High-resolution Electron Diffraction Research Articles

Composition Dictates Octahedral Tilt and Photostability in Halide Perovskites.

Halide perovskites are excellent candidate materials for use in solar cell, LED, and detector devices, in part because their composition can be tuned to achieve ideal optoelectronic properties. Empirical efficiency optimization has led the field toward compositions rich in FA (formamidinium) on the A-site and I on the X-site, with additional small amounts of MA (methylammonium) or Cs A-site cations and Br X-site anions. However, it is not clear how and why the specific compositions of alloyed, that is, mixed component, halide perovskites relate to photo-stability of the materials. Here, this work combines synchrotron grazing incidence wide-angle X-ray scattering, photoluminescence, high-resolution scanning electron diffraction measurements and theoretical modelling to reveal the links between material structure and photostability. Namely, this work finds that increased octahedral titling leads to improved photo-stability that is correlated with lower densities of performance-harming hexagonal polytype impurities. These results uncover the structural signatures underpinning photo-stability and can therefore be used to make targeted changes to halide perovskites, bettering the commercial prospects of technologies based on these materials.

Spherical and porous Cu2O nanocages with Cu2O/Cu(OH)2 Surface: Synthesis and their promising selectivity for catalysing CO2 electroreduction to C2H4

In the production of C2H4, a vital raw material in the synthesis of polyethylene and polyvinyl chloride, Cu2O is a highly promising catalyst with excellent Faradaic efficiency and selectivity. We propose a method involving the partial reduction of Cu(OH)2 to Cu2O by sodium L-ascorbate for the synthesis of spherical and porous Cu2O nanocages (SPNCs) with a surface containing both Cu2O and Cu(OH)2. High-resolution transmission electron microscopy and electron diffraction measurements revealed ∼ 3-nm pores and a (13¯2) high-index facet on the SPNC, respectively. As SPNCs have a porous structure, their specific surface area is greater (31.10 m2 g−1) than that (6.35 m2 g−1) of spherical Cu2O nanocrystals (SNCs) with solid interiors. Furthermore, SPNCs, when applied as electrocatalysts for catalysing the CO2 reduction reaction (CO2RR), demonstrated remarkable mass activities (16.92 mA mg−1 at −1.15 V vs. reversible hydrogen electrode) for C2H4 production, with a Faraday efficiency reaching an impressive 55.3 %. Stability test data showed a consistent CO2RR current density over 6 h, owing to the porous structure and the presence of both Cu(OH)2 and Cu2O on the catalyst surface. Our proposed SPNC catalysts can be employed as effective CO2RR catalysts for producing C2H4, which may help in reducing the present reliance on petrochemical processes.

High-Resolution Electron Diffraction of Hydrated Protein Crystals at Room Temperature.

Structural characterization is crucial to understanding protein function. Compared with X-ray diffraction methods, electron crystallography can be performed on nanometer-sized crystals and can provide additional information from the resulting Coulomb potential map. Whereas electron crystallography has successfully resolved three-dimensional structures of vitrified protein crystals, its widespread use as a structural biology tool has been limited. One main reason is the fragility of such crystals. Protein crystals can be easily damaged by mechanical stress, change in temperature, or buffer conditions as well as by electron irradiation. This work demonstrates a methodology to preserve these nanocrystals in their natural environment at room temperature for electron diffraction experiments as an alternative to existing cryogenic techniques. Lysozyme crystals in their crystallization solution are hermetically sealed via graphene-coated grids, and their radiation damage is minimized by employing a low-dose data collection strategy in combination with a hybrid-pixel direct electron detector. Diffraction patterns with reflections of up to 3 Å are obtained and successfully indexed using a template-matching algorithm. These results demonstrate the feasibility of in situ protein electron diffraction. The method described will also be applicable to structural studies of hydrated nanocrystals important in many research and technological developments.

Impact of Anionic Ordering on the Iron Site Distribution and Valence States in Oxyfluoride Sr2FeO3+xF1-x (x = 0.08, 0.2) with a Layered Perovskite Network.

