二维材料力学行为的压痕测试

准确了解二维材料的力学性能对于推动其应用具有重要意义, 无基底压痕技术是目前最广泛采用的二维材料力学性能测试方法之一, 本文综述了二维材料压痕研究的最新进展以及所面临的问题, 并对将来的研究工作进行了展望.无基底压痕技术是将二维材料转移到带有沟槽或柱形孔的基底上, 制备二维材料"梁"和"鼓"模型, 然后利用原子力显微镜测量其在压针作用下的载荷--位移关系, 最后通过基于连续介质薄膜导出的压痕响应分析模型拟合实验结果, 估算出二维材料的弹性模量和本征强度.由于二维材料的厚度远小于连续介质薄膜, 来自于压头以及基底孔侧壁的范德华力对二维材料的压痕响应具有显著影响, 造成二维材料与传统压痕分析模型中的基本假设不符, 导致不能准确预测二维材料的弹性模量; 另外, 由于传统压痕模型无法准确描述二维材料在大变形下的非线性行为, 以及由缺陷等引起的应力集中, 导致由压痕测试表征的二维材料(特别是多晶二维材料)本征强度具有较大的偏差. 因此, 一方面需要正确了解由压痕技术获得的二维材料力学性能, 另一方面还需对目前的研究方法做进一步的改进和完善.      

Determining the Elastic Modulus of Compliant Thin Films Supported on Substrates from Flat Punch Indentation Measurements

Instrumented indentation is a technique that can be used to measure the elastic properties of soft thin films supported on stiffer substrates, including polymer films, cellulosic sheets, and thin layers of biological materials. When measuring thin film properties using indentation, the effect of the substrate must be considered. Most existing models for determining the properties of thin films from indentation measurements were developed for metal and dielectric films bonded to semiconductor substrates and have been applied to systems with film-substrate modulus ratios between 0.1 and 10. In the present work, flat punch indentation of a thin film either bonded to or in contact with a substrate is examined using finite element modeling. A broad range of film-substrate modulus ratios from 0.0001 to 1 are investigated. As the substrate is effectively rigid compared to the film when the film-substrate modulus ratio is less than 0.0001, the results are also useful for understanding systems with lower film-substrate modulus ratios. The effects of the contact radius, film thickness, elastic properties, and friction between the film and the substrate on the measured stiffness were quantified using finite element modeling in order to understand how the elastic properties of the film can be extracted from indentation measurements. A semi-analytical model was developed to describe the finite element modeling results and facilitate the use of the results to analyze experimental measurements. The model was validated through analysis of indentation measurements of thin polyethylene sheets that were supported on substrates of various stiffness.     

On the determination of the Young’s modulus of thin films using indentation tests

The main difficulty with the characterization of thin coatings using depth-sensing indentation tests is related to the determination of the contributions of the substrate and the film to the measured properties. In this study, three-dimensional numerical simulations of the Vickers hardness test are used in order to examine the influence of the elastic and plastic properties of the substrate and the film on the composite’s Young’s modulus results. The hardness of the film is equal to or higher than the substrate hardness. A study of the stress distributions and the indentation geometry of composites, film/substrate, was performed, taking into account the relative mechanical properties of the film and substrate. In addition, stress evolution during indentation was studied, in order to quantify the critical indentation depth under which the substrate is not elastically deformed. The accurate evaluation of the Young’s modulus of the films using weight functions is also examined: some of these have previously been proposed and one was introduced for this study. Two different fitting procedures were used to compare the results obtained from eight fictive film/substrate combinations using six weight functions. The first procedure, commonly used, considers the substrate’s modulus as a known parameter in the fitting process. In the second, the film and the substrate’s modulus are considered as unknown variables that are calculated simultaneously during the fitting process. The validity of the conclusions obtained using the fictive materials was checked by applying the weight functions to four real composites.     

