ABSTRACT
Understanding and controlling the chemical processes between molten salts and alloys is vital for the safe operation of molten-salt nuclear reactors. Corrosion processes in molten salts are highly dependent on the redox potential of the solution that changes with the presence of fission and corrosion processes, and as such, reactor designers develop electrochemical methods to monitor the salt. However, electrochemical techniques rely on the deconvolution of broad peaks, a process that may be imprecise in the presence of multiple species that emerge during reactor operation. Here, we describe in situ measurements of the concentration and chemical state of corrosion products in molten FLiNaK (eutectic mixture of LiF-NaK-KF) by high-resolution X-ray absorption spectroscopy. We placed a NiCr foil in molten FLiNaK and found the presence of both Ni2+ ions and metallic Ni in the melt, which we attribute to the foil disintegration due to Cr dealloying.
ABSTRACT
Coherent and epitaxial interfaces permit the realization of electric field driven devices controlled by atomic-scale structural and electronic effects at interfaces. Compared to conventional field effect devices where channel conductivity is modulated by carrier density modification, the propagation of atomic-scale distortions across an interface can control the atomic scale bonding, interatomic electron tunneling rates and thus the mobility of the channel material. We use first-principles theory to design an atomically abrupt epitaxial perovskite heterostructure involving an oxide ferroelectric (PbZr0.2Ti0.8O3) and conducting oxide channel (LaNiO3) where coupling of polar atomic motions to structural distortions can induce large, reversible changes in the channel mobility. We fabricate and characterize the heterostructure and measure record values, larger than 1000%, for the conductivity modulation. Our results describe how purely interfacial effects can be engineered to deliver unique electronic device properties and large responses to external fields.
ABSTRACT
The ability to map out electrostatic potentials in materials is critical for the development and the design of nanoscale electronic and spintronic devices in modern industry. Electron holography has been an important tool for revealing electric and magnetic field distributions in microelectronics and magnetic-based memory devices, however, its utility is hindered by several practical constraints, such as charging artifacts and limitations in sensitivity and in field of view. In this article, we report electron-beam-induced-current (EBIC) and secondary-electron voltage-contrast (SE-VC) with an aberration-corrected electron probe in a transmission electron microscope (TEM), as complementary techniques to electron holography, to measure electric fields and surface potentials, respectively. These two techniques were applied to ferroelectric thin films, multiferroic nanowires, and single crystals. Electrostatic potential maps obtained by off-axis electron holography were compared with EBIC and SE-VC to show that these techniques can be used as a complementary approach to validate quantitative results obtained from electron holography analysis.
ABSTRACT
The ability to map out electrostatic potentials in materials is critical for the development and the design of nanoscale electronic and spintronic devices in modern industry. Electron holography has been an important tool for revealing electric and magnetic field distributions in microelectronics and magnetic-based memory devices, however, its utility is hindered by several practical constraints, such as charging artifacts and limitations in sensitivity and in field of view. In this article, we report electron-beam-induced-current (EBIC) and secondary-electron voltage-contrast (SE-VC) with an aberration-corrected electron probe in a transmission electron microscope (TEM), as complementary techniques to electron holography, to measure electric fields and surface potentials, respectively. These two techniques were applied to ferroelectric thin films, multiferroic nanowires, and single crystals. Electrostatic potential maps obtained by off-axis electron holography were compared with EBIC and SE-VC to show that these techniques can be used as a complementary approach to validate quantitative results obtained from electron holography analysis.
ABSTRACT
The breaking of orbital degeneracy on a transition metal cation and the resulting unequal electronic occupations of these orbitals provide a powerful lever over electron density and spin ordering in metal oxides. Here, we use ab initio calculations to show that reversibly modulating the orbital populations on Mn atoms can be achieved at ferroelectric/manganite interfaces by the presence of ferroelectric polarization on the nanoscale. The change in orbital occupation can be as large as 10%, greatly exceeding that of bulk manganites. This reversible orbital splitting is in large part controlled by the propagation of ferroelectric polar displacements into the interfacial region, a structural motif absent in the bulk and unique to the interface. We use epitaxial thin film growth and scanning transmission electron microscopy to verify this key interfacial polar distortion and discuss the potential of reversible control of orbital polarization via nanoscale ferroelectrics.
ABSTRACT
Engineering domains in ferroelectric thin films is crucial for realizing technological applications including non-volatile data storage and solar energy harvesting. Size and shape of domains strongly depend on the electrical and mechanical boundary conditions. Here we report the origin of nonswitchable polarization under external bias that leads to energetically unfavourable head-to-head domain walls in as-grown epitaxial PbZr(0.2)Ti(0.8)O3 thin films. By mapping electrostatic potentials and electric fields using off-axis electron holography and electron-beam-induced current with in situ electrical biasing in a transmission electron microscope, we show that electronic band bending across film/substrate interfaces locks local polarization direction and further produces unidirectional biasing fields, inducing nonswitchable domains near the interface. Presence of oxygen vacancies near the film surface, as revealed by electron-energy loss spectroscopy, stabilizes the charged domain walls. The formation of charged domain walls and nonswitchable domains reported in this study can be an origin for imprint and retention loss in ferroelectric thin films.
ABSTRACT
Epitaxial nanostructures have generated a great deal of interest because of the applications in catalysis, photonics and nanoelectronics. To study the structure and electronic properties at the nanoscale, scanning tunnelling microscopy (STM) has proven a very effective technique due to its extraordinarily high spatial resolution. Growth modes of epitaxial nanostructures depend predominantly on the surface free energy of the deposited material, and that of the substrate onto which it is deposited, leading to layer-by-layer or island growth modes. The strain due to lattice mismatch plays an important role in the formation of semiconductor quantum dot islands via strain-induced transitions in the morphology of epitaxial nanoislands. Examples of the different growth modes observed with STM are presented in this review within a general framework that uses the surface and strain energies to understand the effects that govern nanostructure shapes. Some self-assembled oxide and metal nanostructures, as well as molecular networks, are also discussed.
ABSTRACT
Processing the SrTiO(3)(001) surface results in the self-assembly of reduced titanate nanowires whose widths are approximately 1 nm. We have imaged these nanowires and their defects at elevated temperatures by atomic resolution scanning tunneling microscopy. The nanowire structure is modeled with density functional theory, and defects observed in the center of the nanowire are determined to be Ti(4)O(3) vacancy clusters. The activation energy for Ti(4)O(3) vacancy cluster diffusion is explicitly measured as 4.98±0.17 eV with an exponential prefactor of µ=6.57×10(29) (s(-1).
ABSTRACT
Extended annealing in UHV causes the surface region of SrTiO3(001) to become enriched with TiO2, resulting in the formation of epitaxial islands of anatase TiO2(001). The islands are studied using UHV scanning electron microscopy (SEM), which reveals the changes in morphology during growth induced by misfit strain. Starting from a square island, two types of shape transition are observed. In the first, between 1000 and 1030 degrees C, the anatase islands elongate in length and narrow in width. This growth behavior follows the Tersoff-Tromp model [Phys. Rev. Lett. 70, 2782 (1993)10.1103/PhysRevLett.70.2782]. In the second growth mode, between 930 and 1000 degrees C, the islands relieve strain by the formation of trenches in the middle of each side of the square, thereby evolving into crosses. This shape arises because the lower annealing temperature imposes a kinetic constraint on the detachment of atoms necessary for island narrowing.