Sr2FeO3F, an oxyfluoride compound with an n = 1 Ruddlesden-Popper structure, was identified as a potential interesting mixed ionic and electronic conductor (MIEC). The phase can be synthesized under a range of different pO2 atmospheres, leading to various degrees of fluorine for oxygen substitution and Fe4+ content. A structural investigation and thorough comparison of both argon- and air-synthesized compounds were performed by combining high-resolution X-ray and electron diffraction, high-resolution scanning transmission electron microscopy, Mössbauer spectroscopy, and DFT calculations. While the argon-synthesized phase shows a well-behaved O/F ordered structure, this study revealed that oxidation leads to averaged large-scale anionic disorder on the apical site. In the more oxidized Sr2FeO3.2F0.8 oxyfluoride, containing 20% of Fe4+, two different Fe positions can be identified with a 32%/68% occupancy (P4/nmm space group). This originates due to the presence of antiphase boundaries between ordered domains within the grains. Relations between site distortion and valence states as well as stability of apical anionic sites (O vs F) are discussed. This study paves the way for further studies on both ionic and electronic transport properties of Sr2FeO3.2F0.8 and its use in MIEC-based devices, such as solid oxide fuel cells.

Unveiling the complexity of nanodiamond structures

Understanding nanodiamond structures is of great scientific and practical interest. It has been a long-standing challenge to unravel the complexity underlying nanodiamond structures and to resolve the controversies surrounding their polymorphic forms. Here, we use transmission electron microscopy with high-resolution imaging, electron diffraction, multislice simulations, and other supplementary techniques to study the impacts of small sizes and defects on cubic diamond nanostructures. The experimental results show that common cubic diamond nanoparticles display the (200) forbidden reflections in their electron diffraction patterns, which makes them indistinguishable from new diamond (n-diamond). The multislice simulations demonstrate that cubic nanodiamonds smaller than 5 nm can present the d-spacing at 1.78 Å corresponding to the (200) forbidden reflections, and the relative intensity of these reflections increases as the particle size decreases. Our simulation results also reveal that defects, such as surface distortions, internal dislocations, and grain boundaries can also make the (200) forbidden reflections visible. These findings provide valuable insights into the diamond structural complexity at nanoscale, the impact of defects on nanodiamond structures, and the discovery of novel diamond structures.

Successful Growth of TiO2 Nanocrystals with {001} Facets for Solar Cells

The growth of nanocrystals (NCs) from metal oxide-based substrates with exposed high-energy facets is of particular importance for many important applications, such as solar cells as photoanodes due to the high reactivity of these facets. The hydrothermal method remains a current trend for the synthesis of metal oxide nanostructures in general and titanium dioxide (TiO2) in particular since the calcination of the resulting powder after the completion of the hydrothermal method no longer requires a high temperature. This work aims to use a rapid hydrothermal method to synthesize numerous TiO2-NCs, namely, TiO2 nanosheets (TiO2-NSs), TiO2 nanorods (TiO2-NRs), and nanoparticles (TiO2-NPs). In these ideas, a simple non-aqueous one-pot solvothermal method was employed to prepare TiO2-NSs using tetrabutyl titanate Ti(OBu)4 as a precursor and hydrofluoric acid (HF) as a morphology control agent. Ti(OBu)4 alone was subjected to alcoholysis in ethanol, yielding only pure nanoparticles (TiO2-NPs). Subsequently, in this work, the hazardous chemical HF was replaced by sodium fluoride (NaF) as a means of controlling morphology to produce TiO2-NRs. The latter method was required for the growth of high purity brookite TiO2 NRs structure, the most difficult TiO2 polymorph to synthesize. The fabricated components are then morphologically evaluated using equipment, such as transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), electron diffraction (SAED), and X-ray diffraction (XRD). In the results, the TEM image of the developed NCs shows the presence of TiO2-NSs with an average side length of about 20-30 nm and a thickness of 5-7 nm. In addition, the image TEM shows TiO2-NRs with diameters between 10 and 20 nm and lengths between 80 and 100 nm, together with crystals of smaller size. The phase of the crystals is good, confirmed by XRD. The anatase structure, typical of TiO2-NS and TiO2-NPs, and the high-purity brookite-TiO2-NRs structure, were evident in the produced nanocrystals, according to XRD. SAED patterns confirm that the synthesis of high quality single crystalline TiO2-NSs and TiO2-NRs with the exposed {001} facets are the exposed facets, which have the upper and lower dominant facets, high reactivity, high surface energy, and high surface area. TiO2-NSs and TiO2-NRs could be grown, corresponding to about 80% and 85% of the {001} outer surface area in the nanocrystal, respectively.

