A nanoscratch method for measuring hardness of thin films

Thin solid films were extensively used in the making of solar cells, cutting tools, magnetic recording devices, etc. As a result, the accurate measurement of mechanical properties of the thin films, such as hardness and elastic modulus, was required. The thickness of thin films normally varies from tens of nanometers to several micrometers. It is thus challenging to measure their mechanical properties. In this study, a nanoscratch method was proposed for hardness measurement. A three-dimensional finite element method (3-D FEM) model was developed to validate the nanoscratch method and to understand the substrate effect during nanoscratch. Nanoindentation was also used for comparison. The nanoscratch method was demonstrated to be valuable for measuring hardness of thin solid films.

Hardness of silicon nitride thin films characterised by nanoindentation and nanoscratch deconvolution methods

Plasma enhanced chemical vapour deposition silicon nitride thin films are widely used in microelectromechanical system devices as structural materials because the mechanical properties of those films can be tailored by adjusting deposition conditions. However, accurate measurement of the mechanical properties, such as hardness, of films with thicknesses at nanometric scale is challenging. In the present study, the hardness of the silicon nitride films deposited on silicon substrate under different deposit conditions was characterised using nanoindentation and nanoscratch deconvolution methods. The hardness values obtained from the two methods were compared. The effect of substrate on the measured results was discussed.

Nanoscratch and nanowear testing of TiN coatings on M42 steel

Constant load, progressive load and multipass nanoscratch (nanowear) tests were carried out on 500 and 1500 nm TiN coatings on M42 steel chosen as model systems. The influences of film thickness, coating roughness, scratch direction relative to the grinding grooves on the critical load in the progressive load test and number of cycles to failure in the wear test have been determined. Progress towards the development of a suitable methodology for determining the scratch hardness from nanoscratch tests is discussed. © 2011 W. S. Maney & Son Ltd.

Plasma polymerised thin films for flexible electronic applications

The significant advancement and growth of organic and flexible electronic applications demand materials with enhanced properties. This paper reports the fabrication of a nonsynthetic polymer thin film using radio frequency plasma polymerisation of 3,7-dimethyl-1,6-octadien-3-ol. The fabricated optically transparent thin film exhibited refractive index of approximately 1.55 at 500 nm and rate of deposition was estimated to be 40 nm/min. The surface morphology and chemical properties of the thin films were also reported in this paper. The optical band gap of the material is around 2.8 eV. The force of adhesion and Young's modulus of the linalool polymer thin films were measured using force-displacement curves obtained from a scanning probe microscope. The friction coefficient of linalool polymer thin films was measured using the nanoscratch test. The calculated Young's modulus increased linearly with increase in input power while the friction coefficient decreased.

Nanotribological and nanomechanical properties of plasma-polymerized polyterpenol thin films

Organic plasma polymers are currently attracting significant interest for their potential in the areas of flexible optoelectronics and biotechnology. Thin films of plasma-polymerized polyterpenol fabricated under varied deposition conditions were studied using nanoindentation and nanoscratch analyses. Coatings fabricated at higher deposition power were characterized by improved hardness, from 0.33 GPa for 10 W to 0.51 GPa for 100 W at 500-μN load, and enhanced wear resistance. The elastic recovery was estimated to be between 0.1 and 0.14. Coatings deposited at higher RF powers also showed less mechanical deformation and improved quality of adhesion. The average (R a) and root mean square (R q) surface roughness parameters decreased, from 0.44 nm and 0.56 nm for 10 W to 0.33 nm and 0.42 nm for 100 W, respectively.

Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.

Structural, optical and nanomechanical properties of (1 1 1) oriented nanocrystalline ZnTe thin films

Structural, optical and nanomechanical properties of nanocrystalline Zinc Telluride (ZnTe) films of thickness upto 10 microns deposited at room temperature on borosilicate glass substrates are reported. X-ray diffraction patterns reveal that the films were preferentially oriented along the (1 1 1) direction. The maximum refractive index of the films was 2.74 at a wavelength of 2000 nm. The optical band gap showed strong thickness dependence. The average film hardness and Young's modulus obtained from load-displacement curves and analyzed by Oliver-Pharr method were 4 and 70 GPa respectively. Hardness of (1 1 1) oriented ZnTe thin films exhibited almost 5 times higher value than bulk. The studies show clearly that the hardness increases with decreasing indentation size, for indents between 30 and 300 nm in depth indicating the existence of indentation size effect. The coefficient of friction for these films as obtained from the nanoscratch test was ~0.4.

