Individual Point Defects Research Articles

From solid solution to cluster formation of Fe and Cr in α-Zr

To understand the mechanisms by which the re-solution of Fe and Cr additions increase the corrosion rate of irradiated Zr alloys, the solubility and clustering of Fe and Cr in model binary Zr alloys was investigated using a combination of experimental and modelling techniques — atom probe tomography (APT), x-ray diffraction (XRD), thermoelectric power (TEP) and density functional theory (DFT). Cr occupies both interstitial and substitutional sites in the α-Zr lattice; Fe favours interstitial sites, and a low-symmetry site that was not previously modelled is found to be the most favourable for Fe. Lattice expansion as a function of Fe and Cr content in the α-Zr matrix deviates from Vegard's law and is strongly anisotropic for Fe additions, expanding the c-axis while contracting the a-axis. Matrix content of solutes cannot be reliably estimated from lattice parameter measurements, instead a combination of TEP and APT was employed. Defect clusters form at higher solution concentrations, which induce a smaller lattice strain compared to the dilute defects. In the presence of a Zr vacancy, all two-atom clusters are more soluble than individual point defects and as many as four Fe or three Cr atoms could be accommodated in a single Zr vacancy. The Zr vacancy is critical for the increased apparent solubility of defect clusters; the implications for irradiation induced microstructure changes in Zr alloys are discussed.

Characterization and manipulation of individual defects in insulating hexagonal boron nitride using scanning tunnelling microscopy.

Defects play a key role in determining the properties and technological applications of nanoscale materials and, because they tend to be highly localized, characterizing them at the single-defect level is of particular importance. Scanning tunnelling microscopy has long been used to image the electronic structure of individual point defects in conductors, semiconductors and ultrathin films, but such single-defect electronic characterization remains an elusive goal for intrinsic bulk insulators. Here, we show that individual native defects in an intrinsic bulk hexagonal boron nitride insulator can be characterized and manipulated using a scanning tunnelling microscope. This would typically be impossible due to the lack of a conducting drain path for electrical current. We overcome this problem by using a graphene/boron nitride heterostructure, which exploits the atomically thin nature of graphene to allow the visualization of defect phenomena in the underlying bulk boron nitride. We observe three different defect structures that we attribute to defects within the bulk insulating boron nitride. Using scanning tunnelling spectroscopy we obtain charge and energy-level information for these boron nitride defect structures. We also show that it is possible to manipulate the defects through voltage pulses applied to the scanning tunnelling microscope tip.

Atomically resolved structural determination of graphene and its point defects via extrapolation assisted phase retrieval

Previously reported crystalline structures obtained by an iterative phase retrieval reconstruction of their diffraction patterns seem to be free from displaying any irregularities or defects in the lattice, which appears to be unrealistic. We demonstrate here that the structure of a nanocrystal including its atomic defects can unambiguously be recovered from its diffraction pattern alone by applying a direct phase retrieval procedure not relying on prior information of the object shape. Individual point defects in the atomic lattice are clearly apparent. Conventional phase retrieval routines assume isotropic scattering. We show that when dealing with electrons, the quantitatively correct transmission function of the sample cannot be retrieved due to anisotropic, strong forward scattering specific to electrons. We summarize the conditions for this phase retrieval method and show that the diffraction pattern can be extrapolated beyond the original record to even reveal formerly not visible Bragg peaks. Such extrapolated wave field pattern leads to enhanced spatial resolution in the reconstruction.

Probing individual point defects in graphene via near-field Raman scattering.

The Raman scattering D-peak in graphene is spatially localised in close proximity to defects. Here, we demonstrate the capability of tip-enhanced Raman spectroscopy (TERS) to probe individual point defects, even for a graphene layer with an extremely low defect density. This is of practical interest for future graphene electronic devices. The measured TERS spectra enable a direct determination of the average inter-defect distance within the graphene sheet. Analysis of the TERS enhancement factor of the graphene Raman peaks highlights the preferential enhancement and symmetry-dependent selectivity of the D-peak intensity caused by zero-dimensional Raman scatterers.