MoxWx–1S2 Nanotubes for Advanced Field Emission Application

AbstractTransition metal dichalcogenide (TMDC) nanotubes complement the field of low‐dimensional materials with their quasi‐1D morphology and a wide set of intriguing properties. By introducing different transition metals into the crystal structure, their properties can be tailored for specific purpose and applications. Herein, the characterization and a subsequent preparation of single‐nanotube field emission devices of MoxWx‐1S2 nanotubes prepared via the chemical vapor transport reaction is presented. Energy‐dispersive X‐ray spectroscopy, Raman spectroscopy, and X‐ray diffraction indicate that the molybdenum and tungsten atoms are randomly distributed within the crystal structure and that the material is highly crystalline. High resolution transmission electron microscopy and electron diffraction (ED) patterns further corroborate these findings. A detailed analysis of the ED patterns from an eight‐layer nanotube reveal that the nanotubes grow in the 2H structure, with each shell consists of one bilayer. The work function of the nanotubes is comparable to that of pure MoS2 and lower of pure WS2 NTs, making them ideal candidates for field emission applications. Two devices with different geometrical setup are prepared and tested as field emitters, showing promising results for single nanotube field emission applications.

(Invited) In Situ TEM Studies of Colloidal Inorganic Nanocrystals for Energy Applications

Sustainable technologies will be essential for meeting future energy demands. Therefore, it is critical to be exploring the fundamental science of materials for photovoltaics and catalysis. For these applications, nanomaterials hold great promise due to their unique, size-dependent properties, tunability, and solution processability. Additionally, nanomaterials offer an effective testbed to understand structural transformations in bulk materials, and to take advantage of effects related to having a high surface area to volume ratio.Transmission electron microscopy (TEM) allows a unique window into the atomic structures of nanomaterials by enabling high-resolution imaging, electron diffraction, and compositional analysis. Specifically, this work explores local structural and compositional transformations by examining how colloidal nanocrystals transform under in situ conditions during imaging. Focusing on halide perovskite nanocrystals for photovoltaic applications and metal nanocrystals for catalytic applications, the roles of size, shape, and composition will be explored, as well as the impact of atomic defects.The degradation of halide perovskites is a major issue facing the field and can be mitigated by an in-depth understanding of the structural changes that occur during degradation processes. For instance, the relative stability of different compositions and dissimilar geometries can provide insights into which factors could improve the longevity of photovoltaic devices. Similarly, metallic nanocrystals for heterogeneous catalysis rely on reactive surfaces, which can be identified, examined, and transformed during in situ TEM experiments. This presentation will describe progress toward understanding transformation mechanisms in these two classes of nanocrystals, and it will provide comparative insights across the systems.

Analysis and comparison of electron radiation damage assessments in Cryo-EM by single particle analysis and micro-crystal electron diffraction.

Electron radiation damage to macromolecules is an inevitable resolution limit factor in all major structural determination applications using cryo-electron microscopy (cryo-EM). Single particle analysis (SPA) and micro-crystal electron diffraction (MicroED) have been employed to assess radiation damage with a variety of protein complexes. Although radiation induced sidechain density loss and resolution decay were observed by both methods, the minimum dose of electron irradiation reducing high-resolution limit reported by SPA is more than ten folds higher than measured by MicroED using the conventional dose concept, and there is a gap between the attained resolutions assessed by these two methods. We compared and analyzed these two approaches side-by-side in detail from several aspects to identify some crucial determinants and to explain this discrepancy. Probability of a high energy electron being inelastically scattered by a macromolecule is proportional to number of layers of the molecules in its transmission path. As a result, the same electron dose could induce much more site-specific damage to macromolecules in 3D protein crystal than single particle samples. Major differences in data collection and processing scheme are the key factors to different levels of sensitivity to radiation damage at high resolution between the two methods. High resolution electron diffraction in MicroED dataset is very sensitive to global damage to 3D protein crystals with low dose accumulation, and its intensity attenuation rates at atomic resolution shell could be applied for estimating ratio of damaged and total selected single particles for SPA. More in-depth systematically radiation damage assessments using SPA and MicroED will benefit all applications of cryo-EM, especially cellular structure analysis by tomography.

On the thickness dependence of the polarization switching kinetics in HfO2-based ferroelectric

HfO2-based ferroelectric (FE–HfO2) is a promising material for low-power and high-capacity memory technology. Since thinner ferroelectric films are required for low voltage operation, the impact of film thickness on the switching kinetics of FE–HfO2 needs to be studied in detail. In this paper, metal/ferroelectric/metal capacitors are fabricated with several thicknesses of HfZrO2 (HZO) films and characterized to study the switching kinetics based on the nucleation limited switching (NLS) model. Thinner HZO capacitors show slower polarization switching and asymmetry in program and erase operation, although low-frequency polarization charge density is nearly the same for all thicknesses. Slow switching is due to the large variability of the activation field of FE domains and grain boundaries among small FE grains. The asymmetry is caused by the asymmetric interface property at the top and bottom interfaces. High-resolution TEM and electron diffraction mapping methods provide physical evidence for the above discussions.

