We report the results of a large-scale modelling study of radiation damage effects in the nuclear waste form zirconolite. We particularly focus on the effects of radiation damage in amorphous zirconolite and have developed a new way to analyse the damaged structure in terms of local coordination statistics. On the basis of this analysis, we find that the amorphous structure responds to radiation damage differently from the crystal. Amorphous zirconolite is found to be "softer" than crystalline zirconolite with a much larger number of atoms becoming displaced and changing coordination during a 70 keV cascade. The local coordination and connectivity analysis shows that the amorphous structure continues to evolve as a result of repeated radiation damage, changes which cannot be identified from globally averaged properties such as pair distribution functions. We also find large density inhomogeneities at the local level which we suggest may play an important role for future developments in nuclear waste storage. Finally, we find a correlation between the changes in enthalpy and local coordination, suggesting that measurements of enthalpy change can be linked quantitatively to structural radiation damage. Our results raise an interesting possibility of whether an evolution of the amorphous structure due to radiation damage can converge to a new equilibrium amorphous regime, posing the fundamental question of what that structure may be.
We discuss how structural disorder and amorphization affects solid-state diffusion, and consider zirconolite as a currently important case study. By performing extensive molecular dynamics simulations, we disentangle the effects of amorphization and density, and show that a profound increase of solid-state diffusion takes place as a result of amorphization. Importantly, this can take place at the same density as in the crystal, representing an interesting general insight regarding solid-state diffusion. We find that decreasing the density in the amorphous system increases pre-factors of diffus…
The nature of the amorphous state has been notably difficult to ascertain at the microscopic level. In addition to the fundamental importance of understanding the amorphous state, potential changes to amorphous structures as a result of radiation damage have direct implications for the pressing problem of nuclear waste encapsulation. Here, we develop new methods to identify and quantify the damage produced by high-energy collision cascades that are applicable to amorphous structures and perform large-scale molecular dynamics simulations of high-energy collision cascades in a model zircon syste…
Nanocrystalline metals are promising radiation tolerant materials due to their large interfacial volume fraction, but irradiation-induced grain growth can eventually degrade any improvement in radiation tolerance. Therefore, methods to limit grain growth and simultaneously improve the radiation tolerance of nanocrystalline metals are needed. Amorphous intergranular films are unique grain boundary structures that are predicted to have improved sink efficiencies due to their increased thickness and amorphous structure, while also improving grain size stability. In this study, ball milled nanocry…
Crystalline to amorphous phase transformation during initial lithiation in (100) silicon-wafers is studied in an electrochemical cell with lithium metal as the counter and reference electrode. It is demonstrated that severe stress jumps across the phase boundary lead to fracture and damage, which is an essential consideration in designing silicon based anodes for lithium ion batteries. During initial lithiation, a moving phase boundary advances into the wafer starting from the surface facing the lithium electrode, transforming crystalline silicon into amorphous LixSi. The resulting biaxial com…
This experimental PhD work deals with the generation and transformation processes of point defects induced by UV laser irradiation on amorphous silicon dioxide (silica). The investigation relies on several spectroscopic techniques used to probe the microscopic damage induced by UV laser on the material. The most innovative approach, however, is the measurement in situ of the absorption signals related to laser-induced point defects. This technique yields new information on the kinetics of defect processes, inaccessible to previous works based only on stationary measurements of laser-induced da…
Atomic layer deposition (ALD) provides uniform and conformal thin films that are of interest for a range of applications. To better understand the properties of amorphous ALD films, we need improved understanding of their local atomic structure. Previous work demonstrated measurement of how the local atomic structure of ALD-grown aluminum oxide (AlOx) evolves in operando during growth by employing synchrotron high energy X-ray diffraction (HE-XRD). In this work, we report on efforts to employ electron diffraction pair distribution function (ePDF) measurements using more broadly available trans…
