Nano-Thermal Transport Array: An Instrument for Combinatorial Measurements of Heat Transfer in Nanoscale Films

The nano-Thermal Transport Array is a silicon-based micromachined device for measuring the thermal properties of nanoscale materials in a high-throughput methodology. The device contains an array of thermal sensors, each one of which consists of a silicon nitride membrane and a tungsten heating element that also serves as a temperature gauge. The thermal behavior of the sensors is described with an analytical model. The assumptions underlying this model and its accuracy are checked using the finite element method. The analytical model is used in a data reduction scheme that relates experimental quantities to materials properties. Measured properties include thermal effusivity, thermal conductivity, and heat capacity. While the array is specifically designed for combinatorial analysis, here we demonstrate the capabilities of the device with a high-throughput study of copper multi-layer films as a function of film thickness, ranging from 15 to 470 nm. Thermal conductivity results show good agreement with earlier models predicting the conductivity based on electron scattering at interfaces.Engineering and Applied Science

Stiff, strong, and tough hydrogels with good chemical stability

Most hydrogels have poor mechanical properties, severely limiting their scope of applications. Here a hybrid hydrogel, consisting of hydrophilic and crystalline polymer networks, achieves an elastic modulus of 5 MPa, a strength of 2.5 MPa, and a fracture energy of 14 000 J m−2, while maintaining physical integrity in concentrated electrolyte solutions.Engineering and Applied Science

A model of ideal elastomeric gels for polyelectrolyte gels

The concept of the ideal elastomeric gel is extended to polyelectrolyte gels and verified using a polyacrylamide-co-acrylic acid hydrogel as a model material system. A comparison between mixing and ion osmosis shows that the mixing osmosis is larger than the ion osmosis for small swelling ratios, while the ion osmosis dominates for large swelling ratios. We show further that the non-Gaussian chain effect becomes important in the elasticity of the polymer network at the very large swelling ratios that may occur under certain conditions of pH and salinity. We demonstrate that the Gent model captures the non-Gaussian chain effect well and that it provides a good description of the free energy associated with the stretching of the network. The model of ideal elastomeric gels fits the experimental data very well.Engineering and Applied Science

Variation of stress with charging rate due to strain-rate sensitivity of silicon electrodes of Li-ion batteries

Silicon is a promising anode material for lithium-ion batteries due to its enormous theoretical energy density. Fracture during electrochemical cycling has limited the practical viability of silicon electrodes, but recent studies indicate that fracture can be prevented by taking advantage of lithiation-induced plasticity. In this paper, we provide experimental insight into the nature of plasticity in amorphous LixSi thin films. To do so, we vary the rate of lithiation of amorphous silicon thin films and simultaneously measure stresses. An increase in the rate of lithiation results in a corresponding increase in the flow stress. These observations indicate that rate-sensitive plasticity occurs in a-LixSi electrodes at room temperature and at charging rates typically used in lithium-ion batteries. Using a simple mechanical model, we extract material parameters from our experiments, finding a good fit to a power law relationship between the plastic strain rate and the stress. These observations provide insight into the unusual ability of a-LixSi to flow plastically, but fracture in a brittle manner. Moreover, the results have direct ramifications concerning the rate-capabilities of silicon electrodes: faster charging rates (i.e., strain rates) result in larger stresses and hence larger driving forces for fracture.Engineering and Applied Science

Determining the Elastic Modulus and Hardness of an Ultrathin Film on a Substrate Using Nanoindentation

A data analysis procedure has been developed to estimate the contact area in an elasto-plastic indentation of a thin film bonded to a substrate. The procedure can be used to derive the elastic modulus and hardness of the film from the indentation load, displacement, and contact stiffness data at indentation depths that are a significant fraction of the film thickness. The analysis is based on Yu’s elastic solution for the contact of a rigid conical punch on a layered half-space and uses an approach similar to the Oliver-Pharr method for bulk materials. The methodology is demonstrated for both compliant films on stiff substrates and the reverse combination and shows improved accuracy over previous methods.Engineering and Applied Science

Failure by Simultaneous Grain Growth, Strain Localization, and Interface Debonding in Metal Films on Polymer Substrates

In a previous paper, we have demonstrated that a microcrystalline copper film well bonded to a polymer substrate can be stretched beyond 50% without cracking. The film eventually fails through the co-evolution of necking and debonding from the substrate. Here we report much lower strains to failure (around 10%) for polymer-supported nanocrystalline metal films, whose microstructure is revealed to be unstable under mechanical loading. We find that strain localization and deformation-associated grain growth facilitate each other, resulting in an unstable deformation process. Film/substrate delamination can be found wherever strain localization occurs. We therefore propose that three concomitant mechanisms are responsible for the failure of a plastically deformable but microstructurally unstable thin metal film: strain localization at large grains, deformation-induced grain growth and film debonding from the substrate.Engineering and Applied Science

A scanning AC calorimetry technique for the analysis of nano-scale quantities of materials

We present a scanning AC nanocalorimetry method that enables calorimetry measurements at heating and cooling rates that vary from isothermal to 2 × 10^3 K/s, thus bridging the gap between traditional scanning calorimetry of bulk materials and nanocalorimetry. The method relies on a micromachined nanocalorimetry sensor with a serpentine heating element that is sensitive enough to make measurements on thin-film samples and composition libraries. The ability to perform calorimetry over such a broad range of scanning rates makes it an ideal tool to characterize the kinetics of phase transformations or to explore the behavior of materials far from equilibrium. We demonstrate the technique by performing measurements on thin-film samples of Sn, In, and Bi with thicknesses ranging from 100 to 300 nm. The experimental heat capacities and melting temperatures agree well with literature values. The measured heat capacities are insensitive to the applied AC frequency, scan rate, and heat loss to the environment over a broad range of experimental parameters

High-temperature tensile behavior of freestanding Au thin films

The mechanical behavior of freestanding thin sputter-deposited films of Au is studied at temperatures up to 340 °C, using tensile testing. Films tested at elevated temperatures exhibit a significant decrease in flow stress and stiffness. Furthermore, the flow stress decreases with decreasing film thickness, contravening the usual notion that “smaller is stronger”. This behavior is attributed mainly to diffusion-facilitated grain boundary sliding.Engineering and Applied Science

The Effect of Porogen Loading on the Stiffness and Fracture Energy of Brittle Organosilicates

Integrating porous low-permittivity dielectrics into Cu metallization is one of the strategies to reduce power consumption, signal propagation delays, and crosstalk between interconnects for the next generation of integrated circuits. The porosity and pore structure of these low-k dielectric materials, however, also affect other important material properties in addition to the dielectric constant. In this paper, we investigate the impact of porogen loading on the stiffness and cohesive fracture energy of a series of porous organosilicate glass (OSG) thin films using nanoindentation and the doublecantilever beam (DCB) technique. The OSG films were deposited by plasma-enhanced chemical vapor deposition (PECVD) and had a porosity in the range of 7~45%. We show that the degree of porogen loading during the deposition process changes both the network structure and the porosity of the dielectric, and we resolve the contributions of both effects to the stiffness and fracture energy of the films. The experimental results for stiffness are compared with micromechanical models and finite element calculations. It is demonstrated that the stiffness of the OSG films depends sensitively on their porosity and that considerable improvements in stiffness may be obtained through further optimization of the pore microstructure. The cohesive fracture energy of the films decreases linearly with increasing porosity, consistent with a simple planar through-pore fracture mechanism.Engineering and Applied Science