiched between two electrodes. The organic layers are thin solid films with a thickness from a few nano meters to a few tenths nano meter, respectively. Surface morphology of an organic thin solid film in OLEDs depends on the molecular structure of the organic material and has an affect on device performance. To analyze the effect of surface morphology of an organic thin solid film on fluorescence and electroluminescence (EL) properties, thin solid films of 4-(dicyanomethylene)-2-methyl-6-(julolidin-4-yl-vinyl)-4H-pyran (DCM2) and new red fluorophores, (2E,2′E)-3,3′-[4,4″-bis(dimethylamino)-1,1′:4′,1″-terphenyl-2′,5′-diyl]bis[2-(2-thienyl)acrylonitrile] (ABCV-Th) and (2Z,2′Z)-3,3′-[4,4″-bis(dimethylamino)-1,1′:4′,1″-terphenyl-2′,5′-diyl]bis(2-phenylacrylonitrile) (ABCV-P) were investigated by atomic force microscopy (AFM). The samples for EL and AFM measurement were fabricated by the high-vacuum thermal deposition (8×10⁻⁷ Torr) of organic materials onto the surface of indium tin oxide (ITO)-coated glass substrate, in which the layer structures of samples for AFM measurement and those for EL measurement were ITO/NPB (40 nm)/red emitters (80 nm) and ITO/NPB (40 nm)/red emitters (80 nm)/BCP (30 nm)/Liq (2 nm)/Al (100 nm), respectively. The analysis based on AFM measurements well supported that the photoluminescence properties and the device performance were very much dependent upon surface morphology of an organic thin layer.     

透明导电ITO薄膜的制备及光电特性的研究

采用溶胶-凝胶方法以In（NO3）3.4·5H2O和SnCl4·5H2O为前驱物,用提拉法在石英玻璃基体上制备了ITO透明导电薄膜。详细研究了不同掺Sn比例、不同金属离子浓度、不同提拉速度、不同烘烤温度对ITO薄膜光电特性的影响。结果表明,提拉法制备的薄膜在热处理过程中由凝胶状态向结晶态逐渐转变,方电阻随热处理温度的升高而降低;导电率随薄膜厚度的增加呈非线性增加。     

Study on the c-axis preferred orientation of ZnO film on various metal electrodes

ZnO thin film was deposited on various metal electrodes by reactive sputtering, and c-axis preferred orientation of the film has been studied. ZnO, which has high piezoelectricity, is promising for oscillators or filter devices such as surface acoustic wave (SAW) device, gas sensor, and film bulk acoustic resonator (FBAR). But, for the application of ZnO film for these devices, the film should be grown with c-axis normal to the electrode. In this study, Pt, Al, and Au were deposited on Si wafer, and the surface roughness and crystal structure of the ZnO film on the electrode were investigated using AFM, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Columnar structures of ZnO films were grown with c-axis normal to all electrodes, and among them Pt electrode showed the highest preferred orientation of ZnO film.     

Influence of Mg doping on the morphology and optical properties of ZnO films for enhanced H2 sensing

Highly oriented ZnO and Mg doped ZnO thin films were fabricated on Al₂O₃ substrate by sputtering at room temperature. The effect of Mg doping on the structural, optical, and morphological properties of ZnO film was investigated. The intensity of (002) peak in X‐ray diffraction measurements revealed the influence of Mg doping on the crystallinity and orientation of ZnO film. Photoluminescence (PL) results show that the Ultraviolet (UV) emission peak was shifted to lower wavelength side for Mg:ZnO film indicating the possibility for quantum confinement. UV–vis–NIR optical absorption revealed an improvement in optical transmittance from 70 to 85%, and corresponding optical band gap from 3.25 to 3.54 eV. Atomic force microscope (AFM) images revealed the nano‐size particulate microstructure of the films. The surface topography of Mg doped ZnO film confirmed decreased grain size with large surface roughness and increased surface area, favorable for sensing. Pure ZnO and Mg doped ZnO film were used as active layer and tested for its sensing performance to hydrogen. Compared to undoped ZnO, 22 at.% Mg doped ZnO film showed much higher sensor response to H₂ at a concentration as low as 200 ppm and at a lower operating temperature of 180°C. A linear sensor response was observed for H₂ concentration in the range of 100–500 ppm. Microsc. Res. Tech. 76:1118–1124, 2013. © 2013 Wiley Periodicals, Inc.     

A tribological study of kinetically influenced ultrathin Au and Cu metal overlayers grown on dendrimer mediated Si

Evidence is presented here for deposition kinetic energy influences on the wear properties of Au and Cu films deposited by evaporation and sputtering on clean and poly(amidoamine) (PAMAM) dendrimer modified SiO _x substrates. Ramped load nanoscratch tests show increased resistance to wear in the presence of the dendrimer monolayer. Nanoscratch profiles indicate that the critical load to failure (scratch bearing capacity) is increased in the presence of a dendrimer interlayer. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis of the wear tracks show that following film failure plowing is the predominant mechanism of wear for sputtered or evaporatively deposited Au. No obvious changes in the wear properties (a pure cutting mechanism) of Cu thin films are observed upon changing the kinetic energy of the incoming metal.     