Nanometric Resolved Cathodoluminescence on Few-Layer h-BN Flakes

Within the latest years number of layered materials at reduced dimensions have demonstrated remarkable optical properties. However most studies focused on perfect system and the role of defects as optical active centers remain still largely unexplored. Hexagonal boron nitride (h-BN) is one of the most promising candidates for light emitting devices in the far UV region, presenting a single strong excitonic emission at 5.8 eV. However, a single line appears only in extremely pure monocrystals that can hardly be obtained only though complex synthesis processes. Common h-BN samples present more complex emission spectra that have been generally attributed to the presence of structural defects. Despite a large number of experimental studies up to now it was not possible to attribute specific emission features to well identify defective structures. Here we address this fundamental questions by adopting a theoretical and experimental approach combining few nanometer resolved cathodoluminescence techniques with high resolution transmission electron microscopy images and state of the art quantum mechanical simulations. Very recently, the Orsay team has developed a cathodoluminescence detection system integrated within a scanning transmission electron microscope. This unique experimental set up is now able to provide full emission spectra with a resolution as low as few tens of meV associated with an electron probe size of one nanometer. A cathodoluminescence spectrum-image can thus be recorded in parallel with an HAADF image. Nanometric resolved cathodoluminescence on few-layer chemically exfoliated h-BN crystals have shown that emission spectra are strongly inhomogeneous within individual flakes. Emission peaks close to the free exciton appear in extended regions. Complementary investigations through high resolution transmission electron microscopy allow to associate these emission lines with extended crystal deformation such as stacking faults and folds of the planes. By means of ab-initio calculations in the framework of Many Body Perturbation Theory (GW approximation and Bethe-Salpeter equation) we provide an in-depth description of the electronic structure and spectroscopic response of bulk hexagonal boron nitride in the presence of extended morphological modifications. In particular we show that, in a good agreement with the experimental results, additional excitons are associated to local symmetry changes occurring at crystal stacking faults. Additional features appearing within the band gap present a high spatial localization, typically less than 100 nm, and thus they can be related to individual point defects. When addressed individually through a highly focused electron probe they might have a single photon emitter quantum character. This hypothesis has been recently confirmed by experiments combining our cathodoluminescence system with an Hanbury Brown and Twiss (HBT) interferometer [4].

(Invited) Impact of Size Scale on Electro-Chemo-Mechanical Coupling Properties in MIECs: Bulk and Thin Film (Pr,Ce)O2-δ

Many oxides exhibit advantageous properties in energy conversion and storage applications, such as solid oxide fuel cells (SOFCs), heterogeneous catalysis, photoelectrochemical cells, and batteries, due in part to their high temperature stability, corrosion resistance, and dopant cation solubility, respectively. In particular, mixed ionic and electronic conducting oxides have been demonstrated to aid in increasing reaction kinetics at electrodes in SOFCs due to the simultaneous presence of electrons and oxygen vacancies. With changes in oxygen partial pressure and temperature during normal operation operation, the defect concentration and hence transport characteristics of MIEC oxides inevitably change. In addition, defects are often coupled to a significant lattice dilation, known as chemical expansion, which under some circumstances leads to mechanical failure. Furthermore, as length scales are reduced, the energetics for electron and vacancy formation have been shown to be modified. In this presentation, recent work examining the the interplay of electro-chemo-mechanical properties of bulk ceramic to thin film size scales will be discussed. This work was facilitated by using the model material system, (Pr,Ce)O2-δ (PCO), which, due to the ease of reduction of Pr from 4+ to 3+ valence, exhibits significant MIEC behavior at relatively high oxygen pressures (e.g. air). Impedance spectroscopy was used to study both the oxygen exchange resistance and oxygen content (via chemical capacitance) of cells consisting of PCO thin films deposited on yttria stabilized zirconia substrates. When compared to defect formation energies derived from a detailed thermogravimetric and conductivity model for bulk PCO, films were found to exhibit enhanced reducibility. This phenomenon was further verified using an in situ optical transmission measurement of films, coupled with chemical capacitance, which correlated the amount of absorbing Pr4+ centers to oxygen vacancy concentration. Additionally, oxygen exchange probed by optical transmission relaxation measurements on “bare” films exhibited slower kinetics as compared to corresponding electrochemical measurements. The role of metal electrodes as well as impurities in modifying oxygen exchange rate will be discussed, as well as new means to improve oxygen exchange of the aged “bare” film surface. Lastly, thermo-chemical expansion measurements of bulk and thin film PCO samples will be presented with discussion related to the atomistic role of individual point defects and defect association.