Structural, optical and nanomechanical properties of (1 1 1) oriented nanocrystalline ZnTe thin films

Structural, optical and nanomechanical properties of nanocrystalline Zinc Telluride (ZnTe) films of thickness upto 10 microns deposited at room temperature on borosilicate glass substrates are reported. X-ray diffraction patterns reveal that the films were preferentially oriented along the (1 1 1) direction. The maximum refractive index of the films was 2.74 at a wavelength of 2000 nm. The optical band gap showed strong thickness dependence. The average film hardness and Young's modulus obtained from load-displacement curves and analyzed by Oliver-Pharr method were 4 and 70 GPa respectively. Hardness of (1 1 1) oriented ZnTe thin films exhibited almost 5 times higher value than bulk. The studies show clearly that the hardness increases with decreasing indentation size, for indents between 30 and 300 nm in depth indicating the existence of indentation size effect. The coefficient of friction for these films as obtained from the nanoscratch test was ~0.4.

Bioactivity and mechanical properties of nickel-incorporated hydrogenated carbon nanocomposite thin films

In this paper, the influence of nickel incorporation on the mechanical properties and the in vitro bioactivity of hydrogenated carbon thin films were investigated in detail. Amorphous hydrogenated carbon (a-C : H) and nickel-incorporated hydrogenated carbon (Ni/a-C : H) thin films were deposited onto the Si substrates by using reactive biased target ion beam deposition technique. The films' chemical composition, surface roughness, microstructure and mechanical properties were investigated by using XPS, AFM, TEM, nanoindentation and nanoscratch test, respectively. XPS results have shown that the film surface is mainly composed of nickel, nickel oxide and nickel hydroxide, whereas at the core is nickel carbide (Ni3C) only. The presence of Ni3C has increased the sp(2) carbon content and as a result, the mechanical hardness of the film was decreased. However, Ni/a-C : H films shows very low friction coefficient with higher scratch-resistance behavior than that of pure a-C : H film. In addition, in vitro bioactivity study has confirmed that it is possible to grow dense bone-like apatite layer on Ni/a-C : H films. Thus, the results have indicated the suitability of the films for bone-related implant coating applications. Copyright (C) 2011 John Wiley & Sons, Ltd.

Structure and mechanical properties of Ti-C films deposited using combination of pulsed DC and normal DC magnetron co-sputtering

Titanium-carbon (Ti-C) thin films of different compositions were prepared by a combination of pulsed DC (for Ti target) and normal DC (for graphite target) magnetron co-sputtering on oxidized silicon and fused quartz substrates. At 33.7 at.% of C content, pure hcp Ti transforms into fcc-TiC with a preferential orientation of (2 2 0) along with (1 1 1) and (2 0 0). A clear transformation in the preferential orientation from (2 2 0) to (1 1 1) has been observed when the C content was increased to 56 at.%. At 62.5 at.% of C, TiC precipitates in an amorphous carbon matrix whereas further increase in C leads to X-ray amorphous films. The cross-sectional scanning electron microscope images reveal that the films with low carbon content consists of columnar grains, whereas, randomly oriented grains are in an amorphous carbon matrix at higher carbon content. A dramatic variation was observed in the mechanical properties such as hardness, H, from 30 to 1 GPa and in modulus, E, from 255 to 25 GPa with varying carbon content in the films. Resistance to plastic deformation parameter was observed as 0.417 for films containing 62.5 at.% of C. Nanoscratch test reveals that the films are highly scratch resistant with a coefficient of friction ranging from 0.15 to 0.04. (C) 2012 Elsevier B.V. All rights reserved.

Micro/Nanomechanical and Tribological Properties of thin Diamond-Like Carbon Coatings

The diamond-like carbon (DLC) films with different thicknesses on 9Crl8 bearing steels were prepared using vacuum magnetic-filtering arc plasma deposition. Vickers indentation. nanoin-dentation and nanoscratch tests were used to characterize the DLC films with a wide range of applied loads. Mechanical and tribological behaviors of these submicron films were investigated and interpreted. The hardnesses of 9Crl8 and DLC, determined by nanoindentation, are approximately 8GPa and 60GPa respectively; their elastic moduli are approximately 25OGPa and 600GPa respectively. The friction coefficients of 9Crl8, DLC. organic coating, determined by nanoscratch, are approximately 0. 35, 0. 20 and 0. 13 respectively. It is demonstrated that nanoindentation and nanoscratch tests can provide more information about the near-surface elastic-plastic deformation, friction and wear properties. The correlation of mechanical properties and scratch resistance of DLC films on 9Crl8 steels can provide an assessment for the load-carrying capacity and wear resistance