Influence of deposition temperature and pressure on microstructure and tribological properties of arc ion plated Ag films

The films deposited at low temperature(LT-films) have increasingly attracted theoretical and technical interests since such films exhibit obvious difference in structure and performances compared to those deposited at room temperature.Studies on the tribological properties of LT-films are rarely reported in available literatures.In this paper,the structure,morphology and tribological properties of Ag films,deposited at LT(166 K) under various Ar pressures on AISI 440C steel substrates by arc ion plating(AIP),are studied by X-ray diffraction(XRD),atomic force microscopy(AFM) and a vacuum ball-on-disk tribometer,and compared with the Ag films deposited at RT(300 K).XRD results show that(200) preferred orientation of the films is promoted at LT and low Ar pressure.The Crystallite sizes are 70 nm-80 nm for LT-Ag films deposited at 0.2 Pa and 0.8 Pa and larger than 100 nm for LT-Ag films deposited at 0.4 Pa and 0.6 Pa,while they are 55 nm-60 nm for RT-Ag films deposited at 0.2 Pa-0.6 Pa and 37 nm for RT-Ag films deposited at 0.8 Pa.The surfaces of LT-Ag films are fibre-like at 0.6 Pa and 0.8 Pa,terrace-like at 0.4 Pa,and sphere-like at 0.2 Pa,while the surfaces of RT-Ag films are composed of sphere-like grains separated by voids.Wear tests reveal that,due to the compact microstructure LT-Ag films have better wear resistances than RT-Ag film.These results indicate that the microstructure and wear resistance of Ag films deposited by AIP can be improved by low temperature deposition.     

The Effect of Steel Hardness on the Performance of ZDDP Antiwear Films: A Multi-Technique Approach

X-ray absorption near-edge structure (XANES) analysis has been used to characterize the chemistry of antiwear films formed in a mineral base oil containing a zinc dialkyl dithiophosphate (ZDDP) additive. These films were formed by rubbing the AISI 1095 steel samples under a reciprocating boundary contact. The steel samples were tempered to produce different Vickers hardness values. The phosphorus L-edge XANES spectra show that these films differ slightly in their chemical nature, with longer chain polyphosphates being formed on samples with higher hardness value. The surface morphology of the films was investigated using Atomic force microscopy (AFM) and the film thickness was probed by Focussed ion beam and Scanning electron microscopy (FIB/SEM) techniques. Furthermore, the nanomechanical properties of these antiwear films were investigated by nanoindentation methods. Tribological measurements of the coefficient of friction (μ) and wear scar width (WSW) indicate that the poorest antiwear film was formed on the softest substrate, which exhibited the largest WSW and the highest average μ. FIB/SEM images show that the thicknesses of the antiwear pads and the degree of damage on the substrates both change with the hardness value of the samples.     

Measurements of tribological properties of poly(pyrrole) thin film bearings

We report the results of a recent study on the tribological properties of electropolymerised thin films at light loads and low speeds. Poly(pyrrole) films incorporating different counter-ions have been electrochemically deposited onto gold electrodes on the plano-convex glass substrates and studied extensively. The measuring apparatus has been greatly improved from that reported earlier and now provides simultaneous monitoring of frictional force and wear. High precision capacitive gauging is employed to provide high resolutions of frictional force of better than 100 μN and height variation (wear) of 2 nm. A large number of specimens of poly(pyrrole) grown from five different counter-ions were prepared and their performances evaluated. The film morphology of each type of film was examined by atomic force microscopy (AFM) for control of the variability of film formation. Results are presented for the friction coefficients and wear rates observed for the films typically at a load of 2 N and a sliding speed of 5 mm s⁻¹. The effects of normal loading force and sliding speed on the friction coefficient are also discussed with a load range of 0.2–5 N and a sliding speed up to 30 mm s⁻¹.     

Differences in the nanoscale electrical properties of GaN films grown on sapphire and ZnO substrates by molecular beam epitaxy

Gallium nitride (GaN) films were grown on sapphire and zinc oxide (ZnO) single crystal substrates using plasma‐assisted molecular beam epitaxy. As ZnO for GaN have a better lattice match, the coverage ratio of the GaN (002) plane on the ZnO substrate was significantly higher by about 45%. According to conducting atomic force microscopy and scanning surface potential microscopy measurements, the surface of GaN films grown on the ZnO substrate had two excellent physical characteristics: (a) an 18% reduction of the high contact current region, and (b) a highly uniform work function distribution. Therefore, for future applications in GaN‐based light‐emitting diodes, the use of ZnO as a substrate will prolong the luminescence lifetime and enhance the luminescent monochromaticity.