Conspectus
Isotopic engineering has emerged
as a key approach to study the
nucleation, diffusion, phase transitions, and reactions of materials
at an atomic level. It aims to uncover mass transport pathways, kinetics,
and operational and failure mechanisms of functional materials and
devices. Understanding these phenomena leads to deeper insights into
important physical processes, such as the transport of ions in energy
conversion and storage devices and the role of active sites and supports
during heterogeneous catalytic reactions. Likewise, isotopic engineering
is being pursued as a means of modifying functionality to enable future
technological applications. In this Account, we summarize our recent
work employing isotope labeling (e.g., 18O2 and 57Fe) during thin film synthesis and postgrowth processing
to reveal growth mechanisms, defect chemistry, and elemental diffusion
under working and extreme conditions. Isotope-resolved analysis techniques
with nanometer-scale spatial resolution, such as time-of-flight secondary
ion mass spectrometry and atom probe tomography, facilitate the accurate
quantification of isotopic placement and concentration in our well-defined
heterostructures with precisely positioned, isotope-enriched layers.
By measuring the nanometer-scale redistribution between natural abundance
and isotopically enriched oxygen layers during the deposition of Fe2O3 and Cr2O3 by molecular
beam epitaxy, we identified intermixing processes driven by surface
adatoms occurring both at the film growth surface and within the first
few layers below the surface. Further insights into synthesis mechanisms
were gained by studying the tungsten oxide thin films grown by evaporating
WO3 powder in the presence of background 18O2, revealing minimal incorporation of background oxygen during
the film formation process. Thermal and radiation-enhanced diffusion
in epitaxial Fe and Cr oxides were precisely tracked using 18O and 57Fe tracer layers incorporated into model epitaxial
oxide thin films. This approach has allowed us to access thermal diffusion
behavior at lower temperatures than previously measured, revealing
a potential changeover in diffusion mechanism. Understanding radiation-enhanced
diffusion in model oxides that represent the surface layers on the
structural components of nuclear reactors informs our understanding
of their corrosion behavior under irradiation. Isotopic labeling can
also provide unique insights into the surface exchange reactions and
defect chemistry of electrocatalysts. For instance, tracking the change
in 18O concentration at the surface of an epitaxial LaNiO3 thin film after the electrocatalytic oxygen evolution reaction
revealed the participation of lattice oxygen, confirming a hypothesis
that had been proposed previously. Lastly, we highlight a new direction
wherein we perform in situ processing studies utilizing isotopic tracers
in conjunction with model epitaxial thin films within the atom probe
tomography instrument. This Account illustrates the great potential
of isotopic engineeri...