Person:

McCluskey, Patrick

Micromachined nanocalorimetry sensors have shown excellent performance for high-temperature and high-scanning rate calorimetry measurements. Here, we combine scanning AC nanocalorimetry with in-situ x-ray diffraction (XRD) to facilitate interpretation of the calorimetry measurements. Time-resolved XRD during in-situ operation of nanocalorimetry sensors using intense, high-energy synchrotron radiation allows unprecedented characterization of thermal and structural material properties. We demonstrate this experiment with detailed characterization of the melting and solidification of elemental Bi, In, and Sn thin-film samples, using heating and cooling rates up to 300 K/s. Our experiments show that the solidification process is distinctly different for each of the three samples. The experiments are performed using a combinatorial device that contains an array of individually addressable nanocalorimetry sensors. Combined with XRD, this device creates a new platform for high-throughput mapping of the composition dependence of solid-state reactions and phase transformations.

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.

Combinatorial nanocalorimetry and synchrotron x-ray diffraction were combined to study the martensite-austenite (M-A) phase transformation behavior of Ni-Ti-Hf shape memory alloys. A thin-film library of Ni-Ti-Hf samples with a range of compositions was deposited on a parallel nano-scanning calorimeter device using sputter deposition. Crystallization of each amorphous as-deposited sample by local heating at approximately 104 K/s produced a nanoscale grain structure of austenite and martensite. Individual samples were then cycled through the M-A transformation, while the transformation enthalpy was measured by nanocalorimetry and the low- and high-temperature phase compositions were determined by x-ray diffraction. The techniques enable correlation of the observed behavior during thermal cycling with the thermodynamic and structural properties of the samples.