Measurement of the full stress tensor in a crystal using photoluminescence from point defects: The example of nitrogen vacancy centers in diamond

We introduce a method for measuring the full stress tensor in a crystal utilising the properties of individual point defects. By measuring the perturbation to the electronic states of three point defects with C3v symmetry in a cubic crystal, sufficient information is obtained to construct all six independent components of the symmetric stress tensor. We demonstrate the method using photoluminescence from nitrogen-vacancy colour centers in diamond. The method breaks the inverse relationship between spatial resolution and sensitivity that is inherent to existing bulk strain measurement techniques, and thus, offers a route to nanoscale strain mapping in diamond and other materials in which individual point defects can be interrogated.

Atomistic simulations of surface segregation of defects in solid oxide electrolytes

Abstract We performed atomistic simulations of yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) to study the segregation of point defects near (1 0 0) surfaces. A hybrid Monte Carlo–molecular dynamics algorithm was developed to sample the equilibrium distributions of dopant cations and oxygen vacancies. The simulations predict an increase of dopant concentration near the surface, which is consistent with experimental observations. Oxygen vacancies are also found to segregate in the first anion layer beneath the surface and to be depleted in the subsequent anion layers. While the ionic size mismatch between dopant and host cations has been considered as a driving force for dopant segregation to the surface, our simulations show that the correlation between individual point defects plays a dominant role in determining their equilibrium distributions. This correlation effect leads to more pronounced dopant segregation in GDC than in YSZ, even though the size mismatch between dopant and host cations is much greater in YSZ than in GDC.

Analysis of point defects in AlN epilayers by cathodoluminescence spectroscopy

We present a systematic cathodoluminescence study yielding a clear correlation between the different growth conditions and the appearance and strength of the characteristic luminescence fingerprints of the individual point defects in AlN. In particular, the incorporation of oxygen and the formation of oxygen-related and probably silicon-related DX centers as well as the native Al and N vacancies are still a problem. The thermal activation of the deep defect centers is investigated by temperature dependent cathodoluminescence spectroscopy.

Quantitative Structural Analysis of Binary Nanocrystal Superlattices by Electron Tomography

Binary nanocrystal superlattices, that is, ordered structures of two sorts of nanocolloids, hold promise for a series of functional materials with novel collective properties. Here we show that based on electron tomography a comprehensive, quantitative, three-dimensional characterization of these systems down to the single nanocrystal level can be achieved, which is key in understanding the emerging materials properties. On four binary lattices composed of PbSe, CdSe, and Au nanocrystals, we illustrate that ambiguous interpretations based on two-dimensional transmission electron microscopy can be prevented, nanocrystal sizes and superlattice parameters accurately determined, individual crystallographic point and plane defects studied, and the order/disorder at the top and bottom surfaces imaged. Furthermore, our results suggest that superlattice nucleation and growth occurred at the suspension/air interface and that the unit cells of some lattices are anisotropically deformed upon drying.

Structure and electronic properties of imperfect oxides and nanooxides

Results of studies of the structure and physicochemical properties of perfect (defectless) and imperfect (containing point defects) nanoparticles of metal oxides by the methods of scanning tunnel microscopy (STM) and spectroscopy (STS) are summarized and reviewed. Using nanooxides of various metals (Al, Pt, W, and Ti), as examples, it was demonstrated that the modern STM and STS methods make it possible to measure the electronic spectra of perfect nanoparticles, detect individual and associated point defects, determine spatial distributions of defects, derive spatial and energetic distributions of electrons trapped on point defects (anionic vacancies, intercalation atoms, and adatoms), detect single electron spins (paramagnetic surface complexes), measure phonon and vibration spectra of individual nanoparticles and surface complexes, determine (from measured electronic and phonon spectra) the chemical composition and atomic structure of individual nanoparticles. It was emphasized that modern versions of the STM-STS methods can constitute the foundation of new analytical methods needed in nanometrology and nanodefectoscopy.

