Modification of composite hardness models to incorporate indentation size effects in thin films

The indentation hardness of copper films of thickness 25 to 1400 nm on oxidized silicon substrates is determined by nanoindentation. The load-displacement curves are analysed using the Oliver and Pharr method. An indentation size effect is observed at low relative indentation depths for the copper films. Composite hardness models are applied to the data without an indentation size effect and the Korsunksy and Puchi-Cabrera models are found to give very good fits to this data. The Nix and Gao mechanism based strain gradient plasticity (MSG) model is used to account for the indentation size effect. An attempt is made to modify the existing composite hardness models using the MSG model to incorporate indentation size effect. By modification of both the Korsunsky and Puchi-Cabrera models a good fit to the entire range of data is obtained.     

显微硬度法与纳米压入法测量微米级硬质薄膜硬度的比较

测定了离子束辅助沉积TiN,CrN薄膜的纳米压入硬度（Hnano值）、维氏显微硬度（Hv值）和努氏显微硬度（HK值）。结果发现,HK值比Hv值更接近于Hnano值,相对较为准确。膜的厚度（t）越薄,三种方法测得硬度值差别越大;膜的厚度越厚,差别越小。随着膜的厚度增加,Hk值和Hv值逐渐接近Hnano值。t≈5．0μm时,Hv≈HK≈Hnano对于硬膜软基体模型,如果膜厚〉5．0μm,可以采用显微硬度计较为准确地测量薄膜硬度;膜厚〈5．0μm时,应避免使用显微硬度法而采用纳米压入法。     

Effect of soft substrate on the indentation damage in silicon carbide deposited on graphite

Indentation-induced damage is investigated in silicon carbide (SiC) deposited on graphite substrate. The SiC films have been grown by LPCVD (Low Pressure Chemical Vapor Deposition) method using MTS (CH₃SiCl₃) as a source gas and H₂ as a diluent gas to provide highly dense deposited layer and strong interfacial bonding. The elastic-plastic mismatch is very high to induce distinctive damages in the coating and the substrate layer. The specimens with various coating thicknesses are prepared by changing CVD condition or mechanical polishing. Indentation damages with different sizes are introduced by controlling indentation load in Nanoindentation, Vickers indentation and Hertzian indentation test. Basic mechanical properties such as hardness, toughness, elastic modulus are evaluated against coating thickness. Mechanical properties are sensitive to the indentation load and coating thickness. The results indicate that coating thickness has a vital importance on the design of hard coating/soft substrate system because the soft substrate affects on the mechanical properties.     

Surface softening in silicon by ion implantation

Load-variant microhardness tests have been used to investigate the hardness behaviour of ion-implanted (1 1 1) silicon wafers. A variety of ion doses, energies and species, including n-type, p-type and isovalent ions, have been implanted. At the high doses used (1 to 8 x 10¹⁷ ions cm^2–), all implantations resulted in a surface amorphous layer being formed. The microhardness behaviour has been interpreted in terms of the presence of a surface layer of lower hardness than the substrate. The thickness of this layer has been investigated experimentally using Rutherford backscattering and the results correlated with simple theoretical predictions. Finally, the microhardness behaviour of a soft layer on a harder substrate has been modelled in order to try to predict the hardness variations arising from differing layer thicknesses and different indentation sizes. It is concluded that the amorphous layer produced by implantation appears to show no variation of microhardness with load and has a hardness typically between 400 and 700 Vickers (VHN). Further, the previously reported critical dose of 4 x 10¹⁷ ions cm^–2 necessary to observe significant surface softening seems to correspond to the regime in which the amorphous layer shows a rapid increase with dose.     

Analysis of data from various indentation techniques for thin films intrinsic hardness modelling

Due to the influence of the substrate, direct measurement of the hardness of thin films by standard micro-indentation tests is not always possible. In such situation, determination of the intrinsic film hardness requires the analysis of a set of experimental apparent hardness values obtained for different indentation loads. A number of mathematical equations based on various assumptions were proposed in literature for that purpose.Most of the models were established on the basis of standard Vickers indentation. Using these models to process the data obtained by Knoop indentation does not provide the same intrinsic hardness value, even after Knoop/Vickers standard conversion, than the one obtained from Vickers indentation. The same problem arises when processing the data coming from depth-sensing indentation. A method to obtain comparable hardness values is proposed in the present work by considering an “equivalent” Vickers hardness in the case of Knoop indentations and the corresponding Martens hardness for depth-sensing indentation. This method has been used to determine the intrinsic hardness of titanium nitride film.     