Substrate Effects on the Micro/Nanomechanical Properties of TiN Coatings

Nanoindentation and nanoscratch tests were performed for titanium nitride (TiN) coatings on different tool steel substrates to investigate the indentation/scratch induced deformation behavior of the coatings and the adhesion of the coating–substrate interfaces and their tribological property. In this work, TiN coatings with a thickness of about 500 nm were grown on GT35, 9Cr18 and 40CrNiMo steels using vacuum magnetic-filtering arc plasma deposition. In the nanoindentation tests, the hardness and modulus curves for TiN/GT35 reduced the slowest around the film thickness 500 nm with the increase of indentation depth, followed by TiN/9Cr18 and TiN/40CrNiMo. Improving adhesion properties of coating and substrate can decrease the differences of internal stress field. The scratch tests showed that the scratch response was controlled by plastic deformation in the substrate. The substrate plays an important role in determining the mechanical properties and wear resistance of such coatings. TiN/GT35 exhibited the best load-carrying capacity and scratch/wear resistance. As a consequence, GT35 is the best substrate for TiN coatings of the substrate materials tested.

亚微米氮化钛膜的纳米压痕和划痕测定

采用等离子电弧沉积的方法，分别在GT35和40CrNiMo钢上沉积厚约为0.5μm的氮化钛(TiN)膜。为了筛选基材，采用纳米压痕和划痕技术，评价膜基界面结合和固体润滑效果。纳米压痕结果，GT35，40CrNiMo和TiN的纳米硬度/弹性模量的典型值分别约为11.5 GPa/330GPa, 6.0 GPa/210GPa, 30GPa/450GPa。纳米划痕结果，GT35有较理想的膜基结合能力；GT35，40CrNiMo，TiN及其有机膜的磨擦系数分别约为0.25，0.45，0.15, 0.10。同40CrNiMo相比，GT35是较为理想的基体材料。纳米压痕和划痕技术能提供丰富的近表面的弹塑性变形、断裂和磨擦等的信息，是评价亚微米薄膜力学性能的有效手段。

Direct measurement of plowing friction and wear of a polymer thin film using the atomic force microscope

Nanometer-scale plowing friction and wear of a polycarbonate thin film were directly measured using an atomic force microscope (AFM) with nanoscratching capabilities. During the nanoscratch tests, lateral forces caused discrepancies between the maximum forces for the initial loadings prior to the scratch and the unloading after the scratch. In the case of a nanoscratch test performed parallel to the cantilever probe axis, the plowing friction added another component to the moment acting at the cantilevered end compared to the case of nanoindentation, resulting in an increased deflection of the cantilever. Using free-body diagrams for the cases of nanoindentation and nanoscratch testing, the AFM force curves were analyzed to determine the plowing friction during nanoscratch testing. From the results of this analysis, the plowing friction was found to be proportional to the applied contact force, and the coefficient of plowing friction was measured to be 0.56 +/- 0.02. Also, by the combination of nanoscratch and nanoindentation testing, the energetic wear rate of the polycarbonate thin film was measured to be 0.94 +/- 0.05 mm(3)/(N m).

A Comparati ve Study of Mechanical and Tribological Properties of AISI-304 and AISI-316 Submitted to Glow Discharge Nitriding

Mechanical and tribological properties of AISI 304 and AISI 316 stainless steels submitted to glow discharge ion nitriding are reported. The atmosphere was 20:80 - N2:H2 with substrate temperatures ranging from 300 to 500 °C. Treatment at 300 °C produced expanded austenite (γN) in both steels. Increasing the temperature, the phases γ′-Fe4N and ε- Fe2+xN were present and the latter is the major phase for AISI 304. At 500 °C, the CrN phase was also identified in both steels. Hardnesses of about 13-14 GPa at near surface regions were obtained in both steels. Moreover, AISI 316 nitrided at 500 °C has the deepest hard layer. Tribological tests showed that wear can be reduced by up to a factor of six after the nitriding processes, even for a working temperature of 300 °C. The profiles during and after nanoscratch tests did not reveal significant differences after nitriding processes in both steels.