Search

We report the adiabatic elastic constants of single-crystal thorium dioxide over a temperature range of 77 - 350 K. Time-domain Brillouin scattering (TDBS), an all-optical, non-contact picosecond ultrasonic technique, is used to generate and detect coherent acoustic phonons that propagate in the bulk perpendicular to the surface of the crystal. These coherent acoustic lattice vibrations have been monitored in two hydrothermally grown single-crystal thorium dioxide samples along the (100) and (311) crystallographic directions. The three independent elastic constants of the cubic crystal (C11, C12 and C44) are determined from the measured bulk acoustic velocities. The longitudinal wave along the (100) orientation provided a direct measurement of C11. Measurement of C44 and C12 was achieved by enhancing the intensity of quasi-shear mode in a (311) oriented crystal by adjusting the polarization angle relative to the crystal axes. We find the magnitude of softening of the three elastic constants to be ~2.5% over the measured temperature range. Good agreement is found between the measured elastic constants with previously reported values at room temperature, and between the measured temperature-dependent bulk modulus with calculated values. We find that semi-empirical models capturing lattice anharmonicity adequately reproduce the observed trend. We also determine the acoustic Gruneisen anharmonicity parameter from the experimentally derived temperature-dependent bulk modulus and previously reported temperature-dependent values of volume thermal expansion coefficient and heat capacity. This work presents measurements of the temperature-dependent elasticity in single-crystal thorium dioxide at cryogenic temperature and provides a basis for testing ab initio theoretical models and evaluating the impact of anharmonicity on thermophysical properties., Manuscript submitted to a peer-reviewed journal

We have utilized photoluminescence spectroscopy and optical ellipsometry to characterize the dose-dependence of the photoluminescence emission intensity and changes in optical absorption of thoria single crystals subject to irradiation with energetic protons at room- and elevated-temperatures. The photoluminescence peaks and the optical absorption bands are attributed to creation of new electronic states emerging from defects resulting from displacement damage. These bands are most likely associated with electrons trapped at the oxygen vacancy sites similar to color centers formed in other irradiated oxides and halides. Our experimental observations are supported by a standard density functional theory calculation of the electronic structure in pristine and oxygen vacancy-bearing thoria crystals. The dose-dependence of the intensity of the photoluminescence peaks is used to parameterize a rate theory model that estimates the concentration of color centers in the irradiated crystals. This parameterization provides optimized migration barrier parameters for oxygen interstitials and vacancies that simultaneously capture the optical response of the crystals irradiated at room- and elevated-temperature. These optical spectroscopy techniques offer a promising pathway to characterize the population of color centers formed at the sites of oxygen anion vacancies, particularly in irradiated nuclear fuels, where atomic-level defects cannot be readily imaged using electron microscopy. When combined with other direct and indirect characterization tools, our approach can provide new insight into defect formation and accumulation in energy materials over single atomic to extended length scales.

Phonon lifetimes are a key component of quasiparticle theories of transport, yet first-principles lifetimes are rarely directly compared to inelastic neutron scattering (INS) results. Existing comparisons show discrepancies even at temperatures where perturbation theory is expected to be reliable. In this work, we demonstrate that the reciprocal space voxel ($q$-voxel), which is the finite region in reciprocal space required in INS data analysis, must be explicitly accounted for within theory in order to draw a meaningful comparison. We demonstrate accurate predictions of peak widths of the scattering function when accounting for the $q$-voxel in CaF$_2$ and ThO$_2$. Passing this test implies high fidelity of the phonon interactions and the approximations used to compute the Green's function, serving as critical benchmark of theory, and indicating that other material properties should be accurately predicted; which we demonstrate for thermal conductivity.

The interband transitions of urania (UO2) are validated independently through cathode luminescence of UO2. A picture emerges consistent with density functional theory. While theory is generally consistent with experiment, it is evident that the choice of functional can significantly alter the band gap and some details of the band structure, in particular at the conduction band minimum. Strictly ab initio predictions of the optical properties of the actinide compounds, based on density functional theory alone continues to be somewhat elusive.