基于气压鼓泡法研究石墨烯力学性能

通常假设二维材料为连续介质薄膜,然后采用连续介质薄膜的研究方法进行二维材料力学性能研究,其中气压鼓泡法是一种主要测试方法．但实验观测发现,悬空石墨烯并非处于气压鼓泡测试分析模型中假设的固支边界条件,而是处于一种粘附边界条件：靠近孔壁边界处,有小部分材料通过范德华吸引粘附在基底柱形孔的侧壁上,而且粘附部分可以在极小载荷作用下剥离．这导致石墨烯悬空部分的实际半径大于基底孔半径,即鼓泡实验中的石墨烯是一种松弛薄膜,而非通常认为的预拉伸薄膜．通过有限元数值模拟研究发现,可基于含有名义松弛应变的鼓泡分析模型获得处于粘附边界条件下的石墨烯弹性模量．     

纳米压痕法测磁控溅射铝薄膜屈服应力

为了在考虑残余应力下测量出磁控溅射铝薄膜的屈服应力,提出了一种实验测量方法,通过曲率测试法和球形压头纳米压痕法测出磁控溅射铝薄膜的屈服应力．建立球形压痕力学模型,并用ANSYS对球形压痕进行力学有限元仿真,利用直流磁控溅射技术在硅基上淀积一层1 μm厚的铝薄膜,首先通过曲率测试法测量膜内等双轴残余应力,再利用最小二乘曲线拟合法从薄膜/基底系统的球形压头纳米压痕实验数据中提取出铝薄膜的屈服应力,测得磁控溅射铝薄膜的屈服应力为371 MPa．该方法也可以用来研究其他材料的薄膜和小体积材料的力学特性．     

Analysis of elastic and plastic deformation associated with indentation testing of thin films on substrates

A study has been made of the elastic and plastic deformation associated with submicrometer indentation of thin films on substrates using the finite element method. The effects of the elastic and plastic properties of both the film and substrate on the hardness of the film/substrate composite are studied by determining the average pressure under the indenter as a function of the indentation depth. Calculations have been made for film/substrate combinations for which the substrate is either harder or softer than the film and for combinations for which the substrate is either stiffer or more compliant than the film. It is found, as expected, that the hardness increases with indentation depth when either the yield strength or the elastic modulus of the substrate is higher than that of the film. Correspondingly, the hardness decreases with indentation depth when the yield strength or elastic modulus of the substrate is lower than that of the film. Functional equations have been developed to predict the hardness variation with depth under these different conditions. Finite element simulation of the unloading portion of the load displacement curve permits a determination of the elastic compliance of the film/substrate composite as a function of indentation depth. The elastic properties of the film can be separated from those of the substrate using this information. The results are in good agreement with King's analytical treatment of this problem.     

测量界面软铬层力学性质的纳米压入法

为了测量双层铬的界面软铬层力学性质,提出了化学腐蚀基体法,通过溶解掉基体制备没有基体支撑的自由铬层,将在横截面内线状显示的界面转化为界面表面(铬层与基体相连接的面),避免了横截面不能显示界面表面的缺点。对界面表面进行纳米压入实验和借助于表征薄膜力学性质的表面压入能量法,测得了描述界面软铬层力学性质的弹性模量和压入弹、塑性功等参数。     

用能量法分析层状材料弹性接触问题

利用能量法分析了层状材料（薄膜／基体）弹性接触问题，得到了具有一阶精度的闭合解，给出了求解薄膜弹性模量和泊松比的表达式，并与有限元的数值解进行了比较。二者比较结果表明：在工程材料范围内，理论解与数值解相差在6％以内；同时表明单相材料中剪切模量与弹性模量之间的关系也适用层状材料中的薄膜材料。在数值解的基础上，讨论了薄膜厚度与压头半径的比值对求解精度的影响，发现此比值对精度影响不大。通过对层状材料等效泊松比与等效弹性模量的定义，给出了用压痕实验测定薄膜泊松比与弹性模量的方法。     