Anisotropic diffusion of point defects in a two-dimensional crystal of streptavidin observedby high-speed atomic force microscopy

The diffusion of individual point defects in a two-dimensional streptavidin crystal formedon biotin-containing supported lipid bilayers was observed by high-speed atomicforce microscopy. The two-dimensional diffusion of monovacancy defects exhibitedanisotropy correlated with the two crystallographic axes in the orthorhombicC 222 crystal; in the 2Dplane, one axis (the a-axis) is comprised of contiguous biotin-bound subunit pairs whereas the other axis (theb-axis) is comprised of contiguous biotin-unbound subunit pairs. The diffusivity along theb-axis is approximately 2.4 times larger than that along thea-axis. This anisotropy is ascribed to the difference in the association free energybetween the biotin-bound subunit–subunit interaction and the biotin-unboundsubunit–subunit interaction. The preferred intermolecular contact occurs betweenthe biotin-unbound subunits. The difference in the intermolecular bindingenergy between the two types of subunit pair is estimated to be approximately0.52 kcal mol−1. Another observed dynamic behavior of point defects was fusion of two pointdefects into a larger defect, which occurred much more frequently than the fissionof a point defect into smaller defects. The diffusivity of point defects increasedwith increasing defect size. The fusion and the higher diffusivity of larger defectsare suggested to be involved in the mechanism for the formation of defect-freecrystals.

Phonon-defect scattering in doped silicon by molecular dynamics simulation

Molecular dynamics simulations are used to study the scattering of phonon wave packets of well-defined frequency and polarization from individual point defects and from a field of point defects in Si. The relative amounts of energy in the transmitted and reflected phonon fields are calculated and the parameters that influence the phonon scattering process are determined. The results show that the fractions of transmitted and reflected energies strongly depend on the frequency of the incident phonons and on the mass and concentration of the defects. These results are compared with the classic formula for the scattering strength for point defects derived by Klemens, which we find to be valid when each phonon-defect scattering event is independent. The Klemens formula fails when coupled multiple scattering dominates. The phonon density of states is used to characterize the effects of point defects on mode mixing.

Microscopic study of the H2O vapor treatment of the silicon grain boundaries

We have proposed annealing in H2O vapor as a new effective and low-cost method for passivating polycrystalline silicon grain boundaries and for improving the performance of poly-Si based devices. The effect of H2O vapor treatment was experimentally found to differ from analogous anneal in nitrogen and hydrogen. Mechanism of the H2O vapor treatment was studied by Kelvin force microscopy, used to measure the potential change at individual grain boundaries and point defects. The potential change was dependent on the grain boundary character and it correlated with the crystalline disorder and internal stress observed by microscopic Raman spectroscopy. Effect of H2O vapor passivation was experimentally connected with the potential change at the grain boundaries before and after the treatment.

Characterization of thermal conductivity degradation induced by heavy ion irradiation in ceramic materials

Thermal conductivity degradation of three semi-metallic ceramics: titanium carbide, zirconium carbide and titanium nitride, and a covalent compound: 6H silicon carbide, induced by irradiation with energetic heavy ions at room temperature, is studied and quantified. Irradiations by 25.8 MeV krypton ions at 1016 and 6 × 1016 ions cm−2 doses were used to produce defects in the considered materials. Modulated thermoreflectance microscopy measurements were performed to characterize the resulting subsurfasic degradation of the thermal conductivity for each of the investigated materials. The study considers the two collision domains produced by the inelastic collisions and the elastic collisions that occur during an ion irradiation. A significant thermal conductivity degradation in the two collision domains for all materials is obtained. Elastic collisions are shown to degrade the thermal properties more strongly than the inelastic ones. The scattering of thermal energy carriers is larger in the elastic collision domain because displacement cascades produce a very high concentration of point defects. The degradation coming from electronic interactions is found to be more important in SiC, which can be explained by the presence of large populations of generated extended defects, facing generated individual point defects in the studied semi-metallic materials.

Thermal conductivity degradation induced by heavy ion irradiation at room temperature in ceramic materials

The thermal conductivity degradation induced by irradiation with energetic heavy ions at room temperature is studied and quantified. Three semi-metallic systems: titanium and zirconium carbides, titanium nitride, as well as a covalent compound: 6H silicon carbide were irradiated by 25.8 MeV krypton ions at 1016 and 6 . 1016 ions.cm-2 doses to produce defects. During ion irradiation, inelastic collisions and elastic collisions occur at a different depth in a material. Two collision domains can be defined. Modulated thermoreflectance microscopy measurements were performed at differing frequencies to characterize the thermal conductivity degradation in these two domains for each of the investigated materials. Our results reveal a significant thermal conductivity degradation in the two collision domains for all materials. Elastic collisions are shown to degrade more strongly the thermal properties than inelastic ones. Scattering of thermal energy carriers is larger in elastic collision domain because displacement cascades produce a very high concentration of point defects: vacancies, interstitials and implanted Kr ions. The degradation coming from electronic interactions that seems to be more important in SiC can be explained by the presence of large populations of generated extended defects, facing to generated individual point defects in TiC, TiN or ZrC.