To efficiently capture the energy of the nuclear bond, advanced nuclear reactor concepts seek solid fuels that must withstand unprecedented temperature and radiation extremes. In these advanced fuels, thermal energy transport under irradiation is directly related to reactor performance as well as reactor safety. The science of thermal transport in nuclear fuel is a grand challenge due to both computational and experimental complexities. Here, we provide a comprehensive review of thermal transport research on two actinide oxides: one currently in use in commercial nuclear reactors, uranium dioxide (UO2), and one advanced fuel candidate material, thorium dioxide (ThO2). In both materials, heat is carried by lattice waves or phonons. Crystalline defects caused by fission events effectively scatter phonons and lead to a degradation in fuel performance over time. Bolstered by new computational and experimental tools, researchers are now developing the foundational work necessary to accurately model and ultimately control thermal transport in advanced nuclear fuel. We begin by reviewing research aimed at understanding thermal transport in perfect single crystals. The absence of defects enables studies that focus on the fundamental aspects of phonon transport. Next, we review research that targets defect generation and evolution. Here, the focus is on ion irradiation studies used as surrogates for damage caused by fission products. We end this review with a discussion of modeling and experimental efforts directed at predicting and validating mesoscale thermal transport in the presence of irradiation defects. While efforts into these research areas have been robust, challenging work remains in developing holistic tools to capture and predict thermal energy transport across widely varying environmental conditions., Comment: Publication Date: December 17, 2021

The quasiharmonic approximation (QHA) is the simplest nontrivial approximation for interacting phonons under constant pressure, bringing the effects of anharmonicity into temperature dependent observables. Nonetheless, the QHA is often implemented with additional approximations due to the complexity of computing phonons under arbitrary strains, and the generalized QHA, which employs constant stress boundary conditions, has not been completely developed. Here we formulate the generalized QHA, providing a practical algorithm for computing the strain state and other observables as a function of temperature and true stress. We circumvent the complexity of computing phonons under arbitrary strains by employing irreducible second order displacement derivatives of the Born-Oppenheimer potential and their strain dependence, which are efficiently and precisely computed using the lone irreducible derivative approach. We formulate two complementary strain parametrizations: a discretized strain grid interpolation and a Taylor series expansion in symmetrized strain. We illustrate our approach by evaluating the temperature and pressure dependence of the elastic constant tensor and the thermal expansion in thoria (ThO$_2$) using density functional theory with three exchange-correlation functionals. The QHA results are compared to our measurements of the elastic constant tensor using time domain Brillouin scattering and inelastic neutron scattering. Our irreducible derivative approach simplifies the implementation of the generalized QHA, which will facilitate reproducible, data driven applications.

Fe:ZnSe and other transition metals have broad upper and lower energy manifolds that give rise to broad absorption and fluorescence bands in the mid-infrared spectral region. Energy transfer between Fe2 + ions via re-absorption of fluorescence (due to the spectral overlap of these bands) and phonon-assisted energy transfer (due to the lattice dynamics of ZnSe) becomes more probable with increasing Fe2 + concentration. Here, we treat these processes as additional terms in the rate equations that govern the spontaneous decay of the Fe2 + ion. This treatment gives insight into anomalous behavior seen in the thermal lifetime of the Fe:ZnSe system. We also apply the model to other transition metal-doped II–VI materials.

The vibrational energy of crystals is known to propagate in a fixed number of phonon branches allowed by symmetry. In the realm of nonlinear dynamics, however, additional nonlinear propagating modes are possible. Nonlinear propagating modes have unique properties that are important in many disciplines including optical communications, conducting polymers, biology, magnetism, and nuclear physics. Yet, despite the crucial importance of crystal lattice vibrations in fundamental and applied science, such additional propagating modes have not been observed in ordinary crystals. Here, we show that propagating modes exist beyond the phonons in fluorite-structured thoria, urania, and natural calcium fluoride using neutron scattering and first-principles calculations. These modes are observed at temperatures ranging from 5 K up to 1200 K, extend to frequencies 30–40% higher than the maximum phonon frequency, and travel at velocities comparable to or higher than the fastest phonon. The nonlinear origin of the modes is explained in part via perturbation theory, which approximately accounts for nonlinearity. Given that these modes are still clearly observed at 5 K, they are likely an inherent feature of the quantum ground state. The existence of these waves in three-dimensional crystals may have ramifications for material properties. Under extreme conditions, nonlinear lattice dynamics in a material can manifest and reveal unexpected properties. Here, using inelastic neutron scattering and first-principles calculations the authors find the presence of nonlinear travelling waves in a fluorite structured system, which exhibit characteristics different from regular phonons.

