Ceria and its solid solutions play a vital role in several industrial processes and devices. These include solar energy-to-fuel conversion, solid oxide fuel and electrolyzer cells, memristors, chemical looping combustion, automotive 3-way catalysts, catalytic surface coatings, supercapacitors and recently, electrostrictive devices. An attractive feature of ceria is the possibility of tuning defect-chemistry to increase the effectiveness of the materials in application areas. Years of study have revealed many features of the long-range, macroscopic characteristics of ceria and its derivatives. In this review we focus on an area of ceria defect chemistry which has received comparatively little attention -defect-induced local distortions and short-range associates. These features are non-periodic in nature and hence not readily detected by conventional X-ray powder diffraction. We compile the relevant literature data obtained by thermodynamic analysis, Raman spectroscopy, and X-ray absorption fine structure (XAFS) spectroscopy. Each of these techniques provides insight into material behavior without reliance on longrange periodic symmetry. From thermodynamic analyses, association of defects is inferred. From XAFS, an element-specific probe, local structure around selected atomic species is obtained, whereas from Raman spectroscopy, local symmetry breaking and vibrational changes in bonding patterns is detected.We note that, for undoped ceria and its solid solutions, the relationship between short range order and cation-oxygen-vacancy coordination remains a subject of active debate. Beyond collating the sometimes contradictory data in the literature, we strengthen this review by reporting new spectroscopy results and analysis. We contribute to this debate by introducing additional data and analysis, with the expectation that increasing our fundamental understanding of this relationship will lead to an ability to predict and tailor the defect-chemistry of ceria-based materials for practical applications. monoxide, and NO x from the exhaust stream, precise control of the oxygen-to-fuel ratio is necessary. Ceria has the capacity to serve as an oxygen buffer by actively varying its oxygen nonstoichiometry, supplying oxygen when required for carbon oxidation, and removing it as necessary for NO x reduction. Another promising use of the oxygen storage capacity of ceria is in solar-driven thermochemical water splitting. 15,16 During this cyclic process, ceria releases oxygen at extremely high temperatures (typ. 1500 1C), which can be achieved by solar concentration. Subsequently, the material is cooled to 800-1000 1C, and the oxygen vacancies generated from the prior reduction step are filled with oxygen through a water and CO 2 splitting reaction. Though not treated in this review, it is noteworthy that doping with tetravalent cations, Zr 4+ or Hf 4+ , increases the ease by which the reduction of the host material occurs. 17,18 This behavior is used to increase the oxygen storage capacity in exhaust catalysts, or to decrea...

A protocol for characterizing relaxation of anisotropic strain in thin films of 10 mol% Eu-or Sm-doped ceria is described. The method is based on comparison of Raman spectra and X-ray diffraction patterns from substratesupported films, displaying in-plane compressive strain (initial state), with analogous data from 2 mm diameter self-supported films (i.e., membranes), prepared by partial substrate removal (final state). These membranes are found to be relaxed, i.e., approximately unstrained, but with increased unit cell volume. The effective (i.e., 2-state) Grüneisen parameter of the F 2g Raman active mode for these films is calculated to be 0.4 ± 0.1, which is ≈30% of the literature value for the corresponding ceramics under isostatic pressure. On this basis, it is found that the observed red-shift of the F 2g mode frequency following isothermal strain relaxation of the doped ceria thin films cannot be determined solely by the increase in average unit cell volume. The study presented here may shed light on the suitability of Raman spectroscopy as a technique for characterizing strain in lanthanide-doped ceria thin films.

Thermally evaporated Pb preserves the electronic properties of an organic monolayer (ML) on Si and surface passivation of the Si surface itself. The obtained current-voltage characteristics of Pb/ML/Si junctions agree with results obtained with the well-established Hg contact and preserve both the molecule-induced dipole effect on, and length-attenuation of, the current. We rationalize our findings by the lack of interaction between the Pb and the Si substrate. This method is fast, scalable, and compatible with standard semiconductor processing, results in close to 100% yield, and can help the development of large-scale utilization of silicon-organic hybrid electronics. Our experimental data show a dependence of the transport across the molecules on the substrate orientation, expressed in the smaller distance decay parameter with Si(100) than that with Si(111).

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. We used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorption spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.

Ceria doped with trivalent dopants exhibits nonclassical electrostriction, strong anelasticity, and roomtemperature (RT) mechanical creep. These phenomena, unexpected for a ceramic material with a large Young's modulus, have been attributed to the generation of local strain in the vicinity of the host Ce cations due to symmetrybreaking point defects, including oxygen vacancies. However, understanding why strain is generated at the host rather than at the dopant site, as well as predicting these effects as a function of dopant size and concentration, remains a challenge. We have used the evolutionary-algorithm-based reverse Monte Carlo modeling to reconcile the experimental data of extended X-ray absorption fine structure and X-ray diffraction in a combined model structure. By extracting the details of the radial distribution function (RDF) around the host (Ce) and trivalent dopants (Sm or Y), we find that RDF of the first-nearest neighbor (1NN) of host and dopant cations as well as the second-nearest neighbor (2NN) of the dopant are each best modeled with two separate populations corresponding to short and long interatomic distances. This heterogeneity indicates that fluorite symmetry is not preserved locally, especially for the dopant first-and second-NN sites, appearing at surprisingly low doping fractions (5 mol % Sm and 10 mol % Y). Given that Ce rather than dopant sites act as the source of local strain for electrostriction and RT creep, we conclude that the environment around the dopant does not respond to electrical and mechanical excitations, likely because of its similarity to the double fluorite structure which has poor electrostrictive and anelastic properties. The trends we observe in the RDFs around the Ce sites as a function of dopant size and concentration suggest that the response of these sites can be controlled by the extent of doping: Increasing dopant size to increase strain magnitude at the 1NN shell of Ce and decreasing dopant fraction to decrease strain propagation to the 2NN shell of Ce should produce stronger electrostrictive response and RT creep.