Aluminum Nanoparticles as Fiducials for Nanoscale Temperature Measurements
In plasmon energy expansion thermometry (PEET), electron energy-loss spectroscopy (EELS) is used to determine the plasmon energy in a suitable thermometric material [1]. Since the plasmon energy scales with the material’s density, temperature changes can be determined using knowledge of the material’s thermal expansion coefficient. Many in situ transmission electron microscopy experiments could benefit from having thermometric fiducials, i.e. localized thermometers within the field of view. Nanoparticles of aluminum, with their narrow bulk plasmon resonance and large thermal expansion coefficient [2, 3], are particularly well suited to act as such fiducial thermometers.
Nanoscale temperature measurement during temperature controlled in situ TEM using Al plasmon nanothermometry.
Over recent years, the advent of microelectromechanical system (MEMS)-type microheaters has pushed the limits of temperature controlled in situ transmission electron microscopy (TEM). In particular, by enabling the observation of the structure of materials in their application environments, temperature controlled TEM provides unprecedented insights into the link between the properties of materials and their structure in real-world problems, a clear knowledge of which is necessary for rational development of functional materials with new or improved properties. While temperature is the key parameter in such experiments, accessing the precise temperature of the sample at the nanoscale during observations still remains challenging. In the present work, we have applied aluminium plasmon nanothermometry technique that monitors the temperature dependence of the volume plasmon of Al nanospheres using electron energy loss spectroscopy for in situ local temperature determination over MEMS-type microheaters. With access to local temperatures between room temperature to 550 ∘C, we have assessed the spatial and temporal stabilities of these microheaters when they operate at different setpoint temperatures both under vacuum and in the presence of a static H2 gas environment. Temperature comparisons performed under the two environments show discrepancies between local and setpoint temperatures.
Coated-wire electrodes containing polymer immobilized ionophores blended with poly(vinyl chloride).
Polymers containing covalently attached 18-crown-6 or 2.2.2 cryptand units were incorporated into plasticized PVC membranes and the composite membranes were examined as potassium ion sensor elements. Ionophores were linked to carboxy-PVC and to poly(acrylic acid) via amide linkages to an alkyl spacer unit. Coated-wire electrodes (CWEs) from the immobilized ionophores gave acceptable responses, but conventional ion-selective membrane electrodes (ISEs) prepared by solvent casting were inactive. Dip-cast membranes did give active ISEs. Potassium electrode performance was independent of the loading of the ionophore within the acrylate support polymer, but depended upon the spacer length. Ion selectivity varied with the ionophore loading within the support polymer. Selectivity is a composite of the ionophore selectivity and ion-exchange interactions with the acrylate backbone, giving selectivities akin to carboxylate substituted crown ethers, notably enhanced monovalent/divalent ion discrimination relative to the ionophore in solution. Polymer immobilization extended the lifetime of active electrodes.