The proximity of minerals found in human hard tissues may influence cell phenotype. Since cells respond to a range of environmental cues, this study sought to identify the influence of two apatite-based microparticles, hydroxyapatite (HA) and fluoroapatite (FA), upon dental and bone cells. After bone marrow stromal cells (BMSCs), 7F2 osteoblasts and dental pulp stem cells (DPSCs) were plated into media with or without HA or FA particles, the cells were analyzed for alkaline phosphatase (ALP) production, collagen I production, osteocalcin production, and mineralization for two weeks. The BMSCs and DPSCs in media without any microparticles produced more ALP compared to those with microparticles from Day 5 forward. In addition, the collagen I and osteocalcin production in cultures without microparticles was higher than in cultures containing either HA or FA particles. While some studies have shown increased osteogeonic differentiation in the presence of mineral particles, those studies used nanoparticles that were able to be internalized by the cells and were smaller than the microparticles used in this study.

UO2's electrical properties and U's inherently high fission energy release make a UO2-based direct conversion neutron detector a tantalizing possibility, but the evolution of even rudimentary devices is inhibited by the absence of large, high quality single crystals of UO2. Hydrothermally grown UO2 is incorporated into a prototype device here, and laser light is used as a surrogate for neutron-induced fission events. Excitation sources with wavelengths of 325, 488, 532, and 633 nm are incident on the device for a variety of timescales to test the detection responses, resolution, and saturation behaviors. The non-amplified changes in the current are presented, including when the illumination's diameter, power, and location are altered. Photocurrent changes follow a positively correlated linear trend with power and device efficiency is inversely correlated with illumination wavelength. The impact of illumination time on the detection efficiency is discussed. Illumination event detection is independent of illumination surface area size and largely independent of the illumination location. The ramifications of these results with regard to the development of UO2 as a neutron detector are considered.

This work focuses on the full characterization of dislocation loops induced by proton irradiation in single-crystal ThO2. Irradiation was performed using 2 MeV H+ ions with sample temperature at 600oC and a dose of up to 0.47 displacements per atom (dpa). Transmission electron microscopy (TEM) characterization was performed on a large number of dislocation loops. Burgers vector ( b → ) analysis using standard g → . b → = 0 invisibility criterion revealed different variants of 1 / 3 〈 111 〉 type dislocation loops. TEM analysis of edge-on dislocation loops was used to determine habit planes as { 111 } type. The nature of dislocation loops was revealed using the inside-outside contrast method as interstitial type. Rel-rod dark field images were obtained by selecting streak at g → = 1 / 2 [ 31 1 ¯ ] in diffraction pattern to identify the Frank loops present in the microstructure. Subsequent analysis of a single dislocation loop using atomic resolution scanning transmission electron microscopy (STEM) confirmed the interstitial nature of the loop with { 111 } habit plane.

Advanced nuclear reactor concepts aim to use fuels that must withstand unprecedented temperature and radiation extremes. In these fuels, thermal energy transport under irradiation is directly related to fuel longevity, reactor safety, and is arguably one of the most important performance metrics. Here we provide a comprehensive, first-principles-informed treatment of phonon mediated thermal transport in a defect-bearing actinide oxide with direct comparison to experimental measurements. Pristine and proton irradiated thorium dioxide was chosen as a model system to treat the complexity of thermal transport in the presence of lattice defects. A thermal transport model is implemented using the linearized Boltzmann transport equation (LBTE) with input from first principles calculations and defect evolution models. Density functional theory is used to calculate phonon dispersion in thorium dioxide and used as an input to calculate both intrinsic and extrinsic, defect-induced relaxation times. In addition, a defect evolution model is benchmarked using microstructure characterization of as-irradiated thorium dioxide using a combination of electron microscopy and optical spectroscopy. The output of the LBTE is compared directly to mesoscopic measurements of thermal conductivity on length scales commensurate with defect accumulation. Parametric measurements of conductivity with irradiation dose and temperature suggest a saturation in the reduction of thermal conductivity with increasing defect generation, which is partially captured in our defect evolution model and LBTE framework. This comprehensive, atomistic- to meso-scale treatment provides the necessary basis to investigate thermal transport under irradiation in more complex systems that exhibit strong electron correlation.