High-Resolution Electron Diffraction of Protein Crystals in Their Liquid Environment at Room Temperature Using a Direct Electron Detection Camera

High-Resolution Electron Diffraction of Protein Crystals in Their Liquid Environment at Room Temperature Using a Direct Electron Detection Camera

In Situ Atomic-Scale Observation of Electrochemical (De)potassiation in Te Nanowires.

Potassium-ion batteries (PIBs) have great potential in energy storage due to their high abundance and low cost of potassium resources. Tellurium (Te) is a promising PIB cathode due to its high volumetric capacity and good electronic conductivity. However, the electrochemical (de)potassiation mechanism of Te remains elusive due to the lack of an effective method of directly observing the dynamic reaction at atomic resolution. Here, the phase transformations of single crystal Te on (de)potassiation are clearly revealed by in situ high-resolution transmission electron microscopy and electron diffraction. Te undergoes a consecutive phase transformation during potassiation: from Te to K2 Te3 in the initial potassiation, and then part of the K2 Te3 to K5 Te3 on further potassiation. The reaction has extremely high reversibility in the following depotassiation. By atomic-scale observation, an anisotropic reaction mechanism where K+ intercalates into Te crystalline lattice preferentially through the (001) plane (having a large d-spacing) is established during potassiation. While in the depotassiation process, K ions extract from the polycrystalline Kx Te along the same diffusion path to form single crystal Te, indicating the potassium storage is highly reversible. The strong orientation-dependent (de)potassiation mechanism revealed by this work provides implications for the future design of nanostructured cathodes for high-performance PIBs.

High performance high-power textured Mn/Cu-doped PIN-PMN-PT ceramics

Piezoelectric ceramics with combinatory soft and hard characteristics are highly desired for high-power applications. However, it remains grand challenge to achieve simultaneous presence of hard (e.g. high coercive field, Ec; high mechanical quality factor, Qm) and soft (e.g. high piezoelectric constant, d; high electromechanical coupling factor, k) piezoelectric properties in piezoelectric ceramics since the mechanism controlling the hard behavior (pinned domain walls) will significantly reduce the soft behavior. Here, we address this grand challenge and demonstrate <001> textured MnO2 and CuO co-doped Pb(In1/2Nb1/2)O3- Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) ceramics exhibiting ultrahigh combined soft and hard piezoelectric properties (d33 = 713 pC N−1, k31 = 0.52, Qm≈950, Ec = 9.6 kV cm−1, tan δ = 0.45%). The outstanding electromechanical properties are explained by considering composition/phase selection, crystallographic anisotropy and defect engineering. Phase-field model in conjunction with high resolution electron microscopy and diffraction techniques is utilized to delineate the contributions arising from intrinsic piezoelectric response, domain dynamics, and local structural heterogeneity. These results will have significant impact in the development of high-power transducers and actuators.

Tracing the Active Phase and Dynamics for Carbon Nanofiber Growth on Nickel Catalyst Using Environmental Transmission Electron Microscopy.

Benefitting from outstanding ability of CC reforming and hydrogen activation, nickel is widely applied for heterogeneous catalysis or producing high-quality carbon structures. This high activity simultaneously induces uncontrollable carbon formation, known as coking. However, the activity origin for growing carbon species remains in debate between the on metallic facets induction and nickel carbide segregation. Herein, carbon growth on Ni catalyst is tracked via in situ microscopy methods. Evidence derived from high-resolution transmission electron microscopy imaging, diffraction, and energy loss spectroscopy unambiguously identifies Ni3 C as the active phase, as opposed to metallic Ni nickel or surface carbides as traditionally believed. Specifically, Ni3 C particle grows carbon nanofibers (CNF) layer-by-layer through synchronized oscillation of tip stretch and atomic step fluctuations. There is an anisotropic stress distribution in Ni3 C that provides the lifting force during nanofiber growth. Density functional theory computations show that it is thermodynamically favorable for Ni3 C to decompose into Ni and surface-adsorbed carbon. Carbonaceous deposits aggregate asymmetrically round the particle because partial surface is exposed to the hydrocarbon environment whereas the bottom side is shielded by the support. This induces a carbon concentration gradient within the particle, which drives C migration through Ni3 C phase before it exits as CNF growth.

