The advances in Nanoscience and Nanotechnology have been paved by the continuous development of new techniques adapted to small samples. In that framework, calorimetry is a technique suitable to measure thermodynamic properties and energetic processes, such as phase transitions, through the heat absorbed or released by the system. Taking profit of advances in microfabrication techniques a new family of nanocalorimeters, based on ultra-light calorimetric cells and built up onto thin film dielectric membranes, has emerged demonstrating enhanced sensitivities compared with traditional calorimeters, reaching levels better than 1 nJ K-1 mm-2. This technique has permitted to several research groups to explore new physical phenomena inaccessible before._x000D_ The present research work deals with the development and optimization of this technique: the nanocalorimetry. We enlarge the dynamic ranges of applicability from ultrafast heating rates to quasi-static ones, and we demonstrate its utility in the study of different phase transitions at nanoscale. In the first Chapter, a general introduction sets out the necessity of developing new characterization techniques to give service to the scientific community, and also provides an historical overview about the calorimeters development. Subsequently, Chapter 2 provides an overview about nanocalorimeters microfabrication process, and about design and fabrication of specific experimental setups to carry on nanocalorimetric experiments from 80 to 1200 K in adiabatic conditions. Chapter 3 presents the nanocalorimetric tools used during the Thesis and the improvements that we have implemented. The two major advances achieved are:_x000D_ (i) The expansion of the operating heating rates, where the combination of pulsed and power compensated methods have permitted to cover the ranges from 0.1 to 106 K/s. Moreover, a thorough study of the heat capacity calculation, and the analysis of signal noise led us to obtain a methodology that improves qualitatively the results obtained from data processing._x000D_ (ii) The development of a new quasi-static technique that combines the better specificities of DC techniques, like the huge signal enhancement of adiabatic nanocalorimetry, and the averaging capabilities of AC calorimetry. This new technique has been named microsecond-pulsed heating nanocalorimetry, and it allows measuring second order phase transitions with a very high sensitivity (less than 75 pJ K-1 mm-2 Hz-1/2), with better thermal maps in the sensing area (less than 1 K thermal gradient) than using pulsed methods._x000D_ We deeply study the effect of dimensionality in two different physical systems: the magnetic order-disorder transition in thin films of CoO, and the formation kinetics of thin films of Pd2Si from Pd/Si bilayers. In Chapter 4 we present how microstructure influences the antiferromagnetic interaction in CoO thin films. We study size effects in thin film samples ranging from 1 to 20 nm, and the influence of grains and boundaries sizes from a thermodynamic perspective in samples of 20 nm. We relate thermodynamic properties to magnetic ones by means of nanocalorimetric, structural, and magnetic characterization. In Chapter 5 the formation kinetics of Pd2Si is analyzed. We pursuit understand the reaction kinetics over a wide range of heating rates spanning six orders of magnitude. To achieve this purpose, we combine conventional calorimetry and nanocalorimetry. This study is complemented by the structural characterization of the samples. We also use a kinetic model to obtain the most relevant kinetic parameters by fitting the calorimetric curves.
Nanocalorimetric studies of size effects in magnetic oxides and formation kinetics in silicides.
Molina Ruiz, M. (Author). 17 Dec 2014
Student thesis: Doctoral thesis
Student thesis: Doctoral thesis