The photoelectric work function of nearly stoichiometric (111) and (100) hydrothermally grown UO2 was measured to be 6.28 ± 0.36 eV and 5.80 ± 0.36 eV, respectively. Candidate metals for electrical contacts are identified for both rectifying and non-rectifying contacts based on work function, lattice compatibility, and electrical conductivity.

Atom probe tomography (APT), a 3D microscopy technique, has great potential to reveal atomic scale compositional variations, such as those associated with irradiation damage. However, obtaining accurate compositional quantification by APT for high bandgap materials is a longstanding challenge, given the sensitivity to field evaporation parameters and inconsistent behaviors across different oxides. This study investigates the influence of APT laser energy and specimen base temperature on compositional accuracy in single crystal thoria (ThO2). ThO2 has a broad range of applications, including advanced nuclear fuels, sensors, lasers and scintillators, electrodes, catalysis, and photonics and optoelectronics. The expected stoichiometry of ThO2 is achieved at APT base temperature of 24 K and laser energy of 100 pJ. To overcome mass resolution limitations associated with significant thermal tails, Bayesian methods are applied to deconvolute ion identity within the mass spectra. This approach affirms that the parameters chosen are appropriate for APT analysis of ThO2.

Thermal transport is a key performance metric for thorium dioxide in many applications where defect-generating radiation fields are present. An understanding of the effect of nanoscale lattice defects on thermal transport in this material is currently unavailable due to the lack of a single crystal material from which unit processes may be investigated. In this work, a series of high-quality thorium dioxide single crystals are exposed to 2 MeV proton irradiation at room temperature and 600 °C to create microscale regions with varying densities and types of point and extended defects. Defected regions are investigated using spatial domain thermoreflectance to quantify the change in thermal conductivity as a function of ion fluence as well as transmission electron microscopy and Raman spectroscopy to interrogate the structure of the generated defects. Together, this combination of methods provides important initial insight into defect formation, recombination, and clustering in thorium dioxide and the effect of those defects on thermal transport. These methods also provide a promising pathway for the quantification of the smallest-scale defects that cannot be captured using traditional microscopy techniques and play an outsized role in degrading thermal performance.

The semiconductor and optical properties of UO2 are investigated. The very long drift carrier lifetimes, obtained from current–voltage I(V) and capacitance–voltage C(V) measurements, along with the well-defined optical properties provide little evidence of an abundance of material defects away from the surface region. Schottky barrier formation may be possible, but very much dependent on the choice of contact and surface stoichiometry and we find that Ohmic contacts are in fact favored. Depth resolved photoemission provided evidence of a chemical shift at the surface. Density functional theory, with the Heyd-Scuseria-Ernzerhof (HSE) functional, indicates a band gap of a 2.19 eV and an anti-ferromagnetic ground state. Ellipsometry measurements indicates at UO2 is relatively isotropic with a band gap of approximately 2.0 eV band gap, consistent with theoretical expectations.

An investigation into the crystal chemistry of the alkali thorium silicates resulted in the formation of five novel materials by hydrothermal synthesis. Of these, Rb4Th2Si12O30, and K2ThSi4O10F2 are new structure types crystallizing in space groups P1 and Pnma, respectively. The structure of Rb4Th2Si12O30 reveals a silicate sheet structure with eight-, six-, five-, and four-membered silicate rings. Crystals of a related composition, Cs2ThSi6O15, were also synthesized. They crystallize in space group Cmc21 and have a silicate sheet containing eight-, six-, and four-membered silicate rings. The structure of K2ThSi4O10F2 consists of a tubular silicate column comprised of eight-, six-, and four-membered silicate rings and features chains of fluorine-bridged Th atoms. Two new wadeite analogues Cs2ThSi3O9 and Rb2ThSi3O9 were also discovered and constitute the first actinide representatives in this mineral family. All products were crystallized from reactions of ThO2 and silica with alkali fluorides or hydroxid...