Adhesive elastic contact between a symmetric indenter and an elastic film

This paper examines the frictionless adhesive elastic contact problem of a rigid sphere indenting a thin film deposited on a substrate. The result is then used to model the elastic phase of micro-nanoscale indentation tests performed to determine the mechanical properties of coatings and films. We investigate the elastic response including the effects of adhesion, which, as the scale decreases to the nano level, become an important issue. In this paper, we extend the Johnson–Kendall–Roberts, Derjaguin–Muller–Toporov, and Maugis–Dugdale half-space adhesion models to the case of a finite thickness elastic film coated on an elastic substrate. We propose a simplified model based on the assumption that the pressure distribution is that of the corresponding half-space models; in doing so, we investigate the contact radius/film thickness ratio in a range where it is usually assumed the half-space model. We obtain an analytical solution for the elastic response that is useful for evaluating the effects of the film-thickness, the interface film–substrate conditions, and the adhesion forces. This study provides a guideline for selecting the appropriate film thickness and substrate to determine the elastic constants of film in the indentation tests.     

Oliver–Pharr indentation method in determining elastic moduli of shape memory alloys—A phase transformable material

Instrumented indentation test has been extensively applied to study the mechanical properties such as elastic modulus of different materials. The Oliver–Pharr method to measure the elastic modulus from an indentation test was originally developed for single phase materials. During a spherical indentation test on shape memory alloys (SMAs), both austenite and martensite phases exist and evolve in the specimen due to stress-induced phase transformation. The question, “What is the measured indentation modulus by using the Oliver–Pharr method from a spherical indentation test on SMAs?” is answered in this paper. The finite element method, combined with dimensional analysis, was applied to simulate a series of spherical indentation tests on SMAs. Our numerical results indicate that the measured indentation modulus strongly depends on the elastic moduli of the two phases, the indentation depth, the forward transformation stress, the transformation hardening coefficient and the maximum transformation strain. Furthermore, a method based on theoretical analysis and numerical simulation was established to determine the elastic moduli of austenite and martensite by using the spherical indentation test and the Oliver–Pharr method. Our numerical experiments confirmed that the proposed method can be applied in practice with satisfactory accuracy. The research approach and findings can also be applied to the indentation of other types of phase transformable materials.     

A numerical approach to indentation technique to evaluate material properties of film-on-substrate systems

Spherical indentation approach (Lee et al., 2005, Lee et al., 2010) for the evaluation of bulk material properties is extended to that for elastic–plastic properties of film-on-substrate systems. Our interest focuses on single isotropic, metallic, and elastic–plastic film on a substrate, and we do not consider the size effects in plasticity behavior. We first determine the optimal data acquisition location, where the strain gradient is the least and the effect of friction is negligible. Dimensional analysis affords the mapping parameters as functions of normalized indentation variables. An efficient way is further introduced to reduce both the number of analyses and the regression order of mapping functions. The new numerical approach to the film indentation technique is then proposed by examining the finite element solutions at the optimal point. With the new approach, the values of elastic modulus, yield strength, and strain-hardening exponent of film materials are successfully obtained from the spherical indentation tests. We have shown that the effective property ranges such as indenter properties, substrate modulus, and E/E_s ratio can be extended without additional simulations and even loss of accuracy. For other ranges of variables or other properties, which are not dealt with in this study, this methodology is applicable through resetting FEA variables and finding proper normalized parameters.     

有限厚度模型校准二维MoS2的Bimodal-AFM杨氏模量测量

二维材料因其独特的晶体结构、新奇的物理特性和优异的力学性能, 在微纳机电系统、柔性电子器件等诸多领域有着广阔的应用前景. 弹性模量是二维材料的基本力学特性参量之一, 对其器件应用及应变调控有重要影响. 受限于二维结构和原子级厚度特征, 难以实现二维材料弹性模量的精确测量. 双模原子力显微镜的振幅调制-频率调制模式是一种高效测量二维材料杨氏模量的方法, 但刚性衬底对测量结果的影响不可忽视. 本工作通过双模原子力显微镜直接测得衬底与二维硫化钼的杨氏模量分布图, 并基于有限厚度模型对衬底效应进行修正, 得到了样品的本征杨氏模量值. 利用第一性原理计算得到了二维二硫化钼的弹性系数和杨氏模量, 对比发现实验和计算结果相当. 这说明双模原子力显微镜测量是一种可靠的二维材料杨氏模量直接测试方法, 且该方法无需制备悬空二维材料等繁琐步骤, 避免了常规测试中的不足. 本工作为大面积二维材料薄膜力学性能的程序化测试分析以及高通量力学实验数据的统计分析提供了可靠的实验基础.      