Quantum confinement and effective masses dependence in black phosphorus quantum dots and phosphorene

In the present study, quantum confinement effect in phosphorene and black phosphorus quantum dots is extensively studied from experimental and theoretical viewpoints. These quantum structures were prepared with the help of Benzonitrile solvent using Liquid Phase Exfoliation and solvothermal-assisted Liquid Phase Exfoliation, respectively. On one hand, Fourier-transform infrared spectroscopy shows no sign of phosphorus oxidation in both phosphorene and black phosphorus quantum dots solutions. Furthermore, Raman spectroscopy showed a shift in B2gandAg2 phonon modes for phosphorene and black phosphorus quantum dots as compared to bulk black phosphorus. On the other hand, structural characterization via high-resolution transmission electron microscopy imaging and electron diffraction patterns showed a high degree of crystallinity in both quantum structures with no sign of aggregations. Optical properties characterization showed the expected increase in the bandgap value for both quantum structures, which were supported by theoretical calculations using density functional theory and effective mass approximation. Interestingly, we demonstrate that the quantum confinement observed in phosphorene is weakened to the expected extent, relative to that in BPQDs, by the loss of two confinement dimensions. Appropriate models, describing the bandgap and effective mass dependence as a function of the confinement regime, are presented.

Light-assisted defects migration in cuprous iodide (CuI)

We report light-assisted iodine ion migration in CuI – a popular wide bandgap p-type semiconductor, which was synthesized via iodinating Cu film in iodine solution. In-depth crystallographic analysis was performed with the combination methods of X-ray diffraction (XRD), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), crystal modeling and diffraction simulation. The samples show strong diffraction peaks of γ-CuI, yet still exists β phase diffraction. Loop current-voltage (IV) test shows characteristics of resistive random access memory (RRAM), suggesting the existence of large amount of movable native defects, which forms the conductive filaments. UV irradiation was found to be effective to convert the RRAM device from low resistance state (LRS) to high resistance state (HRS), indicating potential application of novel memory device with electric read-in and optical erasure function. To study the properties of native defects, time-lapsed PL were employed, in which the near band edge defects luminescence, related to VCu, increased, whereas mid-band broad luminescence, related to VI, decreased, with the increase of irradiation time. UV irradiation induced defects evolution was also observed in X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES). Finally, we propose the microscopic physical mechanism of defect migration in CuI with the assistance of UV irradiation. This work reveals the nature of point defects evolution in CuI under light irradiation and is expected to arise more discussions on defects formation, migration and light-defects interaction of CuI material.

New Phenotype and Mineralization of Biogenic Iron Oxide in Magnetotactic Bacteria.

Many magnetotactic bacteria (MTB) biomineralize magnetite crystals that nucleate and grow inside intracellular membranous vesicles originating from invaginations of the cytoplasmic membrane. The crystals together with their surrounding membranes are referred to as magnetosomes. Magnetosome magnetite crystals nucleate and grow using iron transported inside the vesicle by specific proteins. Here, we tackle the question of the organization of magnetosomes, which are always described as constituted by linear chains of nanocrystals. In addition, it is commonly accepted that the iron oxide nanocrystals are in the magnetite-based phase. We show, in the case of a wild species of coccus-type bacterium, that there is a double organization of the magnetosomes, relatively perpendicular to each other, and that the nanocrystals are in fact maghemite. These findings were obtained, respectively, by using electron tomography of whole mounts of cells directly from the environment and high-resolution transmission electron microscopy and diffraction. Structure simulations were performed with the MacTempas software. This study opens new perspectives on the diversity of phenotypes within MTBs and allows to envisage other mechanisms of nucleation and formation of biogenic iron oxide crystals.

Electronic surface reconstruction of TiO2 nanocrystals revealed by resonant inelastic x-ray scattering

The identification of lattice multiphases in TiO2 nanocrystals is studied by high resolution transmission electron microscope and electron diffraction patterns. Based on the spectroscopic analysis using soft x-ray absorption and resonant inelastic soft x-ray scattering, it is believed that the oxygen vacancies at the interface exhibit structural distortion of the TiO68− cluster around the defect site as for the multiphase lattice. We elucidate that the extra 3d electrons nearby induce the inelastic scattering features with the excitation energy dependence owing to different energy relaxation processes, a characteristic of the electron-phonon coupling or the nature of the electron-hole pair at the intermediate state. The manifold dd excitations driven by the strong interaction between Ti-3d and O-2p electrons are noticeably rich, coexisting on both Ti and O sites. This sophisticated experiment can advance the perspective of nanocomposite TiO2 for various interactions of surface Ti3+ in applications of future devices.