Influence of Cu, Cr and C on the irradiation defect in Fe: A molecular dynamics simulation study

The effects of alloying elements, Cu, Cr and C, on the number of residual point defects (vacancies and interstitials), their clustering tendency and constitution have been investigated by performing molecular dynamics cascade simulations on pure Fe, Fe–0.5 at.% Cu, Fe–10 at.% Cr and Fe–0.1 at.% C alloys using MEAM interatomic potentials. Both Cu and Cr form Fe–M and M–M interstitial dumbbells, but have no significant effect on the number and clustering tendency of point defects. Carbon has no effect on the formation and clustering of point defects neither, but shows a strong binding with vacancies and interstitial dumbbells. By combining the simulation results and calculated binding energies between individual point defects, effects of solute atoms on the long-term irradiation-induced microstructure evolution are deduced. Details of cascade simulation results and binding energies between point defects are presented, and influence of solute elements on long-term irradiation defect such as void swelling and formation of solute-rich precipitates are discussed.

Study of cascades damage in Ni by MD with different interatomic potentials

Molecular dynamics (MD) simulations, performed with embedded atom potentials, are used to understand the formation of defects following displacement cascades in Ni. Different empirical potentials, presenting large differences in stacking fault energy (SFE), are used. Simulations were conducted with primary knock-on (PKA) atom energies of 5–40 keV at a temperature of 10 K. Defects include, depending on the potential, individual point defects (vacancies and interstitials), dislocation loops and stacking fault tetrahedra (SFT). The results are related to TEM observations, and the mismatch between these two pictures is discussed. It appears that in a collision cascade, the formation of an SFT does not depend only on the SFE but also on other parameters such as the mobility of vacancies and self-interstitials, or the presence of replacement collision sequences. Based on these calculations we suggest that the formation of clusters of vacancies is a prerequisite to the formation of SFTs.

Point-defect dynamics in two-dimensional colloidal crystals

We study the topological configurations and dynamics of individual point defect vacancies and interstitials in a two-dimensional crystal of colloids interacting via a repulsive Yukawa potential. Our Brownian dynamics simulations show that the diffusion mechanism for vacancy defects occurs in two phases. The defect can glide along the crystal lattice directions, and it can rotate during an excited topological transition configuration to assume a different direction for the next period of gliding. The results for the vacancy defects are in good agreement with recent experiments. For interstitial point defects, which were not studied in the experiments, we find several of the same modes of motion as in the vacancy defect case along with two additional diffusion pathways. The interstitial defects are more mobile than the vacancy defects due to the more two-dimensional nature of the diffusion of the interstitial defects.

In situ HAFM study of the thermal dehydration on gypsum (010) surfaces

Hydrothermal AFM has been used to study the thermal dehydration reaction on gypsum (010) surfaces in solutions at different saturation states, and in the absence of a bulk liquid phase. Experiments were carried out at temperatures ranging from 25 to 130 °C. Whereas supersaturated solutions (β = 1.8–5) caused gypsum growth in the entire temperature range, solutions close to equilibrium (β = 1.02) caused various responses of the gypsum surface. The most prominent was a sharp transition from fast growth to very fast dissolution at ∼120 °C suggesting a sudden nucleation of a phase more stable than gypsum. No structural relation could be found between the parental gypsum (010) surface and the crystallizing phase. In the absence of a bulk liquid phase, dehydration takes place via the nucleation and spreading of etch-pit like pattern. Laterally, the thermal etch pits spread in an unrestricted way. In the vertical direction, pit growth was limited to a few micrometers. Dehydration by monolayer pits and nucleation of the dehydration process at monolayer steps on the (010) surface were never observed. Thus, unlike growth or dissolution, surface energy related to kink sites or individual point defects seems to be insuffi cient to trigger dehydration. The temperature-dependent lateral pit growth yields an activation energy of 119 ± 11 kJ/mol. The product phase disintegrates at the parental surface into nano-size particles without any morphologically noticeable transition zone.