Indentation of a hard film on a soft substrate: Strain gradient hardening effects

The strain gradient work hardening is important in micro-indentation of bulk metals and thin metallic films, though the indentation of thin films may display very different behavior from that of bulk metals. We use the conventional theory of mechanism-based strain gradient plasticity (CMSG) to study the indentation of a hard tungsten film on soft aluminum substrate, and find good agreement with experiments. The effect of friction stress (intrinsic lattice resistance), which is important in body-center-cubic tungsten, is accounted for. We also extend CMSG to a finite deformation theory since the indentation depth in experiments can be as large as the film thickness. Contrary to indentation of bulk metals or soft metallic films on hard substrate, the micro-indentation hardness of a hard tungsten film on soft aluminum substrate decreases monotonically with the increasing depth of indentation, and it never approaches a constant (macroscopic hardness). It is also shown that the strain gradient effect in the soft aluminum substrate is insignificant, but that in the hard tungsten thin film is important in shallow indentation. The strain gradient effect in tungsten, however, disappears rapidly as the indentation depth increases because the intrinsic material length in tungsten is rather small.     

Local mechanical properties of the 6061-T6 aluminium weld using micro-traction and instrumented indentation

The local mechanical properties of a weld zone, in a 6061-T6 aluminium alloy subjected to the modified indirect electric arc technique have been studied. The mechanical properties of the base metal, the weld metal and the heat affected zone were determined by means of usual and instrumented indentation testing, as well as micro-traction testing. To analyse the heat input effect resulting from the welding process, the evolution of the weld zone size was evaluated by means of classical indentation under a constant applied load. The results were presented using a Vickers hardness map representation. This allows monitoring exact hardness variation while leading to the identification of the different zones of the welded joint. Instrumented indentation testing was carried out to determine the local mechanical properties, such as the yield stress, the bulk modulus and the strain-hardening exponent. Obtained results are compared to those derived from tensile tests conducted on micro-specimen cuts taken from the weld zone. It was observed that yield stress values are directly comparable for indentation and micro-traction experiments. As for the elastic properties, no comparison was possible since the bulk modulus is measured by indentation, whereas it is the Young’s modulus by tensile test. The micro-traction testing seems to be more sensitive to represent the work hardening of a material since the corresponding exponent is found to be constant by instrumented indentation.     

氧化铝多孔膜振动性能的实验研究

电化学氧化法制备的氧化铝多孔膜有六角规则密排的纳米孔,其优良的结构特点使其具有良好的用途,可应用于微粒物质分离,氧化剂的载体,微电子机械系统的组件和纳米器件等。在前期研究了这种氧化铝膜的力学性能如拉伸性能和弯曲性能的基础上,本文实验研究了这种氧化铝多孔膜的振动特性即共振频率特性和振动模态,估算了该氧化铝多孔膜的相当弹性模量,与其他方法测得的相当弹性模量基本一致。     

Elastic modulus measurements of vertically aligned multi walled carbon nanotubes carpets by using the nanoindentation technique

Electrical, thermal and mechanical properties of Vertically Aligned Multi Walled Carbon NanoTubes (VA-MWCNT) make them an ideal candidate to replace some of conventional materials in micro and nano-electronic components. Integrating this material in micro components requires a good knowledge of their properties. As the electrical and thermal properties, the MWCNT mechanical properties are difficult to assess. Several techniques have been developed to estimate the CNT Young's modulus and the obtained results cover a large range of scale. In this study, we propose an indirect technique for MWCNT carpet Young's modulus measurements by using the nanoindentation technique. Nanoindentation tests are performed on a metallic film deposited on MWCNT. The measured equivalent reduced modulus takes into account the elastic properties of the metallic thin film and those of the MWCNT substrate. Bec et al. model, introduced in 2006, is used to separate elastic properties, and thus determine the MWCNT reduced Young’s modulus which is estimated between 329 and 352 GPa. Knowing the indenter mechanical properties, we estimate the Young’s modulus in the 461 to507 GPa range.     