Comprehensive Study of Li+/Ni2+ Disorder in Ni-Rich NMCs Cathodes for Li-Ion Batteries

The layered oxides LiNixMnyCozO2 (NMCs, x + y + z = 1) with high nickel content (x ≥ 0.6, Ni-rich NMCs) are promising high-energy density-positive electrode materials for Li-ion batteries. Their electrochemical properties depend on Li+/Ni2+ cation disordering originating from the proximity of the Li+ and Ni2+ ionic radii. We synthesized a series of the LiNi0.8Mn0.1Co0.1O2 NMC811 adopting two different disordering schemes: Ni for Li substitution at the Li site in the samples finally annealed in air, and close to Ni↔Li antisite disorder in the oxygen-annealed samples. The defect formation scenario was revealed with Rietveld refinement from powder X-ray diffraction data, and then the reliability of semi-quantitative parameters, such as I003/I104 integral intensity ratio and c/(2√6a) ratio of pseudocubic subcell parameters, was verified against the refined defect concentrations. The I003/I104 ratio can serve as a quantitative measure of g(NiLi) only after explicit correction of intensities for preferred orientation. Being normalized by the total scattering power of the unit cell, the I003/I104 ratio depends linearly on g(NiLi) for each disordering scheme. The c/(2√6a) ratio appears to be not reliable and cannot be used for a quantitative estimate of g(NiLi). In turn, the volume of the R3¯m unit cell correlates linearly with g(NiLi), at least for defect concentrations not exceeding 5%. The microscopy techniques such as high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and electron diffraction tomography (EDT) allow us to study the materials locally, still, there is no proper quantitative approach for comprehensive analysis of defects. In the present work, the TEM-assisted quantitative Li+/Ni2+ disordering analysis with EDT and HAADF-STEM in six Ni-rich NMC samples with various defects content is demonstrated. Noteworthy, while PXRD and EDT methods demonstrate overall defect amounts, HAADF-STEM allows us to quantitatively distinguish regions with various disordering extents. Therefore, the combination of mentioned PXRD and TEM methods gives the full picture of Li+/Ni2+ mixing defects in Ni-rich NMCs.

Irradiation-Driven Restructuring of UO2 Thin Films: Amorphization and Crystallization

Combustion synthesis in uranyl nitrate-acetylacetone-2-methoxyethanol solutions was used to deposit thin UO2 films on aluminum substrates to investigate the irradiation-induced restructuring processes. Thermal analysis revealed that the combustion reactions in these solutions are initiated at ∼160 °C. The heat released during the process and the subsequent brief annealing at 400 °C allow the deposition of polycrystalline films with 5-10 nm UO2 grains. The use of multiple deposition cycles enables tuning of the film thicknesses in the 35-260 nm range. Irradiation with Ar2+ ions (1.7 MeV energy and a fluence of up to 1 × 1017 ions/cm2) is utilized to generate a uniform distribution of atomic displacements within the films. X-ray fluorescence (XRF) and alpha-particle emission spectroscopy showed that the films were stable under irradiation and did not undergo sputtering degradation. X-ray photoelectron spectroscopy (XPS) showed that the stoichiometry and uranium ionic concentrations remain stable during irradiation. The high-resolution electron microscopy imaging and electron diffraction analysis demonstrated that at the early stages of irradiation (below 1 × 1016 ion/cm2) UO2 films show complete amorphization and beam-induced densification (sintering), resulting in a pore-free disordered film. Prolonged irradiation (5 × 1016 ion/cm2) is shown to trigger a crystallization process at the surface of the films that moves toward the UO2/Al interface, converting the entire amorphous material into a highly crystalline film. This work reports on an entirely different radiation-induced restructuring of the nanoscale UO2 compared to the coarse-grained counterpart. The preparation of thin UO2 films deposited on Al substrates fills an area of national need within the stockpile stewardship program of the National Nuclear Security Administration and fundamental research with actinides. The method reported in this work produces pure, robust, and uniform thin-film actinide targets for nuclear science measurements.