We report the effects of radiation damage on helium diffusion in zircon using data from molecular dynamics simulations. We observe an increase in activation energy for helium diffusion as a result of radiation damage and increasing structural disorder. The activation energy in a heavily damaged region is smaller than in a completely amorphous system which is correlated with remaining order in the cation sublattices of the damaged structure not present in the fully amorphized system. The reduction of activation energy is related to the disappearance of fast diffusion pathways that present in th…
Dynamical screening effects on formation of swift heavy ions damage in GaN
P.N. Lebedev Institute of the Russian Academy of Sciences（俄罗斯科学院列别捷夫物理研究所）；Flerov Laboratory of Nuclear Research, Joint Institute for Nuclear Research（俄罗斯联合核研究所弗廖罗夫核研究实验室）；The Institute of Nuclear Physics（核物理研究所）
Atomistic simulations are used to explore the effect of interfacial structure on residual radiation damage. Specifically, an ordered grain boundary is compared to a disordered amorphous intergranular film, to investigate how interface thickness and free volume impacts point defect recombination. The collision cascades induced by neutron bombardment are simulated and residual point defect populations are analyzed as a function of boundary type and primary knock on atom energy. While ordered grain boundaries easily absorb interstitials, these interfaces are inefficient vacancy sinks. Alternative…
Modulation of structural short-range order due to chemical patterning in multi-component amorphous interfacial complexions
University of California, Irvine（加州大学尔湾分校）；Johns Hopkins University（约翰斯·霍普金斯大学）；Irvine Materials Research Institute, University of California, Irvine（加州大学尔湾分校欧文材料研究所）
Complexions are phase-like interfacial features that can influence a wide variety of properties, but the ability to predict which material systems can sustain these features remains limited. Amorphous complexions are of particular interest due to their ability to enhance diffusion and damage tolerance mechanisms, as a result of the excess free volume present in these structures. In this paper, we propose a set of materials selection rules aimed at predicting the formation of amorphous complexions, with an emphasis on (1) encouraging the segregation of dopants to the interfaces and (2) lowering…
The damage growth and surface modifications in Si(100), induced by 25 keV Si$_5^-$ cluster ions, as a function of fluence, $ϕ$, has been studied using atomic force microscopy (AFM) and channeling Rutherford backscattering spectrometry (CRBS). CRBS results indicate a nonlinear growth in damage from which it has been possible to get a threshold fluence, $ϕ_0$, for amorphization as $2.5\times 10^{13}$ ions-cm$^{-2}$. For $ϕ$ below $ϕ_0$, a growth in damage as well as surface roughness has been observed. At a $ϕ$ of $1\times 10^{14}$ ions-cm$^{-2}$, damage saturation coupled with a much reduced su…
We investigate the fragmentation process of solid materials with crystalline and amorphous phases using the discrete element method. Damage initiates inside spherical samples above the contact zone in a region where the circumferential stress field is tensile. Cracks initiated in this region grow to form meridional planes. If the collision energy exceeds a critical value which depends on the material's internal structure, cracks reach the sample surface resulting in fragmentation. We show that this primary fragmentation mechanism is very robust with respect to the internal structure of the mat…
From phase transformation to amorphization: damage accumulation in Yb-implanted $β-Ga_2O_3$
National Centre for Nuclear Research（国家核研究中心）；Institute of High Pressure Physics UNIPRESS, Polish Academy of Sciences（波兰科学院高压物理研究所）；Helmholtz-Zentrum Dresden-Rossendorf（德累斯顿-罗斯多尔夫亥姆霍兹中心）
Studying the atomic structure of intrinsic defects in two-dimensional transition metal dichalcogenides is difficult since they damage quickly under the intense electron irradiation in transmission electron microscopy (TEM). However, this can also lead to insights into the creation of defects and their atom-scale dynamics. We first show that MoTe 2 monolayers without protection indeed quickly degrade during scanning TEM (STEM) imaging, and discuss the observed atomic-level dynamics, including a transformation from the 1H phase into 1T', three-fold rotationally symmetric defects, and the migrati…
Metal-Oxide-Semiconductor (MOS) structures containing 74Ge nanocrystals (NC-Ge) imbedded inside the SiO_2 layer were studied for their capacitance characterization. Ge atoms were introduced by implantation of 74Ge+ ions with energy of 150 keV into relatively thick (~640nm) amorphous SiO_2 films. The experimental characterization included room temperature measurements of capacitance-voltage (C-V) dependences at high frequencies (100 kHz and 1 MHz). Four groups of MOS structures have been studied: The 1st - "initial" samples, without Ge atoms (before ion implantation). The 2nd - "implanted" samp…