On establishing elastic–plastic properties of a sphere by indentation testing

Instrumented indentation is a popular technique for determining mechanical properties of materials. Currently, the evaluation techniques of instrumented indentation are mostly limited to a flat substrate being indented by various shaped indenters (e.g., conical or spherical). This work investigates the possibility of extending instrumented indentation to non-flat surfaces. To this end, conical indentation of a sphere is investigated where two methodologies for establishing mechanical properties are explored. In the first approach, a semi-analytical approach is employed to determine the elastic modulus of the sphere utilizing the elastic unloading response (the “unloading slope”). In the second method, reverse analysis based on finite element analysis is used, where non-dimensional characteristic functions derived from the force–displacement response are utilized to determine the elastic modulus and yield strength. To investigate the accuracies of the proposed methodologies, selected numerical experiments have been performed and excellent agreement was obtained.     

A Discontinuous Elastic Interface Transfer Model of Thin Film Nanoindentation

A new model of thin film indentation that accounted for an apparent discontinuity in elastic strain transfer at the film/substrate interface was developed. Finite element analysis suggested that numerical values of strain were not directly continuous across the interface; the values in the film were higher when a soft film was deposited on a hard substrate. The new model was constructed based on this discontinuity; whereby, separate weighting factors were applied to account for the influence of the substrate in strain developed in the film and vice-versa. By comparing the model to experimental data from thirteen different amorphous thin film materials on a silicon substrate, constants in each weighting factor were found to have physical significance in being numerically similar to the bulk scale Poisson’s ratios of the materials involved. When employing these material properties in the new model it was found to provide an improved match to the experimental data over the existing Doerner and Nix and Gao models. Finally, the model was found to be capable of assessing the Young’s modulus of thin films that do not exhibit a flat region as long as the bulk Poisson’s ratio is known.     

利用纳米硬度试验法确定Cr/Cu梯度材料的变形特性

利用纳米硬度仪研究了在Cu基底上的Cu／Cr梯度膜的机械性能。梯度膜是通过将Cu靶和Cr靶同时溅射到Cu基底材料上，但两个靶的相对溅射功率随溅射时间变化而制备。利用Oliver and Pharr方法得到了膜随其厚度变化的硬度和弹性模量。然后利用加载／卸载／再加载的方法得到了在不同深度(即膜的厚度)压头平均压力与相对压人深度之间的关系曲线，在此曲线上可以明显反映出材料的屈服特性。     

An inverse problem in film/substrate indentation: extracting both the Young’s modulus and thickness of films

In an indentation test, the effective Young’s modulus of a film/substrate bilayer heterostructure varies with the indentation depth, a phenomenon known as the substrate effect. In previous studies investigating this, only the Young’s modulus of the film was unknown. Once the effective Young’s modulus of a film/substrate structure is determined at a given contact depth, the Young’s modulus of the film can be uniquely determined, i.e., there is a one-to-one relation between the Young’s modulus of the film and the film/substrate effective Young’s modulus. However, at times it is extremely challenging or even impossible to measure the film thickness. Furthermore, the precise definition of the layer/film thickness for a two-dimensional material can be problematic. In the current study, therefore, the thickness of the film and its Young’s modulus are treated as two unknowns that must be determined. Unlike the case with one unknown, there are infinite combinations of film thickness and Young’s modulus which can yield the same effective Young’s modulus for the film/substrate. An inverse problem is formulated and solved to extract the Young’s modulus and thickness of the film from the indentation depth-load curve. The accuracy and robustness of the inverse problem-solving method are also demonstrated.