Fe:ZnSe and other transition metals have broad upper and lower energy manifolds which give rise to broad absorption and fluorescence bands in the mid-IR spectral region. Energy transfer between Fe2p ions via re-absorption of fluorescence (due to the spectral overlap of these bands) and phonon-assisted energy transfer (due to the lattice dynamics of ZnSe) becomes more probable with increasing Fe2p concentration. Here we treat these processes as additional terms in the rate equations which govern the spontaneous decay of the Fe2p ion. This treatment gives insight into anomalous behavior seen in the thermal lifetime of the Fe:ZnSe system. We also apply the model to other transition metal doped II-VI materials.

The infrared-active phonon modes, in single-crystal samples of thorium dioxide (ThO 2) and uranium dioxide (UO 2), were investigated using spectroscopic ellipsometry and compared with density functional theory. Both ThO 2 and UO 2 are found to have one infrared-active phonon mode pair [consisting of one transverse optic (TO) and one associated longitudinal optic (LO) mode], which is responsible for the dominant features in the ellipsometric data. At room temperature, our results for the mode pair’s resonant frequencies and broadening parameters are comparable with previous reflectance spectroscopy characterizations and density functional theory predictions. For ThO 2, our ellipsometry and density function theory results both show that the LO mode broadening parameter is larger than the TO mode broadening. This signifies mode anharmonicity, which can be attributed to the intrinsic phonon–phonon interaction. In addition to the main mode pair, a broad low-amplitude impurity-like vibrational mode pair is detected within the reststrahlen band for both ThO 2 and UO 2. Elevated temperature measurements were performed for ThO 2 in order to study the mechanisms by which the phonon parameters evolve with increased heat. The observed change in the TO resonant frequency is in excellent agreement with previous density functional calculations, which only consider volume expansion of the crystal lattice. This suggests that the temperature-dependent change in the TO frequency is primarily due to volume expansion. The change in the main mode pair’s broadening parameters is nearly linear within the temperature range of this study, which indicates the intrinsic anharmonic scattering (via cubic anharmonicities) as the main decay mechanism.

Boron nitride thin films were grown on sapphire and Si substrates by atomic layer deposition from triethylborane (TEB) and NH3 precursors in the temperature range of 500 to 900 °C. By varying the TEB exposure the film thickness can be controlled with

The effective Debye temperatures ([Formula: see text]) of the surface region of UO

The electronic properties of ThO2 single crystals were studied using x-ray photoemission spectroscopy (XPS). The XPS results show that the Th 4f core level is in an oxidation state that is consistent with that expected for Th in ThO2. The effective Debye temperature is estimated from the temperature dependent photoemission intensities of the Th 4f core level over the temperature range of 290 to 360 K. A Debye temperature of 468±32 K has been determined.

Hydrothermal synthesis of ThO2, UxTh1-xO2, and UOxat temperatures between 670°C and 700°C has been demonstrated. Synthesis at these temperatures is 50-80°C below prior growth studies and represents a new lower bound of successful growth. ThO2single crystals of dimensions 6.49mm x 4.89mm x 3.89 mm and weighing 0.633g have been synthesized at average growth rates near 0.125mm/week. Single crystal UxTh1-xO2crystals with mole fractions up to x≈0.30 have also been grown. The largest alloyed crystal with mole fraction x≈0.23 has dimensions of 2.97mm x 3.23mm x ∼3mm and recorded average growth rates near 0.2mm/week. Four structures were solved from X-ray diffraction data and their crystallographic data reported here. Rocking curve analysis determined a dislocation density of 1.2×109cm-2.

The effective Debye temperatures () of the surface region of UO2 single crystals, prepared by the hydrothermal synthesis technique, were obtained from temperature-dependent x-ray photoemission in the temperature range of 300 K–623 K. A lattice stiffening transition, characterized by different regions of different effective Debye temperature, 500 ± 59 K below 475 K and 165 ± 21 K above 475 K is identified. A comparison of the temperature dependence of the effective UO2 Debye temperature, with the changes in the lattice expansion coefficient for UO2, support strong lattice-phonon interaction arising from the Jahn–Teller distortion.