Wedge indentation of a thin film on a substrate based on micromorphic plasticity

In this article, we use the small strain micromorphic plasticity (MP) to study the wedge indentation of a thin film on a substrate and find qualitative agreement with experiments. A two-dimensional plane strain finite element formulation of the entire MP theory framework is outlined. The generalization of the radial return method for modeling the elasto-plastic deformation is presented. The numerical results show that the MP theory is capable of describing the initial fall in hardness at small depth of indentation and then the rise at larger depth for a soft film on a hard substrate. The indentation force and hardness increase with decreasing film thickness for a given depth. It is also shown that the hardness falls monotonically as the indentation depth increases and never approaches a constant for a hard film on a soft substrate. Contrary to the soft film/hard substrate system, the force and hardness diminish with decreasing film thickness for a given depth. Besides, the influences of internal length scale and hardening modulus of the film on hardness predictions are investigated.     

Changing the surface mechanical properties of silicon and α-Al2O3 by ion implantation

Microhardness indentation testing has been used as a means of introducing controlled localized deformation and fracture in both ion-implanted and unimplanted {1 1 1} silicon and {1 0 ˉ1 2} sapphire single crystal surfaces. The microstructural alterations due to implantation with N ₂ ⁺ and Al⁺ into silicon and Y⁺ into sapphire have been characterized using channelled Rutherford backscattering, transmission electron microscopy and electron channelling in the scanning electron microscope. It was found that sapphire only became amorphous at doses ⪞3×10¹⁶ Y⁺cm⁻² which corresponds to a total energy deposition of ∼3×10²³ keV cm⁻³ (∼44 kJ mm⁻³). The low-load microhardness (<50 gf) was found to be sensitive to the thickness of the amorphous layer produced by implantation into both silicon and sapphire. Compared with the parent crystal, this layer was found both to be softer and to behave in a relatively plastic manner with considerable plastic pile-up occurring around indentations in the higher dose specimens. The indentation fracture behaviour was found to be dominated by the presence of implantation-induced compressive stresses. The resulting effects were: (a) a decrease in the size of the radial crack traces (henceK _IC is apparently increased when evaluated using indentation fracture mechanics), (b) a decrease in the frequency of occurrence of lateral break-out in silicon and subsurface lateral cracking in sapphire, (c) initiation of lateral cracks further below the surface in both silicon and sapphire. Thus in general, it is concluded that hardness and surface plasticity are associated with softer amorphous layers whilst indentation fracture modifications are principally stress related.     

Microstructural, mechanical and magnetic properties of shape memory alloy Ni55Mn23Ga22 thin films deposited by radio-frequency magnetron sputtering

The near-stoichiometric Ni₂MnGa ferromagnetic alloys are one of the smart materials, that are of a great interest when they are deposited as a thin film by r.f. sputtering. These thin films of shape memory alloys are prospective materials for micro and nanosystem applications. However, the properties of the shape memory polycrystalline thin films depend strongly on their structure and internal stress, which develop during the sputtering process as well as during the post-deposition annealing treatment. In this study, about 1 μm Ni₅₅Mn₂₃Ga₂₂ thin films were deposited in the range 0,45 to 1,2 Pa of Ar pressure and P = 40 to 120 W. Their composition, crystallographic structure, internal stress and stress gradient, indentation modulus, hardness, deflection induced by magnetic field and magnetic properties were systematically studied as a function of the temperature of the silicon substrate ranging from 298 to 873 K and the vacuum annealing treatment at 873 K for 21,6 ks and 36 ks. A silicon wafer having a native amorphous thin SiO_x buffer layer was used as a substrate. This substrate influences the microstructure of the films and blocks the diffusion process during the heat treatment.The crystal structure of the martensitic phase in each film was changed systematically from bct or 10 M or 14 M. In addition, the evolution of the mechanical properties such as mean stress, stress gradient, roughness, hardness and indentation modulus with the temperature (of substrate or of heat treatment) were measured and correlated to crystal structure and morphology changes.Moreover, it has been shown that it is necessary to associate a high temperature (873 K) annealing during a long time (21 ks and 36 ks) to obtain good ferromagnetic properties. Thus, for the well annealed films (36 ks at 873 K) the magnetostrain is about - 170 ppm for a magnetic field of 1 MA m^- 1 applied along the beams.As a conclusion, the response of free-standing magnetic shape memory films to a magnetic field of 0,2 MA m^- 1 depends strongly on the martensitic structure, internal mechanical stress (mean and gradient) and magnetic properties. The free-standing annealed film at 873 K for 36 ks points out a considerable magnetic actuation associated with bct or 10 M or 14 M martensitic structures.     

Nanoporous YSZ film in electrolyte membrane of Micro-Solid Oxide Fuel Cell

Yttria stabilized zirconia (YSZ) with 8 mol% Y was deposited by reactive magnetron sputtering onto oxidized (100) silicon substrates. It was possible to switch film texture from (111) to (200) by applying a strong RF substrate bias. Transmission electron microscopy showed that the film deposited under bias is porous and exhibits nanoscaled grains, whereas the film deposited without bias is dense and columnar. The ionic conductivity as a function of temperature revealed an activation energy of 1.04 eV. The mechanical stress could be tuned to low values by thermal post-annealing. Using the dense (111) film as electrolyte layer, and the porous (200) film as an interlayer to a porous Pt anode, an open circuit voltage of 0.85 V was obtained in a micro machined fuel cell structure.     

类金刚石碳膜的复合硬度与本征硬度的研究

在综述现有的测量薄膜（涂层）材料本征硬度方法及模型的基础上，采用超显微硬度仪对不同基体经不同工艺条件沉积的类金刚石碳昨合硬度进行了测量，并借助有限元模型得到的经验公式对测量数据进行拟合处理，得出了各种类金刚石碳膜的本征硬度。硬质合金基体上类金刚石膜本度为０２ＧＰａ，硅基体上经不同工艺条件沉积的类金刚石碳膜本征硬度在２０－３０ＧＰａ范围。在对膜／基得合体系进行Ｍｅｙｅｒ定律修正的基础上，首次提出了一     

多孔硅基热敏薄膜的制备与性能

对MEMS用具有绝热性能的多孔硅基底上沉积的热敏感薄膜进行了研究．首先用电化学方法制备多孔硅,分别在多孔硅基底和硅基底上通过溅射镀膜方法沉积氧化钒、Cu、Au热敏薄膜,测试多孔硅基底和硅基底上的氧化钒及金属薄膜电阻的热敏特性．结果表明,在多孔硅基底表面沉积的热敏薄膜具有与硅基表面热敏薄膜同样的热敏特性且表现出更高的灵敏度;此外,对沉积在不同制备条件得到的多孔硅上的氧化钒薄膜电阻热敏特性进行比较,发现随着孔隙率和厚度的增加,多孔硅的绝热性能提高,其上沉积的氧化钒薄膜电阻热敏特性增强．     

Effective mechanical properties of layered rough surfaces

In contact mechanics of layered rough surfaces, found in various systems such as magnetic storage devices and micro/nanoelectromechanical systems, it is of interest to calculate effective elastic modulus and hardness so as to obtain contact parameters using simple analyses for homogeneous surfaces. In this study, effective elastic modulus and hardness of layered rough surfaces are defined on the basis of real area of contact. A numerical model developed by the first author to simulate the contact of layered rough surfaces is used to derive these equations. Completely nondimensionalized empirical equations for these effective mechanical properties are presented. Separate equations are developed for the contact of a single conical asperity on a flat surface, a single spherical asperity on a flat surface, and for multiple asperity contact between two rough surfaces. These equations establish the dependence of effective mechanical properties on indentation depth, layer thickness, hardness and elastic modulus ratios of layer and substrate and surface roughness/asperity geometry. Comparisons of values predicted by the equations with experimentally obtained results are presented. Contact stress contours obtained from this model are analyzed to get a better understanding of the mechanics of contact.     

压痕硬度测试法的主要研究内容及其应用

详细分析了压痕硬度测试方法自发展以来所研究的主要内容,即建立不同硬度之间的关系、硬度与弹性性能的关系、硬度与强度的关系、硬度与蠕变性能的关系、材料显微组织对硬度的影响以及硬度在薄膜力学测试中的应用等。其中,研究重点主要集中在建立硬度与力学性能参量之间的数学关系方面,即通过压痕硬度测试中获取的有关数据来得到相关的力学参量。同时提出了压痕硬度测试法的研究现状及存在的主要问题。     

Photonic polymer replicas from distributed Bragg reflectors structured porous silicon

Well defined 1-dimentional (1-D) photonic crystals of polymer replicas have been successfully obtained. DBR porous silicon containing nanometer-scale pores are prepared by an anodic electrochemical etch of p(++)-type silicon wafer. The resulting DBR porous silicon film removed from the substrate by applying an electropolishing current has been thermally oxidized in the furnace at 400 degrees C for 3 h. Oxidized DBR PSi/polystyrene composite films are prepared by casting of polymer solution onto a free-standing porous silicon photonic crystal layer. Flexible photonic polymer replicas have been prepared after the removal of oxidized DBR PSi matrix in HF/H2O mixture solution. Polymer replicas exhibit a sharp resonance in the reflectivity spectrum. Optical characteristics of photonic polymer replica indicate that the surface of polymer film has a negative structure of DBR PSi. This replica is stable in aqueous solutions for several days without any degradation.     

Mechanical properties of amorphous and microcrystalline silicon films

Hydrogen-free amorphous silicon (a-Si) films with thickness of 4.5-6.5 μm were prepared by magnetron sputtering of pure silicon. Mechanical properties (hardness, intrinsic stress, elastic modulus), and film structure (Raman spectra, electron diffraction) were investigated in dependence on the substrate bias and temperature. The increasing negative substrate bias or Ar pressure results in simultaneous reducing compressive stress, the film hardness and elastic modulus. Vacuum annealing or deposition of a-Si films at temperatures up to 600 °C saving amorphous character of the films, results in reducing compressive stress and increasing the hardness and elastic modulus. The latter value was always lower than that for monocrystalline Si(111). The crystalline structure (c-Si) starts to be formed at deposition temperature of ∼ 700 °C. The hardness and elastic modulus of c-Si films were very close to monocrystalline Si(111). Phase transformations observed in the samples at indentation depend not only on the load and loading rate but also on the initial phase of silicon. However, the film hardness is not too sensitive to the presence of phase transformations.     

On the factors affecting the critical indenter penetration for measurement of coating hardness

The nanoindentation test is the only viable approach to assess the properties of very thin coatings (<1 μm) since it can operate at the required scale and provides a fingerprint of the indentation response of the coating/substrate system. To measure the hardness of the coating only it is traditionally assumed that, as a rule-of-thumb, when the relative indentation depth (RID, i.e. the penetration divided by the coating thickness) is less than 0.1, the substrate will not affect the measured hardness of the coating. However, it is found that this rule is too strict for some and too loose for other coated systems. In this paper we present a comprehensive investigation of the factors influencing the critical relative indentation depth (CRID) using finite element simulation. The CRID is very sensitive to tip radius for soft coatings on hard substrates. For most coating/substrate combinations at reasonable penetration depths the 0.1 rule-of-thumb is a safe estimate. It is shown that the elastic property mismatch between coating and substrate also has an important effect on the measured hardness and this means that the Oliver and Pharr method generally used to extract hardness from nanoindentation data may give inaccurate results in coating/substrate systems with significant elastic mismatch.     

Tribological properties of oxidised boride coatings grown on AISI 4140 steel

In this study, we investigated the wear behaviour of borided and borided + short-duration oxidized AISI 4140 steel. Boronizing was carried out in a slurry salt bath consisting of borax, boric acid and ferro silicon. Also, short-duration oxidizing treatment was applied to borided steel to produce glass-like boron oxide layer. The short-duration oxidizing was performed at 750 °C for 3 min. Optical and scanning electron microscope (SEM) cross-sectional examinations of borided layer revealed a needle-shaped morphology. The presence of non-oxide boride type ceramics FeB and Fe₂B formed on the surface of steel substrate was confirmed by classical metallographic technique and X-ray diffraction (XRD) analysis. The hardness of borides formed on the surface of steel substrate and unborided steel substrate were 1446–1690 HV_0.1 and 280 HV_0.1, respectively. The wear behaviour of borided steel were characterised by using a pin-on-disc technique. The borided and short-duration oxidized steels, in the form of pins were allowed to slide against a hard AISI 440C stainless steel disc (63 HRc). The sliding velocity of 1 m s^− 1 for borided and short-duration oxidized steel and the nominal load on the pin was 20 N. The highest wear rates were observed on disc slide against the base steel, whilst the lowest wear rates occurred during sliding against the borided and short-duration oxidized steel surfaces. It was observed that the friction coefficient of unborided (hardened + tempered) and borided steels ranged from 0.50 to 0.60, but after short-duration oxidizing, the friction coefficient of borided steel was dropped to 0.12.     

Effect of Loading Rate Upon Conventional Ceramic Microindentation Hardness

The world standards for conventional ceramic hardness have varying requirements for control of loading rate during the indentation cycle. A literature review suggests that loading rate may affect measured hardness in some instances. In view of the uncertainty over this issue, new experiments over a range of indentation loading rates were performed on a steel, sintered silicon carbide, and an aluminum oxynitride. There was negligible effect upon Vickers hardness when loading rate was varied by almost four orders of magnitude from approximately 0.03 N/s to 10 N/s.     

Polymeric waveguides using oxidized porous silicon cladding for optical amplification

We report on a new hybrid approach to realize optical slab waveguides for optical amplification purposes. The structure consists of a dye-doped polymer core (PMMA) deposited over an oxidized porous silicon (PS) cladding layer formed on a silicon wafer. The very low refractive index (n = 1.16) achievable in the cladding allows obtaining monomodal behavior with high confinement factors (Γ_TE = 96%) even for very thin cores (400 nm). Optically excited guided luminescence shows stimulated emission, strong line narrowing and a clear threshold and superlinear behavior with pump energy. By means of the variable stripe length (VSL) technique, values of net optical gain up to 113 dB/cm (constant over 3 mm) and absolute amplification values up to 34 dB have been measured at 694 nm when pumping with 80 mJ/cm² energy pulses. These results validate the use of oxidized PS as a cladding layer in silicon photonics.